CN106966738A - Self-healing ceramic matric composite combustion chamber flame drum and preparation method and application - Google Patents

Self-healing ceramic matric composite combustion chamber flame drum and preparation method and application Download PDF

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CN106966738A
CN106966738A CN201611056545.XA CN201611056545A CN106966738A CN 106966738 A CN106966738 A CN 106966738A CN 201611056545 A CN201611056545 A CN 201611056545A CN 106966738 A CN106966738 A CN 106966738A
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combustion chamber
chamber flame
flame drum
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CN106966738B (en
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罗瑞盈
王天颖
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Beihang University
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Abstract

The present invention relates to a kind of self-healing ceramic matric composite combustion chamber flame drum and preparation method and application, preparation method comprises the following steps:Combustion chamber flame drum precast body is prepared into SiC interfaces with chemical vapour deposition technique;It is densified again using precursor infiltration and pyrolysis method;It is 1.6~1.8g/cm to repeat precursor infiltration and pyrolysis method to the density of obtained silicon carbide substrate3;SiC matrix layer and BCx base layers are prepared using chemical vapor infiltration area method on the surface of silicon carbide substrate, density is obtained for 2.0~2.5g/cm3Carbon borosilicate self-healing matrix, then at 1000 DEG C carry out 1~3h modifications, obtain composite combustion chamber flame drum.The composite combustion chamber flame drum that the present invention is provided, can improve bending strength, heat-resisting ability, oxidation resistance, self-healing performance and the efficiency gas of combustion chamber flame drum, reduce the quality of combustion chamber flame drum and the discharge of discarded object.

Description

Self-healing ceramic matric composite combustion chamber flame drum and preparation method and application
Technical field
The present invention relates to aviation technical field of structural materials, and in particular to a kind of self-healing ceramic matric composite burning Room burner inner liner and preparation method and application.
Background technology
Combustion chamber is one of core component of aero-engine, and its major function is to turn the chemical energy of fuel by burning It is changed into heat energy, to improve the ability that combustion gas expands in turbine and jet pipe.In the structure composition of combustion chamber, burner inner liner is tissue The place of burning, is the critical component for ensureing that air share split, burning are abundant, blending is uniform and being winding is effectively cooled wall.Combustion Reliability, economy and the life-span for burning room depend greatly on the reliability and significant degree of burner inner liner, therefore develop The combustion chamber flame drum of high performance and long service life plays vital effect for improving engine performance.
Combustion chamber flame drum belongs to high-temperature component in engine components, the environment temperature being chronically at 1300 DEG C with On, the temperature in use and military service performance of existing superalloy turbine part are usually taken high-temperature component close to the limit The safeguard procedures such as air cooling and thermal barrier coating.But, the application of cold air can not only reduce engine combustion efficiency;Part can also be made Complicatedization, increase design and difficulty of processing.High Performance Aeroengine pursues constantly lifting turbine inlet temperature, and thrust-weight ratio is During 12-15, inlet temperature is up to more than 1800 DEG C, the temperature in use and military service performance of existing superalloy turbine part before turbine Close to the limit, even if taking cooling technology and Thermal Barrier Coating Technologies, it is also difficult to which the design for meeting aero-engine of future generation will Ask.It is an advanced technology to prepare combustion chamber flame drum using refractory ceramics based composites, and ceramic matric composite has The features such as high temperature resistant, density are low, corrosion-resistant and anti-oxidant, disclosure satisfy that hot-end component is used under higher temperature environment, not only It is beneficial to significantly loss of weight, can also saves cold air even without cooling, so as to improves overall pressure tatio (Overall Pressure Ratios, OPR), realize and 300~500 DEG C of operating temperature, structure loss of weight 50% are further lifted on the basis of high temperature alloy heatproof ~70%, the crucial heat resistant structure that certainly will turn into high thrust-weight ratio aero-engine prepares material.
Existing carbon/silicon carbide ceramic matrix composite has excellent performance, is that instead of high temperature alloy as aero-engine The candidate materials of hot junction component material, but under high-temperature oxidation environment, SiCfThe micro-crack produced in composite and hole Hole easily turns into Oxidant (O2And H2O) and exhaust gas corrosion passage, cause interface phase and fiber oxidation in SiC constituent elements by Damage;In addition, the stress in Service Environment can promote matrices of composite material to ftracture, the damage and corrosion of accelerated material, influence Its long-life requirement of being on active service under high temperature combustion environment, so that seriously restriction SiC ceramic based composites are in engine combustion The application of room burner inner liner.
The content of the invention
For defect of the prior art, present invention aims at provide a kind of self-healing ceramic matric composite combustion chamber Burner inner liner and preparation method and application, with improve the bending strength of combustion chamber flame drum, heat-resisting ability, oxidation resistance and Efficiency gas, reduces the quality of combustion chamber flame drum and the discharge of NOx, COx the like waste, and assign combustion chamber flame drum certainly Healing properties, when there is crackle and hole in material, can in-situ authigenic into glass phase, reach the effect of active packing, prevent Oxidant inwardly spreads, the oxide etch damage of reduction interface and fiber, improves the life-span of combustion chamber flame drum.
To achieve the above object, the technical scheme that provides of the present invention is:
In a first aspect, the invention provides a kind of preparation method of composite combustion chamber flame drum, comprising the following steps: S1:Combustion chamber flame drum precast body is prepared into SiC interfaces with chemical vapour deposition technique;Wherein, the reaction of chemical vapour deposition technique Gas is trichloromethyl silane;S2:Using the mixed solution of Polycarbosilane and dimethylbenzene as precursor solution, the production that step S1 is obtained Thing is densified using precursor infiltration and pyrolysis method;Repeat using precursor infiltration and pyrolysis method to obtained silicon carbide substrate Density is 1.6~1.8g/cm3;S3:SiC matrix layer and BCx are prepared using chemical vapor infiltration area method on the surface of silicon carbide substrate Base layer, obtains density for 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, using trichloromethyl silane as deposition gas SiC matrix layer is prepared, BCx base layers are prepared using boron chloride and methane as deposition gas;S4:Carbon borosilicate self-healing matrix is existed 1~3h modifications are carried out at 1000 DEG C, composite combustion chamber flame drum is obtained.It should be noted that changing in step S4 Property processing, be in order in the hole of carbon borosilicate self-healing intrinsic silicon and a large amount of fine and close Pyrex phases are filled on surface;Through Composite combustion chamber flame drum after multi-component multi-layer self-healing matrix modification, under water oxygen combustion gas stress coupling environment, carbon boron The substantial amounts of glass phase of silicon self-healing intrinsic silicon self-healing constituent element formation, on the one hand can prevent the carborundum phase oxidation of inside rotten Erosion is impaired, on the other hand makes carbon borosilicate self-healing matrix densification, composite combustion chamber flame drum is obtained so as to improve Bending strength and modulus.
In the further embodiment of the present invention, in step S1, chemical vapour deposition technique is specially:With trichloromethyl silicon Alkane is reaction gas, and hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 1100~1230 DEG C, and pressure is 1~5kPa, deposition Time is 5~15h;Wherein, the volume ratio of hydrogen and trichloromethyl silane is 1:8~1:12.It should be noted that preparing SiC interfaces be single-phase, interfacial thickness is preferably 3~10 μm.In combustion chamber flame drum (silicon carbide fibre) precast body surface One layer of carborundum is deposited, can make to form weak interface combination between fiber and matrix so that fiber can pass through unsticking and extraction Effective consumed energy, so as to get composite show obvious ductile rupture feature in destruction, be conducive to composite wood Expect the raising of mechanical property.
In the further embodiment of the present invention, in step S2, precursor infiltration and pyrolysis method includes:In vacuum condition Under, the obtained products of step S1 are impregnated in 4~6h in the mixed solution of Polycarbosilane and dimethylbenzene, then done for 100~140 DEG C It is dry;Dried product is cracked into 3~6h in nitrogen or argon gas in 800~1200 DEG C;Repeat precursor infiltration and pyrolysis method Step, the density to obtained silicon carbide substrate is 1.6~1.8g/cm3;Wherein, the mixed solution of Polycarbosilane and dimethylbenzene The mass fraction of middle Polycarbosilane is 20%~50%.It should be noted that dipping process can be carried out in impregnating autoclave, true Under empty condition, according to capillarity and diffusion, Polycarbosilane can penetrate into the inside of combustion chamber flame drum precast body, and Fill hole therein;Pintsch process is that by polymer Polycarbosilane is converted into ceramic base, obtains silicon carbide-based Body.
In the further embodiment of the present invention, in step S3, the preparation method of SiC matrix layer is specially:With trichlorine Methyl-monosilane (CH3SiCl3) it is deposition gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 800~1100 DEG C, deposition Time is 10~30h, and pressure is 1kPa;Wherein, the flow of hydrogen is 100~400ml/min, the flow of argon gas for 100~ 300ml/min;The preparation method of BCx base layers is specially:Using boron chloride and methane as deposition gas, hydrogen and argon gas are load Gas, depositing temperature is 900~1000 DEG C, and sedimentation time is 10~30h, and pressure is 1kPa;Wherein, the stream of boron chloride and methane Amount is than being 2:1~6:1, the flow velocity of hydrogen and argon gas is 50~80mL/min.
In the further embodiment of the present invention, in step S3, on the surface of silicon carbide substrate, alternately prepare successively SiC matrix layer and BCx base layers, obtain density for 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, carbon borosilicate from The outermost layer of healing matrices is SiC matrix layer.It should be noted that:On the surface of silicon carbide substrate, SiC matrix is first prepared Layer, then BCx base layers are prepared, circulate according to this, obtain density for 2.0~2.5g/cm3Carbon borosilicate self-healing matrix, and protect The outermost layer for demonstrate,proving carbon borosilicate self-healing matrix is SiC matrix layer, that is to say, that in obtained carbon borosilicate self-healing matrix, SiC matrix layer is at least two layers, and BCx base layers are at least one layer;The order setting of base layer allows for PIP methods and prepared SiC matrix there is thermal matching, when the thermal coefficient of expansion of matrix is similar, it is possible to reduce material is in hot environment because of thermal expansion The crackle that coefficient difference is produced, therefore first deposit on the surface of silicon carbide substrate one layer of SiC matrix, redeposited one layer of BCx matrix, Circulate according to this, successively alternating deposit SiC matrix and BCx matrixes;And last layer is set to SiC matrix, allows for SiC matrix There is more high temperature tolerance and inoxidizability than BCx matrix.
In the further embodiment of the present invention, on the surface of composite combustion chamber flame drum, rare earth silicic acid is prepared Salt environment barrier coating;The raw material of rare earth silicate Environmental Barrier Coatings on Si-based Ceramics includes the first component and the second component, and the first component is not come Stone, ytterbium silicate (Yb2SiO5), polyvinyl butyral (PVB) and phosphate, the second component is ethanol;Wherein:First component and The mass ratio of two components is 1:1~1:3, mass fraction of the polyvinyl butyral in the first component is 4%~8%, phosphate Mass fraction in the first component is 0.4%~1.0%, and the mass ratio of mullite and ytterbium silicate is 88:12.Need explanation It is:Rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared on the surface of composite combustion chamber flame drum, that is, in composite burning Set up and shield together between the adverse circumstances that room flame barrel component surface and engine superhigh temperature, Korrosionsmedium, high velocity air wash away Barrier coating, can reduce influence of the engine environmental to composite combustion chamber flame drum component performance, it is to avoid the stabilization of material Property deteriorates, and prevents that the mechanical property of material is decreased obviously, can further improve the ring of composite combustion chamber flame drum Border tolerance and resistance to combustion gas corrosion performance.
In the further embodiment of the present invention, the preparation method of rare earth silicate Environmental Barrier Coatings on Si-based Ceramics includes:By first Component and second component 12~16h of ball milling mixing, by obtained mixture brushing on the surface of composite combustion chamber flame drum, Then 2~5h is sintered at 1400 DEG C~1500 DEG C.
In the further embodiment of the present invention, combustion chamber flame drum precast body is to use silicon carbide fibre with three-dimensional four Footwork braiding is formed, wherein, braid angle is 20~45 °, the volume fraction 30%~50% of silicon carbide fibre.Need explanation It is:Combustion chamber flame drum is the core component of engine chamber, including flame tube head and cylinder, and cylinder includes inwall and outer Wall;During braiding, flame tube head and inside and outside wall are woven respectively, and the precast body of three parts is then sutured into skill using fiber Art connects together shaping, and obtained product is carried out into high-temperature heat treatment, to remove the glue and impurity on surface, is burnt Room burner inner liner precast body;Using three-dimensional four step braiding combustion chamber flame drum precast body, combustion chamber flame drum can be improved prefabricated The intensity of body, it is ensured that excellent mechanical property, coupling part use fiber suturing skill, can avoid ceramic matric composite with High temperature alloy fastener is destroyed because caused by difference of linear expansion is big, it is ensured that bonding strength, while cancelling cooling system.
Second aspect, the invention provides the composite combustion chamber flame drum prepared according to above-mentioned method.
The third aspect, the invention provides the above-mentioned composite combustion chamber flame drum prepared to prepare engine outstanding It is to prepare the application in aero-engine.
The technical scheme that the present invention is provided, has the following advantages:
(1) present invention prepares precast body using three dimensional knitting method, not only makes precast body in many axial planes in space and between face It is complete continuous, fundamentally avoid two-dimension laminate precast body intensity and modulus be poor in a thickness direction, interlaminar shear strength is low and The relatively low shortcoming of damage tolerance, and 3 D weaving precast body comprehensive mechanical property is good, and thermal shock resistance properties is excellent.
(2) silicon carbide interface that the present invention is used has more preferable inoxidizability compared with carbon interface, is pyrolyzed carbon boundary layer Easily aoxidized more than 400 DEG C, composite can be because intensity occurs in the rapid oxidation at carbon interface under high-temperature oxidation environment Dramatic decrease, and silicon carbide interface with applied at elevated temperature environment oxidation resistance it is strong, it is not oxidizable, play interface transmission and carry The effect of lotus, makes material have more preferable mechanical property in hot environment.
(3) present invention prepares self-healing using PIP+CVI United Technologies (precursor infiltration and pyrolysis method+chemical vapor infiltration area method) Modified matrix is closed, the silicon carbide substrate of certain density is prepared using PIP techniques (precursor infiltration and pyrolysis method) first, presoma holds The hole of fiber interfascicular is easily immersed, the densification degree of fiber interfascicular is high after ceramic, then use CVI technique (chemical gas Mutually ooze area method) BCx and SiC matrix are alternately prepared, solve composite caused by single PIP methods (precursor infiltration and pyrolysis method) Final densities it is low and brought by volume contraction component internal stress and micro-crack the problems such as, using the process integration in the present invention Prepared ceramic matric composite and component have higher final densities and relatively low porosity, reduce material and component exists The defects such as the internal stress and micro-crack that are produced in preparation process, are also solved individually using CVI techniques (chemical vapor infiltration area method) It is difficult to the problem of composite consistency is not high enough caused by fiberfill fibers interfascicular space when preparing self-healing matrix.
(4) Environmental Barrier Coatings on Si-based Ceramics that the present invention is prepared using brushing method to prepared ceramic matric composite, combustion chamber fire Flame cylinder long-term use temperature 1300~1500 DEG C even more than, the long-term use substantially beyond SiC/SiC composites Temperature, makes the surface stability of SiC/SiC composite combustion chamber flame drums occur drastically to deteriorate, causes the mechanics of composite Performance is decreased obviously, and causes its life-span to substantially reduce, and Environmental Barrier Coatings on Si-based Ceramics is disliked in composite material surface and aero-engine high temperature One of barrier coatings is set up between bad use environment, prevents or reduces influence of the engine environmental to composite wood material list, prepare at present Plasma spraying method being used the technique of Environmental Barrier Coatings on Si-based Ceramics, the present invention can be greatly reduced using slurry brushing method and is prepared into more Sheet and manufacturing cycle.
(5) technical scheme that provides of the present invention, can improve the bending strength of combustion chamber flame drum, heat-resisting ability and anti- Oxidability, reduces the quality of combustion chamber flame drum, and weight loss effect reaches 50% or so, high mechanical properties;And structure design Simply, cooling system is saved, increases efficiency gas, the discharge of NOx and COx the like waste is reduced;Furthermore, combustion chamber of the invention Burner inner liner has self-healing performance by modified BCx+SiC matrixes, when crackle and hole occurs in material, in crackle and hole Place can in-situ authigenic into glass phase, reach the effect of active packing, prevent Oxidant from inwardly spreading, reduction interface and fibre The oxide etch damage of dimension, meets the long-life use requirement of combustion chamber flame drum.The invention provides a kind of high-temperature behavior is steady Fixed, the carbon/silicon carbide ceramic matrix composite combustion chamber flame drum with self-healing matrix of excellent in mechanical performance, is solved existing Flame tube structure design is complicated, and weight is big, and difficulty of processing is big, and heatproof is low and needs air cooling, and fuel gas buring is insufficient, material easily quilt The technical problems such as exhaust gas corrosion.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description Obtain substantially, or recognized by the practice of the present invention.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that retouched The embodiment stated is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, sheet The every other embodiment that field those of ordinary skill is obtained under the premise of creative work is not made, belongs to the present invention The scope of protection.
Experimental method in following embodiments, is conventional method unless otherwise specified.
Test material used, is to be commercially available from conventional reagent shop unless otherwise specified in following embodiments.
Quantitative test in following examples, is respectively provided with three repetition experiments, and data are the average value of three repetition experiments Or mean+SD.
The present invention provides a kind of preparation method of composite combustion chamber flame drum, comprises the following steps:
S1:Combustion chamber flame drum precast body is prepared into SiC interfaces with chemical vapour deposition technique;Wherein, chemical vapor deposition The reaction gas of method is trichloromethyl silane;Combustion chamber flame drum precast body is to use silicon carbide fibre with three-dimensional four step braiding Into, wherein, braid angle is 20~45 °, the volume fraction 30%~50% of silicon carbide fibre;Chemical vapour deposition technique is specially: Using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 1100~1230 DEG C, and pressure is 1 ~5kPa, sedimentation time is 5~15h;Wherein, the volume ratio of hydrogen and trichloromethyl silane is 1:8~1:12.
S2:Using the mixed solution of Polycarbosilane and dimethylbenzene as precursor solution, the product that step S1 is obtained is using first Body infiltration pyrolysis method is driven to be densified;Repeat to use precursor infiltration and pyrolysis method to obtained silicon carbide substrate density for 1.6~1.8g/cm3;Precursor infiltration and pyrolysis method includes:Under vacuum, the obtained products of step S1 are impregnated in poly- carbon 4~6h in the mixed solution of silane and dimethylbenzene, then 100~140 DEG C of dryings;By dried product in nitrogen or argon gas 3~6h is cracked in 800~1200 DEG C;The step of repeating precursor infiltration and pyrolysis method, the density to obtained silicon carbide substrate is 1.6~1.8g/cm3;Wherein, in the mixed solution of Polycarbosilane and dimethylbenzene the mass fraction of Polycarbosilane for 20%~ 50%.
S3:SiC matrix layer and BCx base layers are prepared using chemical vapor infiltration area method on the surface of silicon carbide substrate, obtained Density is 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, SiC matrix is prepared by deposition gas of trichloromethyl silane Layer, BCx base layers are prepared using boron chloride and methane as deposition gas;SiC matrix layer preparation method be specially:With trichloromethyl Silane is deposition gas, and hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 800~1100 DEG C, and sedimentation time is 10~30h, Pressure is 1kPa;Wherein, the flow of hydrogen is 100~400ml/min, and the flow of argon gas is 100~300ml/min;BCx matrixes Layer preparation method be specially:Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, depositing temperature is 900~ 1000 DEG C, sedimentation time is 10~30h, and pressure is 1kPa;Wherein, the flow-rate ratio of boron chloride and methane is 2:1~6:1, hydrogen The flow velocity of gas and argon gas is 50~80mL/min;On the surface of silicon carbide substrate, SiC matrix layer and BCx are alternately prepared successively Base layer, obtains density for 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, the outermost of carbon borosilicate self-healing matrix Side layer is SiC matrix layer.
S4:Carbon borosilicate self-healing matrix is subjected to 1~3h modifications at 1000 DEG C, composite combustion chamber fire is obtained Flame cylinder.
S5:On the surface of composite combustion chamber flame drum, rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared;Rare earth silicate ring The raw material of border barrier coating includes the first component and the second component, and the first component is mullite, ytterbium silicate, polyvinyl butyral and phosphorus Acid esters, the second component is ethanol;Wherein:The mass ratio of first component and the second component is 1:1~1:3, polyvinyl butyral exists Mass fraction in first component is 4%~8%, and mass fraction of the phosphate in the first component is 0.4%~1.0%, not The mass ratio for coming stone and ytterbium silicate is 88:12;The preparation method of rare earth silicate Environmental Barrier Coatings on Si-based Ceramics includes:By the first component and Two component 12~16h of ball milling mixing, by obtained mixture brushing on the surface of composite combustion chamber flame drum, Ran Hou 1400 DEG C~1500 DEG C 2~5h of the lower sintering of argon gas protection.
The preparation method of the composite combustion chamber flame drum provided with reference to specific embodiment the present invention is made into one Walk explanation.
Embodiment one
By silicon carbide fibre three-dimensional four step braiding combustion chamber flame drum precast body, wherein braid angle is 40 °, carborundum The volume fraction of fiber is 35%;Obtained combustion chamber flame drum precast body chemical vapour deposition technique is prepared into SiC interfaces, its In using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, and the volume ratio of hydrogen and trichloromethyl silane is 1:10, depositing temperature is 1130 DEG C, and pressure is 4.5kPa, and sedimentation time is 8h, and the SiC interfacial thicknesses prepared are 6 μm.
Product obtained above is impregnated into 6h with the mixed solution of Polycarbosilane and dimethylbenzene under vacuum, then 120 DEG C of dryings;Dried product is cracked into 4h in nitrogen in 1000 DEG C;Precursor infiltration and pyrolysis 10 cycles of method are repeated, The density of obtained silicon carbide substrate is 1.73g/cm3;Wherein, Polycarbosilane in the mixed solution of Polycarbosilane and dimethylbenzene Mass fraction is 30%.Obtained silicon carbide substrate is alternately prepared into SiC matrix layer and BCx matrixes using chemical vapor infiltration area method Layer, first prepares SiC matrix layer:Using trichloromethyl silane as deposition gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 980 DEG C, sedimentation time is 15h, and pressure is 1kPa;Wherein, the flow of hydrogen is 150ml/min, and the flow of argon gas is 180ml/ min;BCx base layers are prepared again:Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, and depositing temperature is 980 DEG C, sedimentation time is 15h, and pressure is 1kPa;Wherein, the flow-rate ratio of boron chloride and methane is 4:1, the flow velocity of hydrogen and argon gas It is 60mL/min;Above-mentioned method is recycled successively and prepares SiC matrix layer and BCx base layers, obtains density for 2.3g/ cm3Carbon borosilicate self-healing matrix, also, carbon borosilicate self-healing matrix outermost layer for SiC matrix layer.By obtained carbon boron Silicon self-healing matrix carries out 1.5h modifications at 1000 DEG C, obtains composite combustion chamber flame drum.
Rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared in obtained composite combustion chamber flame drum:Rare earth silicate environment hinders The raw material of coating includes the first component and the second component, and the first component is mullite, ytterbium silicate, polyvinyl butyral and phosphoric acid Ester, the second component is ethanol;Wherein:The mass ratio of first component and the second component is 1:3, polyvinyl butyral is in the first component In mass fraction be 4%, mass fraction of the phosphate in the first component is 0.6%, the mass ratio of mullite and ytterbium silicate For 88:12;By the first component and the second component ball milling mixing 15h, by obtained mixture brushing in composite combustion chamber fire The surface of flame cylinder, then sinters 3h under 1450 DEG C of argon gas protections, obtains finished product.
Embodiment two
By silicon carbide fibre three-dimensional four step braiding combustion chamber flame drum precast body, wherein braid angle is 30 °, carborundum The volume fraction of fiber is 35%;Obtained combustion chamber flame drum precast body chemical vapour deposition technique is prepared into SiC interfaces, its In using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, and the volume ratio of hydrogen and trichloromethyl silane is 1:9, depositing temperature is 1150 DEG C, and pressure is 3kPa, and sedimentation time is 6h, and the SiC interfacial thicknesses prepared are 4 μm.
Product obtained above is impregnated into 5h with the mixed solution of Polycarbosilane and dimethylbenzene under vacuum, then 120 DEG C of dryings;Dried product is cracked into 6h in nitrogen in 950 DEG C;Precursor infiltration and pyrolysis 8 cycles of method are repeated, are obtained The density of the silicon carbide substrate arrived is 1.62g/cm3;Wherein, in the mixed solution of Polycarbosilane and dimethylbenzene Polycarbosilane matter It is 35% to measure fraction.Obtained silicon carbide substrate is alternately prepared into SiC matrix layer and BCx matrixes using chemical vapor infiltration area method Layer, first prepares SiC matrix layer:Using trichloromethyl silane as deposition gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 900 DEG C, sedimentation time is 13h, and pressure is 1kPa;Wherein, the flow of hydrogen is 200ml/min, and the flow of argon gas is 300ml/ min;BCx base layers are prepared again:Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, and depositing temperature is 950 DEG C, sedimentation time is 13h, and pressure is 1kPa;Wherein, the flow-rate ratio of boron chloride and methane is 3:1, the flow velocity of hydrogen and argon gas It is 65mL/min;Above-mentioned method is recycled successively and prepares SiC matrix layer and BCx base layers, obtains density for 2.1g/ cm3Carbon borosilicate self-healing matrix, also, carbon borosilicate self-healing matrix outermost layer for SiC matrix layer.By obtained carbon boron Silicon self-healing matrix carries out 2h modifications at 1000 DEG C, obtains composite combustion chamber flame drum.
Rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared in obtained composite combustion chamber flame drum:Rare earth silicate environment hinders The raw material of coating includes the first component and the second component, and the first component is mullite, ytterbium silicate, polyvinyl butyral and phosphoric acid Ester, the second component is ethanol;Wherein:The mass ratio of first component and the second component is 1:2, polyvinyl butyral is in the first component In mass fraction be 5%, mass fraction of the phosphate in the first component is 0.6%, the mass ratio of mullite and ytterbium silicate For 88:12;By the first component and the second component ball milling mixing 12h, by obtained mixture brushing in composite combustion chamber fire The surface of flame cylinder, then argon gas sinters 3h at 1400 DEG C, obtains finished product.
Embodiment three
By silicon carbide fibre three-dimensional four step braiding combustion chamber flame drum precast body, wherein braid angle is 20 °, carborundum The volume fraction of fiber is 30%;Obtained combustion chamber flame drum precast body chemical vapour deposition technique is prepared into SiC interfaces, its In using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, and the volume ratio of hydrogen and trichloromethyl silane is 1:8, depositing temperature is 1100 DEG C, and pressure is 1kPa, and sedimentation time is 10h, and the SiC interfacial thicknesses prepared are 8 μm.
Product obtained above is impregnated into 4h with the mixed solution of Polycarbosilane and dimethylbenzene under vacuum, then 100 DEG C of dryings;Dried product is cracked into 4h in nitrogen in 900 DEG C;The cycle of precursor infiltration and pyrolysis method 8 is repeated, is obtained Silicon carbide substrate density be 1.64g/cm3;Wherein, in the mixed solution of Polycarbosilane and dimethylbenzene Polycarbosilane quality Fraction is 50%.Obtained silicon carbide substrate is alternately prepared into SiC matrix layer and BCx base layers using chemical vapor infiltration area method, First prepare SiC matrix layer:Using trichloromethyl silane as deposition gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 800 DEG C, sedimentation time is 10h, and pressure is 1kPa;Wherein, the flow of hydrogen is 100ml/min, and the flow of argon gas is 100ml/min; BCx base layers are prepared again:Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, and depositing temperature is 980 DEG C, is sunk The product time is 10h, and pressure is 1kPa;Wherein, the flow-rate ratio of boron chloride and methane is 2:1, the flow velocity of hydrogen and argon gas is 50mL/min;Above-mentioned method is recycled successively and prepares SiC matrix layer and BCx base layers, obtains density for 2.05g/cm3's Carbon borosilicate self-healing matrix, also, the outermost layer of carbon borosilicate self-healing matrix is SiC matrix layer.By obtained carbon borosilicate certainly Healing matrices carry out 1h modifications at 1000 DEG C, obtain composite combustion chamber flame drum.
Rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared in obtained composite combustion chamber flame drum:Rare earth silicate environment hinders The raw material of coating includes the first component and the second component, and the first component is mullite, ytterbium silicate, polyvinyl butyral and phosphoric acid Ester, the second component is ethanol;Wherein:The mass ratio of first component and the second component is 1:1, polyvinyl butyral is in the first component In mass fraction be 4%, mass fraction of the phosphate in the first component is 0.4%, the mass ratio of mullite and ytterbium silicate For 88:12;By the first component and the second component ball milling mixing 12h, by obtained mixture brushing in composite combustion chamber fire The surface of flame cylinder, then the Ar-sintering 2h at 1400 DEG C, obtains finished product.
Example IV
By silicon carbide fibre three-dimensional four step braiding combustion chamber flame drum precast body, wherein braid angle is 45 °, carborundum The volume fraction of fiber is 50%;Obtained combustion chamber flame drum precast body chemical vapour deposition technique is prepared into SiC interfaces, its In using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, and the volume ratio of hydrogen and trichloromethyl silane is 1:12, depositing temperature is 1230 DEG C, and pressure is 5kPa, and sedimentation time is 8h, and the SiC interfacial thicknesses prepared are 9 μm.
Product obtained above is impregnated into 6h with the mixed solution of Polycarbosilane and dimethylbenzene under vacuum, then 140 DEG C of dryings;Dried product is cracked into 6h in nitrogen in 1200 DEG C;Precursor infiltration and pyrolysis 12 cycles of method are repeated, The density of obtained silicon carbide substrate is 1.8g/cm3;Wherein, Polycarbosilane in the mixed solution of Polycarbosilane and dimethylbenzene Mass fraction is 50%.Obtained silicon carbide substrate is alternately prepared into SiC matrix layer and BCx matrixes using chemical vapor infiltration area method Layer, first prepares SiC matrix layer:Using trichloromethyl silane as deposition gas, hydrogen is carrier gas, and argon gas is carrier gas, and depositing temperature is 1100 DEG C, sedimentation time is 30h, and pressure is 1kPa;Wherein, the flow of hydrogen is 400ml/min, and the flow of argon gas is 200ml/ min;BCx base layers are prepared again:Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, and depositing temperature is 1000 DEG C, sedimentation time is 30h, and pressure is 1kPa;Wherein, the flow-rate ratio of boron chloride and methane is 6:1, the flow velocity of hydrogen and argon gas It is 80mL/min;Above-mentioned method is recycled successively and prepares SiC matrix layer and BCx base layers, obtains density for 2.5g/ cm3Carbon borosilicate self-healing matrix, also, carbon borosilicate self-healing matrix outermost layer for SiC matrix layer.By obtained carbon boron Silicon self-healing matrix carries out 3h modifications at 1000 DEG C, obtains composite combustion chamber flame drum.
Rare earth silicate Environmental Barrier Coatings on Si-based Ceramics is prepared in obtained composite combustion chamber flame drum:Rare earth silicate environment hinders The raw material of coating includes the first component and the second component, and the first component is mullite, ytterbium silicate, polyvinyl butyral and phosphoric acid Ester, the second component is ethanol;Wherein:The mass ratio of first component and the second component is 1:3, polyvinyl butyral is in the first component In mass fraction be 8%, mass fraction of the phosphate in the first component is 1.0%, the mass ratio of mullite and ytterbium silicate For 88:12;By the first component and the second component ball milling mixing 16h, by obtained mixture brushing in composite combustion chamber fire The surface of flame cylinder, then the Ar-sintering 5h at 1500 DEG C, obtains finished product.
The composite combustion chamber flame drum that the embodiment of the present invention one to example IV is prepared carries out performance measurement, And using TiAl high temperature alloys combustion chamber flame drum of the prior art as comparative example, concrete outcome is as shown in table 1 below:
The performance of the composite combustion chamber flame drum of table 1
It should be noted that situation about enumerating except above-described embodiment one to example IV, from other preparation methods Parameter is also feasible.
The self-healing ceramic matric composite aero-engine for the offer that the preparation method provided by the present invention is obtained is fired Room burner inner liner is burnt, is had the following advantages:(1) present invention prepares precast body using three dimensional knitting method, not only precast body is existed It is complete continuous between in many axial planes in space and face, fundamentally avoid two-dimension laminate precast body intensity and modulus in a thickness direction Difference, the shortcoming that interlaminar shear strength is low and damage tolerance is relatively low, and 3 D weaving precast body comprehensive mechanical property is good, thermal shock Excellent performance.(2) silicon carbide interface that the present invention is used has more preferable inoxidizability compared with carbon interface, is pyrolyzed carbon boundary layer Easily aoxidized more than 400 DEG C, composite can be because intensity occurs in the rapid oxidation at carbon interface under high-temperature oxidation environment Dramatic decrease, and silicon carbide interface with applied at elevated temperature environment oxidation resistance it is strong, it is not oxidizable, play interface transmission and carry The effect of lotus, makes material have more preferable mechanical property in hot environment.(3) present invention is (first using PIP+CVI United Technologies Drive body infiltration pyrolysis method+chemical vapor infiltration area method) self-healing modification matrix is prepared, using PIP techniques, (precursor dipping splits first Solution) silicon carbide substrate of certain density is prepared, presoma easily immerses the hole of fiber interfascicular, the fiber interfascicular after ceramic Densification degree it is high, BCx and SiC matrix are alternately then prepared using CVI techniques (chemical vapor infiltration area method), solved single Composite final densities are low caused by PIP methods (precursor infiltration and pyrolysis method) and the component internal stress brought by volume contraction And the problems such as micro-crack, had using the ceramic matric composite and component prepared by the process integration in the present invention higher most Whole density and relatively low porosity, reduce the defects such as internal stress and micro-crack that material and component produce in preparation process, Solve and be difficult to fiberfill fibers interfascicular space when individually preparing self-healing matrix using CVI techniques (chemical vapor infiltration area method) and lead The problem of composite consistency of cause is not high enough.(4) present invention uses brushing method to prepared ceramic matric composite system Standby Environmental Barrier Coatings on Si-based Ceramics, the long-term use temperature of combustion chamber flame drum 1300~1500 DEG C even more than, substantially beyond The long-term use temperature of SiC/SiC composites, makes the surface stability of SiC/SiC composite combustion chamber flame drums occur suddenly Play deteriorates, and causes the mechanical property of composite to be decreased obviously, causes its life-span to substantially reduce, and Environmental Barrier Coatings on Si-based Ceramics is in composite wood Barrier coatings together are set up between material surface and aero-engine high temperature hostile use environment, prevents or reduces engine environmental to multiple The influence of condensation material list, plasma spraying method is used the technique that Environmental Barrier Coatings on Si-based Ceramics is prepared at present more, and the present invention is applied using slurry Brush method can greatly reduce preparation cost and manufacturing cycle.
Using the technical scheme that provides of the present invention, can improve the bending strength of combustion chamber flame drum, heat-resisting ability and Oxidation resistance, reduces the quality of combustion chamber flame drum, and weight loss effect reaches 50% or so, high mechanical properties;And structure is set Meter is simple, saves cooling system, increases efficiency gas, reduces the discharge of NOx and COx the like waste;Furthermore, burning of the invention Room burner inner liner has self-healing performance by modified BCx+SiC matrixes, when crackle and hole occurs in material, in crackle and hole At hole can in-situ authigenic into glass phase, reach the effect of active packing, prevent Oxidant from inwardly spreading, reduction interface and The oxide etch damage of fiber, meets the long-life use requirement of combustion chamber flame drum.The invention provides a kind of high-temperature behavior Stable, the carbon/silicon carbide ceramic matrix composite combustion chamber flame drum with self-healing matrix of excellent in mechanical performance, is solved existing There is flame tube structure design complicated, greatly, difficulty of processing is big, and heatproof is low and needs air cooling, and fuel gas buring is insufficient, and material is easy for weight By technical problems such as exhaust gas corrosions.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changed, replacing and modification, and the essence of appropriate technical solution is departed from various embodiments of the present invention skill The scope of art scheme, it all should cover among the claim of the present invention and the scope of specification.

Claims (10)

1. a kind of preparation method of composite combustion chamber flame drum, it is characterised in that comprise the following steps:
S1:Combustion chamber flame drum precast body is prepared into SiC interfaces with chemical vapour deposition technique;Wherein, the chemical vapor deposition The reaction gas of method is trichloromethyl silane;
S2:Using the mixed solution of Polycarbosilane and dimethylbenzene as precursor solution, the product that the step S1 is obtained is using first Body infiltration pyrolysis method is driven to be densified;Repeat the density to obtained silicon carbide substrate using the precursor infiltration and pyrolysis method For 1.6~1.8g/cm3
S3:SiC matrix layer and BCx base layers are prepared using chemical vapor infiltration area method on the surface of the silicon carbide substrate, obtained Density is 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, the SiC is prepared by deposition gas of trichloromethyl silane Base layer, the BCx base layers are prepared using boron chloride and methane as deposition gas;
S4:The carbon borosilicate self-healing matrix is subjected to 1~3h modifications at 1000 DEG C, composite combustion chamber fire is obtained Flame cylinder.
2. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:The step S1 In, the chemical vapour deposition technique is specially:Using trichloromethyl silane as reaction gas, hydrogen is carrier gas, and argon gas is carrier gas, is sunk Accumulated temperature degree is 1100~1230 DEG C, and pressure is 1~5kPa, and sedimentation time is 5~15h;Wherein, the hydrogen and three chloromethane The volume ratio of base silane is 1:8~1:12.
3. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:The step S2 In, the precursor infiltration and pyrolysis method includes:Under vacuum, the obtained products of the step S1 are impregnated in Polycarbosilane With 4~6h in the mixed solution of dimethylbenzene, then 100~140 DEG C of dryings;By the dried product in nitrogen or argon gas 3~6h is cracked in 800~1200 DEG C;The step of repeating the precursor infiltration and pyrolysis method, it is close to obtained silicon carbide substrate Spend for 1.6~1.8g/cm3;Wherein, the mass fraction of Polycarbosilane is in the mixed solution of the Polycarbosilane and dimethylbenzene 20%~50%.
4. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:The step S3 In, the preparation method of the SiC matrix layer is specially:Using trichloromethyl silane as deposition gas, hydrogen is carrier gas, and argon gas is dilution Gas, depositing temperature is 800~1100 DEG C, and sedimentation time is 10~30h, and pressure is 1kPa;Wherein, the flow of the hydrogen is 100~400ml/min, the flow of the argon gas is 100~300ml/min;The preparation method of the BCx base layers is specially: Using boron chloride and methane as deposition gas, hydrogen and argon gas are carrier gas, and depositing temperature is 900~1000 DEG C, and sedimentation time is 10 ~30h, pressure is 1kPa;Wherein, the flow-rate ratio of the boron chloride and the methane is 2:1~6:1, the hydrogen and described The flow velocity of argon gas is 50~80mL/min.
5. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:The step S3 In, on the surface of the silicon carbide substrate, the SiC matrix layer and the BCx base layers are alternately prepared successively, obtaining density is 2.0~2.5g/cm3Carbon borosilicate self-healing matrix;Wherein, the outermost layer of the carbon borosilicate self-healing matrix is the SiC Base layer.
6. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:Described compound The surface of material combustion room burner inner liner, prepares rare earth silicate Environmental Barrier Coatings on Si-based Ceramics;The original of the rare earth silicate Environmental Barrier Coatings on Si-based Ceramics Material includes the first component and the second component, and first component is mullite, ytterbium silicate, polyvinyl butyral and phosphate, institute The second component is stated for ethanol;Wherein:The mass ratio of first component and second component is 1:1~1:3, the polyethylene Mass fraction of the butyral in first component is 4%~8%, the phosphate quality in first component point Number is 0.4%~1.0%, and the mass ratio of the mullite and the ytterbium silicate is 88:12.
7. the preparation method of composite combustion chamber flame drum according to claim 6, it is characterised in that:The rare earth silicon The preparation method of hydrochlorate Environmental Barrier Coatings on Si-based Ceramics includes:By first component and the second component 12~16h of ball milling mixing, will The mixture brushing arrived on the surface of the composite combustion chamber flame drum, then at 1400 DEG C~1500 DEG C sintering 2~ 5h。
8. the preparation method of composite combustion chamber flame drum according to claim 1, it is characterised in that:The combustion chamber Burner inner liner precast body is to use silicon carbide fibre to be formed with three-dimensional four step braiding, wherein, braid angle is 20~45 °, the carbon The volume fraction 30%~50% of SiClx fiber.
9. the composite combustion chamber flame drum that the method described in any one of claim 1~8 is prepared.
10. composite combustion chamber flame drum described in claim 9 is being prepared during engine especially prepares aero-engine Application.
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