CN107010961B - The serialization process for calcining and its device of SiC fiber - Google Patents

The serialization process for calcining and its device of SiC fiber Download PDF

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CN107010961B
CN107010961B CN201710339218.3A CN201710339218A CN107010961B CN 107010961 B CN107010961 B CN 107010961B CN 201710339218 A CN201710339218 A CN 201710339218A CN 107010961 B CN107010961 B CN 107010961B
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fiber
temperature
pressure
firing
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CN107010961A (en
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王小宙
王浩
王军
简科
邵长伟
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National University of Defense Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
    • F27B5/04—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated adapted for treating the charge in vacuum or special atmosphere
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
    • F27B5/06—Details, accessories, or equipment peculiar to furnaces of these types
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
    • F27M2001/00—Composition, conformation or state of the charge
    • F27M2001/15—Composition, conformation or state of the charge characterised by the form of the articles
    • F27M2001/1504—Ceramic articles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
    • F27M2003/00—Type of treatment of the charge
    • F27M2003/04—Sintering

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Ceramic Products (AREA)
  • Inorganic Fibers (AREA)

Abstract

The present invention provides the serialization process for calcining and its device of a kind of SiC fiber, the following steps are included: carrying out being fired into SiC fiber under an inert atmosphere to non-fusible polycarbosilane fiber, it is burnt into step: a, removing the easy deposit small molecule being burnt into gas at 400~600 DEG C, and be (0.1~9.5) × 10 in pressure4Under Pa, 800~1200 DEG C are warming up to from 400~600 DEG C according to 10 DEG C/h~100 DEG C/h of heating rate；B, keeping inert gas flow is 200L/ hours until pressure rises to (1.1~3) × 105After Pa, 1200~2000 DEG C are warming up to by 30 DEG C/h~300 DEG C/h of heating rate and keeps the temperature 0.5~5 hour, is naturally cooling to room temperature later；The present invention is on the basis of existing firing furnace, in conjunction with the firing process of polycarbosilane fiber, regulates and controls the evolution and discharge of thermal decomposition product in sintering process, improve the densification degree of fiber, the performance and batch firing yield that fiber can be improved, are prepared with important meaning for the engineering of SiC fiber.

Description

The serialization process for calcining and its device of SiC fiber
Technical field
The present invention relates to ceramic fibre technical field, be specifically related to a kind of SiC fiber serialization process for calcining and its Device.
Background technique
Continuous SiC fiber has high intensity, high-modulus, excellent resistance to high temperature oxidation, creep-resistant property and and ceramic matrix There is good compatibility, be the ideal reinforcement for preparing high-performance ceramic based composites, is filled in aerospace, high-performance weapon Standby field has broad application prospects.Precursor pyrolysis and hot pressing is to prepare thin diameter continuous SiC fiber common method, and this method is main Using organometallic polymer as precursor, after its solvable/molten characteristic molding, by high temperature pyrolysis, it is allowed to from organic matter It is changed into inorganic matter.This method have reaction unit require low, cost of investment is low, conducive to large-scale production, prepared fiber The features such as performance is good, this method is widely used in the preparation of continuous SiC fiber and its composite material at present.
It includes the synthesis of Polycarbosilane, the melting of Polycarbosilane spinning that precursor pyrolysis and hot pressing, which prepares continuous SiC fiber, Silk, polycarbosilane fiber non-fusible and non-fusible polycarbosilane fiber high temperature firing.Among these, non-fusible Polycarbosilane is fine The high temperature firing of dimension is last procedure prepared, is related to material from organic to inorganic conversion, determines final fiber Composition, structure and performance, are that precursor pyrolysis and hot pressing prepares one of committed step of continuous SiC fiber.Currently, mainly adopting both at home and abroad With under inert atmosphere normal pressure be burnt into technique carry out continuous SiC fiber firing (US4110386, US4100233, US4342712, US4399232, US4515742), the simple process is easily-controllable, lower to equipment requirement.But in the process Non-fusible polycarbosilane fiber can crack, and generate more small organic molecule segment, especially in engineering preparation process, greatly Chemical reaction deposit can occur in fiber surface between amount small organic molecule, cause the adhesion between fiber, influence the power of fiber Learn performance and knitting property.In addition, the fiber defect by cracking is more, it, can certain journey by further high-temperature process The consistency of fiber is improved on degree, but the densification effect of fiber still needs to further increase with efficiency under condition of normal pressure.Although Researcher also carried out SiC fiber vacuum firing (J.Am.Ceram.Soc., 84 [3] 566-70 (2001)；JOURNAL OF MATERIALS SCIENCE38 (2003) 16531660), the work such as HIGH PRESSURE TREATMENT (US7687016), achieve certain effect Fruit, but system pressure is too small when vacuum processing, easily causes weightless excessive, composition variation play in fiber organic-inorganic conversion process The problems such as strong, while also will cause fiber and occurring actively to aoxidize, it is unable to get high-performance ceramic fiber.And HIGH PRESSURE TREATMENT (10-20 Atmospheric pressure) it is high to equipment requirement, it can not large-scale production.
Summary of the invention
The purpose of the present invention is to provide a kind of serialization process for calcining of SiC fiber and its device, which is solved The discharge of polycarbosilane fiber sintering process small molecular fugitive constituent evolution at present is difficult, densification degree is not high；Vacuum firing is easy Causing fiber, acutely, fiber occurs actively to aoxidize for weightless excessive, composition variation in organic-inorganic conversion process, is unable to get height The technical issues of performance ceramic fibre.
The present invention provides a kind of serialization process for calcining of SiC fiber, comprising the following steps: under an inert atmosphere to not melting Change polycarbosilane fiber to carry out being fired into SiC fiber, be burnt into step:
A, once-firing is carried out when being warming up to 400~800 DEG C, is later 0.1 × 10 in pressure4~9.5 × 104Under Pa, press 800~1200 DEG C are continuously heating to according to 10 DEG C/h~100 DEG C/h of speed；B, keeping inert gas flow is 200L/ Hour is until pressure rises to (1.1~3) × 105After Pa, 1200 are warming up to by 30 DEG C/h~300 DEG C/h of heating rate ~2000 DEG C and heat preservation 0.5~5 hour, it is naturally cooling to room temperature later；
The oxygen content of non-fusible polycarbosilane fiber is lower than 5wt%, and gel content is greater than 70wt%, 1000 DEG C of ceramic yields Greater than 60wt%, fibre diameter is 5~30 μm.
The method provided by the present invention makes firing furnace be in low pressure in the organic-inorganic transformation stage by air inlet and extract system 0.1×104~9.5) × 104The state of Pa, and combine once-firing in favor of the evolution and discharge of easy deposit small molecule；In height Warm densification stage makes firing furnace be in micro-positive pressure 1.1 × 105P~3 × 105The state of Pa, by the different stages of reaction Using different pressure, the densification degree of gained fiber surface is effectively increased.Since small molecule all escapes, avoid The problem of gained fiber surface is adhered.Preferable reaction surface is provided for subsequent densification reaction.This method to equipment requirement compared with It is low, simple process is controllable, suitable for mass production, continuous SiC fiber preparation on have good application prospect.
In order to keep pressure, it the means such as can for example seal using all kinds of conventional means and avoid pressure change.
Further, inert gas is that nitrogen, argon gas or helium are any.
It further, is 10~300 DEG C/h to 400 DEG C~800 DEG C of heating rate from room temperature, temperature-rise period Described in inert gas flow be 10L/ hours~1000L/ hours.It heats up by this condition, is conducive to subsequent small molecule object Matter escapes.
Further, inert atmosphere forming method the following steps are included: first vacuumize in triplicate reduce pressure to≤ 10Pa pours inert gas later and increases pressure to 105Pa。
Another aspect of the present invention has passed through a kind of burning apparatus of such as serialization process for calcining of above-mentioned SiC fiber, packet Feeder, firing furnace and water circulating pump are included, feeder and firing furnace pass through pipeline connection, flowmeter are arranged on connecting pipeline And valve；Water circulating pump and firing furnace pass through pipeline connection, and valve is arranged on connecting pipeline.Using the equipment, pass through recirculated water Pump, is able to achieve the condensation to the small-molecule substance generated in sintering process.
It further, further include tail gas liquid seal device, tail gas liquid seal device is connected with water circulating pump by pipeline.
Further, surge tank is also set up on the pipeline that firing furnace is connected with water circulating pump.
Further, vacuum pump is additionally provided on the pipeline that surge tank is connected with water circulating pump.
Technical effect of the invention:
1, the present invention provides the serialization process for calcining of SiC fiber, using conventional high temperature firing furnace, converts in organic-inorganic Stage makes firing furnace be in low pressure ((0.1~9.5) × 10 by air inlet and extract system4Pa state), in favor of easily heavy The evolution and discharge of product small molecule, avoid small-molecule substance from forming adhesion coating in fiber surface；In the consolidation stage, by into Gas and tail gas liquid seal device, make firing furnace be in micro-positive pressure ((1.1~3) × 105Pa state), in favor of the densification of fiber Change, to realize that the controllable conversion of low pressure and high pressure is burnt into during firing furnace, an once-firing.Being made has smooth heavily fortified point The fibrous material of hard surface.
2, the serialization burning apparatus of SiC fiber provided by the invention, it is lower to equipment requirement, simple process is controllable, suitable Batch production is closed, has good application prospect in continuous SiC fiber engineering preparation.
3, the serialization process for calcining of SiC fiber provided by the invention, the fibre density being burnt into, mechanical strength are higher, Heat resistance is good.
Specifically please refer to retouching as follows for the various embodiments of the serialization process for calcining proposition of SiC fiber according to the present invention It states, above and other aspect of the invention will be made apparent.
Detailed description of the invention
Fig. 1 is SiC fiber burning apparatus schematic diagram used in the preferred embodiment of the present invention；
Fig. 2 is gained SiC fiber gained after high-temperature process in the preferred embodiment of the present invention 1~2 and comparative example 1~2 The SEM of sample schemes.
Marginal data:
1, feeder；2, gas flowmeter；31, the first valve；32, the second valve；33, third valve；34, the 4th valve Door；35, the 5th valve；4, firing furnace；5, surge tank；6, vacuum pump；7, water circulating pump；8, tail gas liquid seal device.
Specific embodiment
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.
Embodiment
Material and instrument used are commercially available in following embodiment.
Burning apparatus used is equal as shown in Figure 1, equipment therefor includes: feeder 1, gas in following embodiment and comparative example Flowmeter body 2, firing furnace 4, surge tank 5, vacuum pump 6, water circulating pump 7 and tail gas liquid seal device 8.Feeder 11 passes through pipeline It is connected with firing furnace 4.Interval setting gas flowmeter 2 and the first valve on the connecting pipeline of feeder 1 and firing furnace 4 31.Surge tank 5, vacuum pump 6, water circulating pump 7, tail gas liquid seal device 8 are connected by pipeline with firing furnace 4 respectively.Surge tank 5, the second valve 32, are respectively equipped on the pipeline that vacuum pump 6, water circulating pump 7, tail gas liquid seal device 8 are connected with firing furnace 4 Three valves 33, the 4th valve 34 and the 5th valve 35.
Embodiment 1
It is 1.1wt% by oxygen content, gel content 96.0wt%, 1000 DEG C of ceramic yields are 78wt%, fibre diameter It is packed into high temperature firing furnace (4) for 18.6 μm of non-fusible polycarbosilane fibers, closes the first valve 31, the 4th valve 34, the Five valves 35 open the second valve 32, third valve 33, open vacuum pump (6), vacuumize until firing furnace pressure is down to 5Pa；It closes the second valve 32, third valve 33, opens the first valve 31, by feeder (1) and gas flowmeter (2), Nitrogen is filled with into firing furnace until it is 10 that furnace pressure, which increases,5Pa；It repeats above operation, replaces nitrogen three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 100L/ hours；Then according to 10 DEG C/h of heating rate Firing furnace temperature is risen to 400 DEG C；
The 5th valve 35 is closed, the 4th valve 34 is opened, opens water circulating pump, control firing furnace pressure is 104Pa；Then 800 DEG C are risen to by furnace temperature is burnt into according to 10 DEG C/h of heating rates；
The second valve 32, the 4th valve 34 are closed, adjusting charge flow rate by gas flowmeter (2) is 200L/ hours straight It is 3 × 10 to firing furnace pressure5Pa；
The second valve 32, the 5th valve 35 are opened, adjusting liquid level in mercury fluid-tight system is 1.47m, keeps firing Furnace pressure is 3 × 105Pa, adjustment gas flow are 200L/ hours, will be burnt into furnace temperature according to 30 DEG C/h of heating rates Degree rises to 1600 DEG C, and keeps the temperature 1 hour, after with furnace be down to room temperature, obtain SiC fiber, sample is denoted as 1, tensile strength of fiber 3.05GPa, modulus 305GPa, 11.1 μm of diameter, fibre density 2.81g/cm3。
Embodiment 2
It is 4.8wt% by oxygen content, gel content 76wt%, 1000 DEG C of ceramic yields are 72wt%, and fibre diameter is 19.3 μm of non-fusible polycarbosilane fiber is packed into high temperature firing furnace (4), closes the first valve 31, the 4th valve 34, the Five valves 35 open the second valve 32, third valve 33, open vacuum pump (6), vacuumize until firing furnace pressure is down to 10Pa；It closes the second valve 32, third valve 33, opens the first valve 31, by feeder (1) and gas flowmeter (2), Inert gas argon gas is filled with into firing furnace until it is 10 that furnace pressure, which increases,5Pa；It repeats above operation, replaces argon gas three repeatedly It is secondary；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 1000L/ hours；Then according to 300 DEG C/h of heating speed Firing furnace temperature is risen to 800 DEG C by degree；
It closes the 5th valve 35, opens the 4th valve 34, open water circulating pump, control firing furnace pressure is 9.5 × 104Pa；Then 1200 DEG C are risen to by furnace temperature is burnt into according to 100 DEG C/h of heating rate；
The second valve 32, the 4th valve 34 are closed, adjusting charge flow rate by gas flowmeter (2) is 200L/ hours straight It is 1.1 × 10 to firing furnace pressure5Pa；
The second valve 32, the 5th valve 35 are opened, adjusting liquid level in mercury fluid-tight system is 0.07m, keeps firing Furnace pressure is constant, and adjustment gas flow is 10L/ hours, rises to according to 300 DEG C/h of heating rates by furnace temperature is burnt into 1300 DEG C, and keep the temperature 0.5 hour, after with furnace be down to room temperature, obtain SiC fiber, sample is denoted as 2, tensile strength of fiber 2.56GPa, modulus 243GPa, 11.4 μm of diameter, fibre density 2.64g/cm3。
Embodiment 3
By oxygen content 0.5wt%, gel content 99.2wt%, 1000 DEG C of ceramic yields are 81wt%, and fibre diameter is 19.2 μm of non-fusible polycarbosilane fiber is packed into high temperature firing furnace (4), closes the first valve 31, the 4th valve the 34, the 5th Valve 35 opens the second valve 32, third valve 33, opens vacuum pump (6), vacuumizes until firing furnace pressure is down to 1Pa； The second valve 32, third valve 33 are closed, the first valve 31 is opened, by feeder (1) and gas flowmeter (2), to burning It is 10 at helium is filled in furnace up to furnace pressure increases5Pa；It repeats above operation, replacement of helium is three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 10L/ hours；It then will according to 10 DEG C/h of heating rate Firing furnace temperature rises to 600 DEG C；
It closes the 5th valve 35, opens the 4th valve 34, open water circulating pump, control firing furnace pressure is 0.1 × 104Pa；Then 1200 DEG C are risen to by furnace temperature is burnt into according to 100 DEG C/h of heating rate；
The second valve 32, the 4th valve 34 are closed, adjusting charge flow rate by gas flowmeter (2) is 200L/ hours straight It is 2 × 10 to firing furnace pressure5Pa；
The second valve 32, the 5th valve 35 are opened, liquid level 0.73m in mercury fluid-tight system is adjusted, keeps firing furnace Interior pressure is constant, and adjustment gas flow is 100L/ hours, rises to according to 300 DEG C/h of heating rates by furnace temperature is burnt into 1200 DEG C, and keep the temperature 1 hour, after with furnace be down to room temperature, obtain SiC fiber, tensile strength of fiber 2.84GPa, modulus 297GPa, 11.1 μm of diameter, fibre density 2.85g/cm3。
Embodiment 4
By oxygen content 1.6wt%, gel content 98.1wt%, 1000 DEG C of ceramic yields are 74wt%, and fibre diameter is 20.5 μm of non-fusible polycarbosilane fiber is packed into high temperature firing furnace (4), closes the first valve 31, the 4th valve the 34, the 5th Valve 35 opens the second valve 32, third valve 33, opens vacuum pump (6), vacuumizes until firing furnace pressure is down to 2Pa； The second valve 32, third valve 33 are closed, the first valve 31 is opened, by feeder (1) and gas flowmeter (2), to burning It is 10 at argon gas is filled in furnace up to furnace pressure increases5Pa；It repeats above operation, replaces argon gas three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 100L/ hours；Then according to 60 DEG C/h of heating rate Firing furnace temperature is risen to 400 DEG C；
It closes the 5th valve 35, opens the 4th valve 34, open water circulating pump, control firing furnace pressure is 0.5 × 104Pa；Then 900 DEG C are risen to by furnace temperature is burnt into according to 60 DEG C/h of heating rate；
The second valve 32, the 4th valve 34 are closed, adjusting charge flow rate by gas flowmeter (2) is 200L/ hours straight It is 2.5 × 10 to firing furnace pressure5Pa；
The second valve 32, the 5th valve 35 are opened, liquid level 1.1m in mercury fluid-tight system is adjusted, is kept in firing furnace Pressure is constant, and adjustment gas flow is 100L/ hours, rises to 2000 for furnace temperature is burnt into according to 100 DEG C/h of heating rates DEG C, and keep the temperature 1 hour, after with furnace be down to room temperature, obtain SiC fiber, tensile strength of fiber 2.99GPa, modulus 301GPa, diameter 12.0 μm, fibre density 2.77g/cm3。
Embodiment 5
By oxygen content 1.2wt%, gel content 96.4wt%, 1000 DEG C of ceramic yields are 77wt%, and fibre diameter is 21.2 μm of non-fusible polycarbosilane fiber is packed into high temperature firing furnace (4), closes the first valve 31, the 4th valve the 34, the 5th Valve 35 opens the second valve 32, third valve 33, opens vacuum pump (6), vacuumizes until firing furnace pressure is down to 5Pa； The second valve 32, third valve 33 are closed, the first valve 31 is opened, by feeder (1) and gas flowmeter (2), to burning It is 10 at argon gas is filled in furnace up to furnace pressure increases5Pa；It repeats above operation, replaces argon gas three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 100L/ hours；Then according to 60 DEG C/h of heating rate Firing furnace temperature is risen to 400 DEG C；
The 5th valve 35 is closed, the 4th valve 34 is opened, opens water circulating pump, control firing furnace pressure is 8 × 104Pa； Then 1000 DEG C are risen to by furnace temperature is burnt into according to 10 DEG C/h of heating rate；
The second valve 32, the 4th valve 34 are closed, adjusting charge flow rate by gas flowmeter (2) is 200L/ hours straight It is 1.8 × 10 to firing furnace pressure5Pa；
The second valve 32, the 5th valve 35 are opened, liquid level 0.58m in mercury fluid-tight system is adjusted, keeps firing furnace Interior pressure is constant, and adjustment gas flow is 200L/ hours, rises to according to 300 DEG C/h of heating rates by furnace temperature is burnt into 1500 DEG C, and keep the temperature 3 hours, after with furnace be down to room temperature, obtain SiC fiber, tensile strength of fiber 2.84GPa, modulus 294GPa, 12.5 μm of diameter, fibre density 2.71g/cm3。
Comparative example 1
It is 1.1wt% by oxygen content, gel content 96.0wt%, 1000 DEG C of ceramic yields are 78wt%, fibre diameter It is packed into high temperature firing furnace (4) for 18.6 μm of non-fusible polycarbosilane fibers, closes the first valve 31, the 4th valve 34, the Five valves 35 open the second valve 32, third valve 33, open vacuum pump (6), vacuumize until firing furnace pressure is down to 5Pa；It closes the second valve 32, third valve 33, opens the first valve 31, by feeder (1) and gas flowmeter (2), Nitrogen is filled with into firing furnace until it is 10 that furnace pressure, which increases,5Pa；It repeats above operation, replaces nitrogen three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 100L/ hours；Keeping furnace pressure is 105Pa is constant, according to 60 DEG C/h of heating rate rises to 400 DEG C for furnace temperature is burnt into；Then according to 10 DEG C/h of heating rate by firing furnace Temperature rises to 800 DEG C；Keeping furnace pressure is 105Pa is constant, and adjustment gas flow is 200L/ hours, according to 30 DEG C/h Heating rate rises to 1600 DEG C for furnace temperature is burnt into, and keeps the temperature 1 hour, after with furnace be down to room temperature, obtain SiC fiber, sample note It is 3, tensile strength of fiber 2.54GPa, modulus 289GPa, 11.6 μm of diameter, fibre density 2.68g/cm3。
Comparative example 2
It is 4.8wt% by oxygen content, gel content 76wt%, 1000 DEG C of ceramic yields are 72wt%, and fibre diameter is 19.3 μm of non-fusible polycarbosilane fiber is packed into high temperature firing furnace (4), closes the first valve 31, the 4th valve 34, the Five valves 35 open the second valve 32, third valve 33, open vacuum pump (6), vacuumize until firing furnace pressure is down to 10Pa；It closes the second valve 32, third valve 33, opens the first valve 31, by feeder (1) and gas flowmeter (2), Argon gas is filled with into firing furnace until it is 10 that furnace pressure, which increases,5Pa；It repeats above operation, replaces argon gas three times repeatedly；
The first valve 31, the second valve 32, the 5th valve 35 are opened, third valve 33, the 4th valve 34 are closed, opens and supplies Device of air (1) and gas flowmeter (2), adjusting gas flow are 1000L/ hours；Then according to 300 DEG C/h of heating speed Firing furnace temperature is risen to 400 DEG C by degree；Keeping furnace pressure is 105Pa is constant, will burn according to 100 DEG C/h of heating rates 1200 DEG C are risen at furnace temperature；Keep firing furnace pressure constant, adjustment gas flow is 10L/ hours, according to 300 DEG C/h Heating rate rise to 1300 DEG C for furnace temperature is burnt into, and keep the temperature 0.5 hour, after with furnace be down to room temperature, obtain SiC fiber, sample Product are denoted as 4, tensile strength of fiber 2.44GPa, modulus 247GPa, and 11.6 μm of diameter, fibre density 2.51g/cm3。
The heat resistance of 1~2 gained fiber of Examples 1 to 2 and comparative example detects test:
Fiber sample 1,2,3,4 is put into graphite furnace simultaneously, vacuumizes displacement argon gas three times, is then protected in argon atmosphere Under shield, according to 10 DEG C/min of heating rate rise to 1800 DEG C and keep the temperature 1 hour, take out sample be denoted as respectively 1-1,2-1,31, 4-1, sample topography is as shown in Figure 2 after processing.Character before and after sample treatment is as shown in table 1.
1 fiber sample of table, 1~4 mechanical property contrast table
From table 1 it follows that the fiber that the method provided by the present invention is prepared, it is submissive with excellent mechanical property and Heat resistance.It can be seen in fig. 2 that the fiber being prepared into using the method provided by the present invention is by high-temperature process, surface is smooth, structure It is fine and close.And the fiber surface grain coarsening that method is prepared in comparative example 1~2 is serious, fibre structure is loose, and consistency is low.
Those skilled in the art will be clear that the scope of the present invention is not limited to example discussed above, it is possible to carry out to it Several changes and modification, the scope of the present invention limited without departing from the appended claims.Although oneself is through in attached drawing and explanation The present invention is illustrated and described in book in detail, but such illustrate and describe is only explanation or schematical, and not restrictive. The present invention is not limited to the disclosed embodiments.
By to attached drawing, the research of specification and claims, those skilled in the art can be in carrying out the present invention Understand and realize the deformation of the disclosed embodiments.In detail in the claims, term " includes " is not excluded for other steps or element, And indefinite article "one" or "an" be not excluded for it is multiple.The certain measures quoted in mutually different dependent claims The fact does not mean that the combination of these measures cannot be advantageously used.Any reference marker in claims is not constituted pair The limitation of the scope of the present invention.

Claims (1)

1. a kind of serialization process for calcining of SiC fiber, which comprises the following steps: under an inert atmosphere to not melting Change polycarbosilane fiber to carry out being fired into the SiC fiber, the firing step:
A, once-firing is carried out when being warming up to 400~800 DEG C, later 0.1 × 104~9.5 × 104Under Pa, according to 10 DEG C/it is small When~100 DEG C/h of speed is continuously heating to 800~1200 DEG C；
B, keeping inert gas flow is 200L/ hours until pressure rises to 1.1 × 105~3 × 105After Pa, by 30 DEG C/h ~300 DEG C/h of speed is warming up to 1200~2000 DEG C and keeps the temperature 0.5~5 hour, is naturally cooling to room temperature later；
The oxygen content of the non-fusible polycarbosilane fiber is lower than 5wt%, and gel content is greater than 70wt%, 1000 DEG C of ceramic yields Greater than 60wt%, fibre diameter is 5~30 μm；
The inert gas is that nitrogen, argon gas or helium are any；
It is 10~300 DEG C/h from room temperature to 400 DEG C~800 DEG C of heating rate, inert gas described in temperature-rise period Flow is 10L/ hours~1000L/ hours；
The inert atmosphere forming method is the following steps are included: first vacuumize reduces pressure to≤10Pa, Zhi Houchong in triplicate Enter the inert gas and increases pressure to 105Pa。
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