CN106747671B - The preparation method of superhigh temperature thermostructural composite boundary layer - Google Patents

The preparation method of superhigh temperature thermostructural composite boundary layer Download PDF

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CN106747671B
CN106747671B CN201610390103.2A CN201610390103A CN106747671B CN 106747671 B CN106747671 B CN 106747671B CN 201610390103 A CN201610390103 A CN 201610390103A CN 106747671 B CN106747671 B CN 106747671B
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superhigh temperature
boundary layer
silicon carbide
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layer
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CN106747671A (en
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罗瑞盈
王连毅
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Beihang University
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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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

Abstract

The invention provides a kind of preparation method of superhigh temperature thermostructural composite boundary layer, this method is provided with the composite material interface layer of three-decker between the fiber and matrix of superhigh temperature thermostructural composite, is respectively outwards silicon carbide layer, porous mullite layer, silicon carbide layer from fiber.Silicon carbide layer can prevent elements diffusion, protect matrix not lost with fibre property；Porous mullite layer has excellent high-temperature oxidation resistance, high-temperature stability is good, and loose structure plays a part of inducing the performance of the toughening mechanisms such as micro-crack deflection, effective guarantee fiber-bridged, spike protein gene；MULTILAYER COMPOSITE boundary layer is advantageous to micro-crack deflection.Therefore the superhigh temperature thermostructural composite with the boundary layer is with excellent high-temperature oxidation resistance and excellent mechanical behavior under high temperature.

Description

The preparation method of superhigh temperature thermostructural composite boundary layer
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of system of superhigh temperature thermostructural composite boundary layer Preparation Method.
Background technology
Carborundum have excellent elevated temperature strength, high-temperature stability and obtain extensive concern, but monomer silicon carbide ceramics is tough Property is low, is easily caused material catastrophic failure.Silicon carbide fiber reinforced silicon carbide is prepared with continuous carbofrax fibre toughening silicon carbide Composite can be obviously improved monomer ceramics toughness, inhale ripple material in high-temperature structural material, frit reaction heap and thermal structure The fields such as material have broad application prospects.
Interface be mutually silicon carbide fiber reinforced silicon carbide composite material mechanical property and the realization of other performances it is crucial because One of element, suitable interface phase, appropriate interface phase thickness effectively can induce matrix micro-cracks to deflect, make fiber-bridged, fibre The toughening mechanisms such as dimension extraction are played.
Silicon carbide fiber reinforced silicon carbide composite material generally use pyrolytic carbon and hexagonal boron nitride are as interface phase.Its In, pyrolytic carbon has special layered crystal structure, prepares wide material sources, good with the compatibility of fiber and matrix, has good Mechanical property.But pyrolytic carbon easily aoxidizes, at high temperature, after boundary layer is all oxidized, fiber and matrix will be by Oxidation forms silicon oxide layer, so as to which most at last together with fiber and bond matrix, the strong combination at interface can prevent the sliding of fiber And extraction, cause material to show as fragility, have impact on the performance of silicon carbide fiber reinforced silicon carbide composite material mechanical behavior under high temperature. In addition, using with being used as boundary layer with the hexagonal boron nitride of pyrolytic carbon similar crystal structure, compared with pyrolytic carbon, its with compared with Good antioxygenic property, the glassy state boron oxide formed after oxidation can make up the gap between fibrous matrix, hinder the diffusion of oxygen, Therefore composite material exhibits go out preferable inoxidizability.But there is problems with hexagonal boron nitride as boundary layer：(1) prepare logical Frequently with source of the gas (boron trifluoride, ammonia) there is corrosivity to silicon carbide fibre, the damage of fiber can be caused；(2) boron nitride circle Combination inside the phase of face and its between fiber is weaker, generally requires subsequent high temperature heat treatment to improve its combination, but high warm Processing particularly can cause to damage to silicon carbide fibre to the silicon carbide fibre of elevated oxygen level；(3) boron nitride oxidation product oxygen Change boron in high temperature, particularly readily volatilized loss when higher than 1300 DEG C, lose its inhibition to oxygen, while the oxygen of liquid The silica of Oxidation of SiC formation can be dissolved by changing boron, form low melting point silicon boron compound, increase the diffusivity of oxygen, promote carbon The consumption of SiClx；(4) boron oxide of glassy state or silicon boron glass can form strong combination with fiber and matrix, destroy composite Weak binding interface, reduce the toughness of composite.
There is the problem of high-temperature oxidation resistance difference in pyrolytic carbon and hexagonal boron nitride boundary layer, seriously constrain carborundum fibre The performance of dimension enhancing composite material of silicon carbide mechanical behavior under high temperature, therefore, develops oxidation resistant interface phase, improves silicon carbide fibre It is significantly to strengthen composite material of silicon carbide mechanical behavior under high temperature.
The content of the invention
It is an object of the invention to provide a kind of preparation method of superhigh temperature thermostructural composite boundary layer, it is intended to solves existing There is the problem of its high-temperature oxidation resistance of the superhigh temperature thermostructural composite of technology is poor, restricts mechanical behavior under high temperature performance.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of superhigh temperature thermostructural composite boundary layer, including：
Silicon carbide layer is prepared on the surface of initial fiber precast body, prepares one-level fiber preform；
Porous mullite layer is prepared on the surface of the one-level fiber preform, prepares secondary fiber precast body；
Silicon carbide layer is prepared on the surface of the secondary fiber precast body.
On this basis, further, porous mullite layer is prepared on the surface of the one-level fiber preform, prepares two The step of level fiber preform, it is specially：
Using aluminium secondary butylate as silicon source, tetraethyl orthosilicate is as silicon source, and ethyl acetoacetate is as chelating agent, by quality Than being dissolved in for the aluminium secondary butylate, tetraethyl orthosilicate, ethyl acetoacetate of the first predetermined ratio in ethanol, stir, prepare First mixed liquor；
It will be added to the mass ratio of aluminium secondary butylate for the water of the second predetermined ratio in first mixed liquor, stirring is equal It is even, prepare the second mixed liquor；
The one-level fiber preform is subjected to vacuum impregnation in second mixed liquor, insulation makes its gelation, makes The fiber preform of standby gelation；
Using the technique of Pintsch process, mullite layer is prepared on the surface of the fiber preform of the gelation, prepares two Level fiber preform.
On this basis, further, first predetermined ratio is 50:1:26.
Or further, second predetermined ratio is 1:2.
It is further, described to prepare carbonization on the surface of initial fiber precast body on the basis of above-mentioned any embodiment Silicon layer, prepare one-level fiber preform the step of in, long-pending technique is oozed using gas phase and prepares silicon carbide layer.
On this basis, further, the gas phase is oozed in long-pending technique, using trichloromethyl silane as silicon source.
Or further, the gas phase is oozed in long-pending technique, using argon gas as diluent gas.
Or further, the gas phase is oozed in long-pending technique, accumulated temperature degree is oozed for 1000 DEG C.
It is further, described to be prepared on the surface of the secondary fiber precast body on the basis of above-mentioned any embodiment In the step of silicon carbide layer, long-pending technique is oozed using gas phase and prepares silicon carbide layer.
On the basis of above-mentioned any embodiment, further, the initial fiber precast body is Hi-Nicalon fibers Or Hi-Nicalon type S fibers.
The beneficial effects of the invention are as follows：
The invention provides a kind of preparation method of superhigh temperature thermostructural composite boundary layer, this method warms in superelevation The composite material interface layer of three-decker is provided between the fiber and matrix of structural composite material, is respectively outwards to be carbonized from fiber Silicon layer, porous mullite layer, silicon carbide layer.Silicon carbide layer can prevent elements diffusion, protect matrix not lost with fibre property； Porous mullite layer has excellent high-temperature oxidation resistance, and high-temperature stability is good, and loose structure plays induction micro-crack deflection The toughening mechanisms such as effect, effective guarantee fiber-bridged, spike protein gene performance；MULTILAYER COMPOSITE boundary layer is advantageous to micro-crack Deflection.Therefore the superhigh temperature thermostructural composite with the boundary layer is with excellent high-temperature oxidation resistance and excellent height Warm mechanical property.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 shows a kind of preparation method of superhigh temperature thermostructural composite boundary layer provided in an embodiment of the present invention Flow chart；
Fig. 2 shows a kind of composite oxidation quality and the graph of a relation of time provided in an embodiment of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not Limit the present invention.
Specific embodiment one
As shown in figure 1, the embodiments of the invention provide a kind of preparation method of superhigh temperature thermostructural composite boundary layer, Including：
Step S101, silicon carbide layer is prepared on the surface of initial fiber precast body, prepare one-level fiber preform；
Step S102, porous mullite layer is prepared on the surface of one-level fiber preform, prepares secondary fiber precast body；
Step S103, silicon carbide layer is prepared on the surface of secondary fiber precast body.
The embodiment of the present invention is compound provided with three-decker between the fiber and matrix of superhigh temperature thermostructural composite Material interface layer, it is respectively outwards silicon carbide layer, porous mullite layer, silicon carbide layer from fiber.Silicon carbide layer can prevent member Element diffusion, protects matrix not lost with fibre property；Porous mullite layer has excellent high-temperature oxidation resistance, high-temperature stable Property it is good, loose structure plays a part of inducing the toughening mechanisms such as micro-crack deflection, effective guarantee fiber-bridged, spike protein gene Play；MULTILAYER COMPOSITE boundary layer is advantageous to micro-crack deflection.Therefore the superhigh temperature thermostructural composite with the boundary layer has There are excellent high-temperature oxidation resistance and excellent mechanical behavior under high temperature.
The embodiment of the present invention prepares the raw material of porous mullite layer to sol-gal process and mode does not limit, it is preferred that Preparing the mode of porous mullite layer can be specially：Using aluminium secondary butylate as silicon source, tetraethyl orthosilicate is as silicon source, acetyl Ethyl acetate is molten for aluminium secondary butylate, tetraethyl orthosilicate, the ethyl acetoacetate of the first predetermined ratio by mass ratio as chelating agent Solution stirs in ethanol, prepares the first mixed liquor；It will be added with the mass ratio of aluminium secondary butylate for the water of the second predetermined ratio Into the first mixed liquor, stir, prepare the second mixed liquor；One-level fiber preform is subjected to vacuum in the second mixed liquor Dipping, heating make its gelation, then using the technique of Pintsch process, mullite are prepared on the surface of one-level fiber preform Layer, prepares secondary fiber precast body.
The embodiment of the present invention to silicon source aluminium secondary butylate, silicon source tetraethyl orthosilicate, chelating agent ethyl acetoacetate mass ratio Do not limit, it is preferred that aluminium secondary butylate, tetraethyl orthosilicate, the mass ratio of ethyl acetoacetate can be 50:1:26.
The embodiment of the present invention is not limited the quality of the water for preparing the second mixed liquor, it is preferred that water and sec-butyl alcohol The mass ratio of aluminium can be 1:2.
The embodiment of the present invention is not limited the technique that silicon carbide layer is prepared in step S101 and step S103, it is preferred that Long-pending technique can be oozed using gas phase and prepare silicon carbide layer.
The embodiment of the present invention is oozed long-pending technological parameter to gas phase and not limited, it is preferred that trichloromethyl silane can be used to make For silicon source.It is that the atomicity such as Si and C, is easy to get in trichloromethyl silane molecule using benefit of the trichloromethyl silane as silicon source To the SiC of chemical molecular metering, and ooze that accumulated temperature degree is wider, and technique is easily controllable, therefore long-pending SiC is oozed as the most frequently used gas phase Gas.
The embodiment of the present invention is oozed long-pending technological parameter to gas phase and not limited, it is preferred that can use argon gas as carrier gas Body.It is that for argon gas as rare gas, chemical property is stable, is not involved in gas phase and oozes product using benefit of the argon gas as diluent gas Reaction, it is cheap, it can effectively be played as diluent gas and slow down reaction rate, increase the effect of gas molecule free path, Be advantageous to obtain uniform, fine and close SiC interfaces phase.
The embodiment of the present invention is oozed long-pending technological parameter to gas phase and not limited, it is preferred that it can be 1000 DEG C to ooze accumulated temperature degree.
Table 1 oozes the relation of accumulated temperature degree and bending strength
Ooze accumulated temperature degree (DEG C) Bending strength (MPa)
900 329
950 573
1000 860
1050 683
1100 554
As shown in table 1, the bending strength of composite changes with accumulated temperature degree is oozed.
Method in the embodiment of the present invention is not limited the type of be applicable fiber preform, it is preferred that initial fine It is Hi-Nicalon fibers or Hi-Nicalon type S fibers to tie up precast body.Hi- as 2nd generation silicon carbide fibre Nicalon fibers, the mass fraction of its oxygen reduce, and the mass fraction of free carbon is of a relatively high, and the size of carborundum grain is compared with the 1st Dai great, the heat resistance of fiber improve, and keep the temperature of the maximum tensile strength to bring up to 1300 from 1200 DEG C of 1st generation ℃；Hi-Nicalon type S fibers are made up of sub-micron β-SiC crystal grain, a small amount of carbon and trace oxygen, embody high Young mould Measure, good heat endurance at high creep resistant and antioxygenic property and 1600 DEG C.
On the basis of above-mentioned any embodiment, the embodiment of the present invention can also include：To the three-level fiber preform It is densified, prepares superhigh temperature thermostructural composite.
The embodiment of the present invention is not limited the mode that three-level fiber preform is densified, it is preferred that it can be specially： Vacuum impregnation and Pintsch process are carried out to three-level fiber preform, prepare superhigh temperature heat structure intermediate product；To superhigh temperature thermojunction Structure intermediate product is weighed, when superhigh temperature heat structure intermediate product is more than or equal to relative to the weightening of three-level fiber preform During predetermined ratio, repeat to carry out vacuum impregnation and Pintsch process to superhigh temperature heat structure intermediate product；When in superhigh temperature heat structure Between product when being less than predetermined ratio relative to the weightening of three-level fiber preform, from the superhigh temperature heat structure intermediate product conduct Superhigh temperature thermostructural composite.Superhigh temperature heat structure composite wood is prepared by the way of multiple vacuum impregnation and Pintsch process Material, its technical maturity, efficiency high.
The embodiment of the present invention to superhigh temperature heat structure intermediate product prepared after vacuum impregnation and Pintsch process relative to The weightening of three-level fiber preform does not limit, it is preferred that superhigh temperature heat structure intermediate product is relative to three-level fiber preform Weightening predetermined ratio be 1%.
In the embodiment of the present invention, in the step of carrying out vacuum impregnation to three-level fiber preform, to selected dipping Agent does not limit, it is preferred that can use the xylene solution of Polycarbosilane as impregnating agent.
The embodiment of the present invention is not limited the Solute mass fraction of the xylene solution of Polycarbosilane, and the two of Polycarbosilane Toluene solution mass fraction is higher, and pyrolysis gained ceramic yield is higher, simultaneously, it is contemplated that dipping effect, the diformazan of Polycarbosilane The mass fraction of benzole soln should be more low better, to ensure that viscosity is low as far as possible, it is preferred, therefore, that the dimethylbenzene of Polycarbosilane The Solute mass fraction of solution is 50%.As shown in table 2, when the Solute mass fraction of the xylene solution of Polycarbosilane is 50% When~70%, composite viscosity is 83~1027mPas.
The Solute mass fraction of xylene solution and the relation of viscosity of the Polycarbosilane of table 2
The Solute mass fraction (%) of the xylene solution of Polycarbosilane Viscosity (mPas)
70 1027
60 525
50 83
The embodiment of the present invention is oozed long-pending technological parameter to gas phase and not limited, it is preferred that gas phase is oozed in long-pending technique, can be used Trichloromethyl silane is silicon source, and argon gas is diluent gas, and hydrogen is carrier gas.Its specific process parameter can be as follows：With three chloromethanes Base silane is silicon source, and argon gas is diluent gas, and air velocity is 50~80cm3/ min, thinner ratio are 9~11, and hydrogen is carrier gas, Air velocity is 150~200cm3/ min, pressure is 5~10kPa in stove, oozes accumulated temperature degree for 900 DEG C~1100 DEG C, oozes the long-pending time For 2h.
The gas phase of table 3 oozes the relation of long-pending technological parameter and composite bending strength
As shown in table 3, as gas phase oozes the change of long-pending technological parameter, the bending strength of composite also changes therewith.
Specific embodiment two
It is basic the embodiments of the invention provide a kind of preparation method of superhigh temperature thermostructural composite boundary layer, and herein On to the composite with the boundary layer, its performance is tested, flow is as follows：
Step 1, SiC layer is prepared on 3D Hi-Nicalon fiber preforms：To 3D Hi-Nicalon fiber preforms Cleaned, be put into progress gas phase in gaseous phase deposition stove and ooze product.Oozing long-pending technique is：With trichloromethyl silane (MTS) for silicon source, put In 60 DEG C of bubbling tanks, with hydrogen (H2) it is carrier gas, air velocity 200cm3/ min, argon gas (Ar) are diluent gas, gas velocity Spend for 70cm3/ min, mixed gas pressure intensity 5kPa, accumulated temperature degree are oozed for 1000 DEG C, it is 2h to ooze the long-pending time；
Step 2, porous 3Al2O3 is prepared on step 1 gained fiber3·2SiO22Layer：
1) using aluminium secondary butylate (ASB) as silicon source, tetraethyl orthosilicate (TEO) is used as silicon source, ethyl acetoacetate (EAcAc) As chelating agent, according to mass ratio (ASB：TEO：EAcAc it is) 50:1:26, it is dissolved in ethanol, stirs, obtains quality Fraction is 20% solution.
2) according to mass ratio (H2O：ASB it is) 1:2 add distilled water into mixed liquor, and stir and be allowed to uniformly hydrolyze.
3) step 1 gained fiber is placed in vacuum impregnation tank and impregnated, and 5h is incubated at 70 DEG C, be allowed to gelation.
4) N is led to2Protection, 100 DEG C are heated in cvd furnace and is incubated 1h, the organic simple substance to dissociate in the gel that volatilizees, then 500 DEG C of insulation 1h are warming up to 5 DEG C/min, organic cracking is converted into inorganic matter, is then warming up to 1200 DEG C with 1 DEG C/min 1h is incubated, makes Al2O3And SiO2Reaction produces mullite, then is cooled to room temperature with 1 DEG C/min, obtains porous 3Al2O3·2SiO2 Layer；
Step 3, SiC layer is prepared on step 2 gained fiber：With trichloromethyl silane (MTS) for silicon source, 60 DEG C of drums are placed in Steep in tank, with hydrogen (H2) it is carrier gas, air velocity 200cm3/ min, argon gas (Ar) are diluent gas, and air velocity is 70cm3/ min, mixed gas pressure intensity 5kPa, accumulated temperature degree are oozed for 1000 DEG C, it is 2h to ooze the long-pending time；
Step 4, SiC is prepared on step 3 gained precast body using PIP methodsf/ SiC ceramic matrix composite material：
1) xylene solution by mass fraction for 50% Polycarbosilane, Vaccum Permeating is put into step 3 gained precast body In stain machine, vacuum impregnation.
2) 1) gained precast body is put into heat in gaseous phase deposition stove and cracked, cracking technology is：Under argon gas protection, with 5 DEG C/after min is warming up to 1200 DEG C and is incubated 1h, room temperature is cooled to 5 DEG C/min；
3) repeat 1), 2) process, untill material weightening is less than 1%.
Step 5, the progress still air high-temperature oxidation resistant in tube furnace is carried out to the composite obtained by step 4 to examine Core：Examination condition is：Tubular type in-furnace temperature is 1100 DEG C, air velocity 4.4cm/s, total duration 300h.Respectively 0,5h, 10h, 25h, 50h, 100h, 150h, 200h, 250h, 300h measure sample weight, and the result of appraisal are as shown in Fig. 2 curve 1 is this The hot arc composite oxidation quality change that inventive embodiments provide, curve 2 are the hot junction composite oxidation with carbon interface Mass change.Contrast finds that curve 1 and curve 2 early stage of mass change difference are obvious, the phase rapid weight loss before oxidation of curve 2, anti- Oxidability is poor, and the extension of curve 1 over time is slightly increased weight by comparison, and later stage mass change is identical with the trend of curve 2, This is due to caused by matrix SiC is aoxidized.
Step 6, to step 4 gained SiCf/ SiC ceramic matrix composite material carries out bending strength test：Specimen size is 45*4*3mm, Span is 30mm, loading velocity 0.5mm/min, the bending strength tested before and after its 1100 DEG C oxidation 10h.And with PyC interfaces SiCf/ SiC ceramic matrix composite material is contrasted.As shown in table 4, numbering 1 is the hot arc composite that the embodiment of the present invention refers to, is compiled Numbers 2 be the hot arc composite with carbon interface.Contrast finds that bending strength of the numbering 1 when to aoxidize is slightly below numbering 2, but It is the bending strength loss 54% of numbering 2 after 10h is aoxidized, and the bending strength of numbering 1 shows the present invention without significant change The hot junction composite that embodiment refers to excellent normal temperature and mechanical behavior under high temperature, with good oxidation resistance.
Table 4 aoxidizes the bending strength of front and rear composite
The invention provides a kind of preparation method of superhigh temperature thermostructural composite boundary layer, this method warms in superelevation The composite material interface layer of three-decker is provided between the fiber and matrix of structural composite material, is respectively outwards to be carbonized from fiber Silicon layer, porous mullite layer, silicon carbide layer.Silicon carbide layer can prevent elements diffusion, protect matrix not lost with fibre property； Porous mullite layer has excellent high-temperature oxidation resistance, and high-temperature stability is good, and loose structure plays induction micro-crack deflection The toughening mechanisms such as effect, effective guarantee fiber-bridged, spike protein gene performance；MULTILAYER COMPOSITE boundary layer is advantageous to micro-crack Deflection.Therefore the superhigh temperature thermostructural composite that prepared by this method has excellent high-temperature oxidation resistance and excellent high temperature Mechanical property.
Although present invention has been a certain degree of description, it will be apparent that, do not departing from the spirit and scope of the present invention Under the conditions of, the appropriate change of each condition can be carried out.It is appreciated that the invention is not restricted to the embodiment, and it is attributed to right It is required that scope, it includes the equivalent substitution of each factor.

Claims (9)

  1. A kind of 1. preparation method of superhigh temperature thermostructural composite boundary layer, it is characterised in that including：
    Silicon carbide layer is prepared on the surface of initial fiber precast body, prepares one-level fiber preform；
    Porous mullite layer is prepared on the surface of the one-level fiber preform, prepares secondary fiber precast body；
    Silicon carbide layer is prepared on the surface of the secondary fiber precast body；
    Wherein, porous mullite layer is prepared on the surface of the one-level fiber preform, the step of preparing secondary fiber precast body, Specially：
    It is by mass ratio as chelating agent as silicon source, ethyl acetoacetate as silicon source, tetraethyl orthosilicate using aluminium secondary butylate Aluminium secondary butylate, tetraethyl orthosilicate, the ethyl acetoacetate of first predetermined ratio are dissolved in ethanol, are stirred, and prepare first Mixed liquor；
    It will be added to the mass ratio of aluminium secondary butylate for the water of the second predetermined ratio in first mixed liquor, stir, make Standby second mixed liquor；
    The one-level fiber preform is subjected to vacuum impregnation in second mixed liquor, insulation makes its gelation, prepares solidifying The fiber preform of gel；
    Using the technique of Pintsch process, mullite layer is prepared on the surface of the fiber preform of the gelation, it is fine to prepare two level Tie up precast body.
  2. 2. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 1, it is characterised in that described First predetermined ratio is 50:1:26.
  3. 3. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 1, it is characterised in that described Second predetermined ratio is 1:2.
  4. 4. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 1, it is characterised in that described Prepare silicon carbide layer on the surface of initial fiber precast body, in the step of preparing one-level fiber preform, long-pending work is oozed using gas phase Skill prepares silicon carbide layer.
  5. 5. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 4, it is characterised in that described Gas phase is oozed in long-pending technique, using trichloromethyl silane as silicon source.
  6. 6. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 4, it is characterised in that described Gas phase is oozed in long-pending technique, using argon gas as diluent gas.
  7. 7. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 4, it is characterised in that described Gas phase is oozed in long-pending technique, oozes accumulated temperature degree for 1000 DEG C.
  8. 8. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 1, it is characterised in that described In the step of surface of the secondary fiber precast body prepares silicon carbide layer, long-pending technique is oozed using gas phase and prepares silicon carbide layer.
  9. 9. the preparation method of superhigh temperature thermostructural composite boundary layer according to claim 1, it is characterised in that described Initial fiber precast body is Hi-Nicalon fibers or Hi-Nicalon type S fibers.
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