CN115124349A - Ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion and preparation method and application thereof - Google Patents

Ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion and preparation method and application thereof Download PDF

Info

Publication number
CN115124349A
CN115124349A CN202210631409.8A CN202210631409A CN115124349A CN 115124349 A CN115124349 A CN 115124349A CN 202210631409 A CN202210631409 A CN 202210631409A CN 115124349 A CN115124349 A CN 115124349A
Authority
CN
China
Prior art keywords
temperature
ceramic material
ultrahigh
hot
pressing sintering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210631409.8A
Other languages
Chinese (zh)
Other versions
CN115124349B (en
Inventor
赵长浩
肖学仁
张军
王国林
杨玲伟
刘丽萍
马昊军
罗杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ultra High Speed Aerodynamics Institute China Aerodynamics Research and Development Center
Original Assignee
Ultra High Speed Aerodynamics Institute China Aerodynamics Research and Development Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ultra High Speed Aerodynamics Institute China Aerodynamics Research and Development Center filed Critical Ultra High Speed Aerodynamics Institute China Aerodynamics Research and Development Center
Priority to CN202210631409.8A priority Critical patent/CN115124349B/en
Publication of CN115124349A publication Critical patent/CN115124349A/en
Application granted granted Critical
Publication of CN115124349B publication Critical patent/CN115124349B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
    • 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
    • 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
    • C04B35/645—Pressure sintering
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/11—Thermal or acoustic insulation
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3804—Borides
    • C04B2235/3813—Refractory metal borides
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • 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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

The invention relates to a high-temperature steam corrosion resistant ultrahigh-temperature ceramic material and a preparation method and application thereof. The high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is prepared from 70-81% of ZrB in percentage by volume 2 4-6% of TiB 2 And 15-25% of SiC. The preparation method comprises the following steps: reacting ZrB 2 、TiB 2 Uniformly mixing with SiC by ball milling to obtain a mixture; carrying out hot-pressing sintering on the mixture, and then cooling to prepare the ultrahigh-temperature ceramic material; the hot-pressing sintering temperature is 1800-2000 ℃, the hot-pressing sintering pressure is 25-35 MPa, and the hot-pressing sintering time is 0.5-2 h. The invention adds nucleation component in superhigh temperature ceramic materialTiB 2 Modifying the material to form TiSiO in the high-temperature oxidation process 4 Oxide layer, SiO of improved material 2 The oxide layer is easy to react with water vapor, thereby the problem of ablation damage is solved.

Description

High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ultra-high temperature ceramic materials, and particularly relates to an ultra-high temperature ceramic material resistant to high-temperature water vapor corrosion, and a preparation method and application thereof.
Background
The engine is the core component of various aviation and aerospace aircrafts, and the thrust-weight ratio, fuel economy and reliability of the engine are decisive factors of the performance of the aircrafts. With the continuous development of aircraft technology, the requirement on the thrust-weight ratio of an engine is continuously improved, and the main way for improving the thrust-weight ratio is to adopt fuel with higher heat value to improve the temperature of a combustion chamber of the engine. The thrust-weight ratio of the engine is 15-20, and the temperature of a combustion chamber needs to reach 2000-2200 ℃. The ever increasing temperatures place higher demands on the materials of the engine combustion chamber and require a certain protection against the water vapour produced by the combustion of high calorific value fuels. The materials which can be used for the engine combustion chamber at present mainly comprise nickel-based high-temperature alloy, C/SiC composite material, ultrahigh-temperature ceramic material and the like.
In an aircraft engine combustion chamber, the nickel-based superalloy is the most commonly used high-temperature resistant material at present, the temperature resistance limit of the common forged nickel-based superalloy is usually lower than 1000 ℃, the temperature resistance limit of the nickel-based superalloy can be improved to 1100 ℃ by a directional solidification alloy technology or a single crystal alloy technology, and the nickel-based superalloy is insensitive to water vapor. The temperature resistance can be reduced to 1200 ℃ by further introducing an advanced ceramic thermal barrier coating, and the working temperature of the high-temperature alloy can be further increased by nearly 400 ℃ to 1600 ℃ by means of designing an advanced air film cooling channel in the engine blade, so that the thrust-weight ratio and the combustion efficiency of the gas turbine are greatly improved. Although the nickel-based high-temperature alloy is widely applied to aeroengines and gas turbines, particularly single crystal blades have stable performance and can meet the requirement of long-time running of the engines, the following two defects exist in future-oriented engine combustion chamber application, and further application of the nickel-based high-temperature alloy is limited: a. the temperature resistance limit of the material is low, the temperature resistance limit of the single crystal nickel-based high-temperature alloy blade is about 1100 ℃, the alloy material cannot be applied to higher temperature due to the limitation of the characteristics of the alloy material, and compared with a casting material and a directional crystal material, a single crystal is the temperature resistance limit of the material; b. because the temperature resistance limit of the material is low, the improvement of the temperature resistance limit of the material depends on a cooling air film, however, the burden of an engine can be further increased while the temperature of the blade is reduced by an air film cooling system, the structure of the blade is more and more complex due to the increase of various air holes, and the forming process of the blade is more difficult.
The C/SiC composite material has excellent performances of high temperature resistance, high strength, oxidation resistance, ablation resistance and the like, and compared with a high-temperature alloy, the density of the C/SiC composite material is 1/5 below the density of the high-temperature alloy. The C/SiC composite material can generate compact SiO on the surface in a high-temperature oxidation environment 2 The protective layer has oxidation resistance, ablation resistance and the like superior to those of C/C composite materials, has a wider application temperature range, can be used for a long time below 1650 ℃, and is mainly used for thermal protection systems of aircraft engines, rocket engines and aerospace aircrafts. The gas turbine engine combustors manufactured in the united states, french phantom 2000 fighters and high-speed fighters, use M55 engines and M88 aircraft engine nozzles, all of which are C/SiC composite materials. The C/SiC composite material is adopted by an exhaust cone and a rocket nozzle of a rocket for launching the European Ariane satellite, a novel liquid rocket engine developed by the NASA LisSisi research center and the like. The C/SiC composite material has higher temperature resistance limit than that of the nickel-based alloy, and has more applications in the aspects of aircraft engines, solid fuel engines, conventional liquid engines and the like, but the C/SiC composite material mainly has the following two defects in the application of future high thrust-weight ratio engines: a. weak resistance to water vapor corrosionA great deal of research shows that the oxidation rate of the C/SiC composite material can be improved by more than one order of magnitude under the water-oxygen high-temperature environment of mixing water vapor and oxygen, and the surface of the C/SiC composite material is dense SiO when the temperature is increased to more than 1400 DEG C 2 The layer becomes porous due to water corrosion, loses the protective capability on the matrix and leads to further acceleration of oxidation; b. the temperature resistance limit is low, even in an anhydrous dry oxidation environment, the temperature resistance limit of the C/SiC composite material is only 1650 ℃, and the requirement of the working temperature of the future high thrust-weight ratio engine above 2000 ℃ cannot be met.
Ultra-high temperature ceramic materials (UHTC) broadly refer to borides, carbides and nitrides of the transition metals zirconium, hafnium, tantalum having melting points in excess of 3000 ℃. In all ultra-high temperature ceramics, ZrB 2 Has lower density, higher thermal conductivity and better oxidation resistance, wherein ZrB 2 the-SiC superhigh temperature ceramic material has more excellent comprehensive performance, can keep stable for a long time in an oxidation environment of 2000 ℃, and is considered as an ideal candidate material for a scramjet engine combustion chamber and a high thrust-weight ratio rocket engine. In an oxidizing environment, the material is oxidized to form B 2 O 3 、SiO 2 、ZrO 2 The oxides play a vital role in the oxidation resistance process, and borosilicate glass formed on the surface has good surface self-healing property within the range of 1300-1600 ℃, so that the diffusion of an oxidation medium to the interior of the composite material is effectively blocked, and the long-time protection is provided for the material. Within the range of 1600 plus 2200 ℃, the protective layer of the silicon oxide and zirconium silicate glass formed on the surface can effectively resist the corrosion of high-temperature oxidation medium, thereby improving the oxidation protection capability and the ablation resistance of the ultrahigh-temperature ceramic material. The ultrahigh-temperature ceramic material can keep stable for a long time at 2200 ℃ or higher in a high-temperature dry oxidation environment, and has good ablation resistance and oxidation resistance. However, under the wet oxidation condition of water vapor, due to key antioxidant component B in the material 2 O 3 、SiO 2 Is sensitive to water vapor and can easily react with the water vapor to form volatile products (HBO) 2 、Si(OH) 4 ) The oxidation rate of the material is greatly accelerated, and the rapid ablation is easy to occur. In addition, theIn future high thrust-weight ratio liquid fuel engines, the combustion temperature is high and the water vapor content is high, so that the rapid ablation of the ultra-high temperature ceramic heat-proof material can be caused.
Therefore, the three typical engine thermal protection materials, namely the nickel-based high-temperature alloy and the C/SiC composite material, are difficult to be applied to the future high thrust-weight ratio engine environment due to the limitation of the temperature resistance limit of the materials; the temperature resistance limit of the ultra-high temperature ceramic material can meet the requirement of the high thrust-weight ratio engine, but the ultra-high temperature ceramic material has poor water vapor protection capability in a gas environment, and if the water vapor protection capability of the ultra-high temperature ceramic material can be improved, the ultra-high temperature ceramic material is expected to become a future heat protection material for the high thrust-weight ratio engine.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a high-temperature steam corrosion resistant ultrahigh-temperature ceramic material and a preparation method and application thereof. The invention effectively improves the protection capability of the ultrahigh-temperature ceramic material to water vapor in a high-temperature oxidation environment, and can be used as a thermal protection material for a combustion environment of a high thrust-weight ratio engine in the future.
The invention provides a high-temperature steam corrosion resistant ultrahigh-temperature ceramic material in a first aspect, wherein the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by 70-81% of ZrB in percentage by volume 2 4-6% of TiB 2 And 15-25% of SiC.
Preferably, the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion is prepared by a hot-pressing sintering process; in the hot-pressing sintering process, the temperature of the hot-pressing sintering is 1800-2000 ℃, preferably 1900 ℃, the pressure of the hot-pressing sintering is 25-35 MPa, preferably 30MPa, and the time of the hot-pressing sintering is 0.5-2 h, preferably 1 h; preferably, the heating rate of the temperature raised to the hot-pressing sintering temperature is 5-15 ℃/min; more preferably, in the hot-pressing sintering process, after the hot-pressing sintering is performed, the cooling procedure adopted is as follows: and reducing the temperature of the hot-pressing sintering to 1300 ℃ at a cooling rate of 5-15 ℃/min, and then cooling to room temperature along with the furnace.
Preferably, the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is oxidized by a high-temperature steam-containing steam flow fieldAfter chemical reaction, TiSiO is formed 4 And oxidizing the layer, thereby improving the high-temperature water vapor corrosion resistance of the ultrahigh-temperature ceramic material.
Preferably, the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material consists of 76 percent of ZrB in percentage by volume 2 5% of TiB 2 And 19% SiC.
Preferably, the high-temperature water vapor corrosion resistant ultrahigh-temperature ceramic material is formed by compounding a first ultrahigh-temperature ceramic material and a second ultrahigh-temperature ceramic material.
Preferably, the first ultrahigh-temperature ceramic material consists of 73.5 percent by volume of ZrB 2 5.5% of TiB 2 And 21% SiC; the second ultrahigh-temperature ceramic material consists of 76 percent of ZrB by volume percentage 2 5% of TiB 2 And 19% SiC.
In a second aspect, the present invention provides a method for preparing the superhigh temperature ceramic material which is resistant to high temperature steam corrosion, which comprises the following steps:
(1) reacting ZrB 2 Powder, TiB 2 Uniformly mixing the powder and the SiC powder by ball milling to obtain a mixture;
(2) carrying out hot-pressing sintering on the mixture, and then cooling to prepare the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material;
the hot-pressing sintering temperature is 1800-2000 ℃, the hot-pressing sintering pressure is 25-35 MPa, and the hot-pressing sintering time is 0.5-2 h.
Preferably, the heating rate of the temperature raised to the hot-pressing sintering temperature is 5-15 ℃/min; and/or the cooling is: and reducing the temperature of the hot-pressing sintering to 1300 ℃ at a cooling rate of 5-15 ℃/min, and then cooling to room temperature along with the furnace.
Preferably, when the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion is compounded by a first ultrahigh-temperature ceramic material and a second ultrahigh-temperature ceramic material, in the step (1), a first mixed material and a second mixed material corresponding to the components of the first ultrahigh-temperature ceramic material and the second ultrahigh-temperature ceramic material are respectively obtained; in the step (2), the first mixture is prepared into slurry and then is subjected to tape casting to obtain a first epitaxial layer, then the slurry prepared from the second mixture is adopted to carry out tape casting on the basis of the first epitaxial layer to obtain a second epitaxial layer on the basis of the first epitaxial layer, and then hot-pressing sintering and cooling are carried out to obtain the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion.
In a third aspect, the invention provides an application of the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion in the first aspect or the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion in the second aspect as a heat protection material for an engine with a high thrust-weight ratio.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention adds nucleation component TiB with proper volume content into the ultra-high temperature ceramic material 2 Modifying the material to form TiSiO in the high-temperature oxidation process 4 Oxide layer, compared to SiO 2 The oxide layer is easy to be corroded by high-temperature water vapor, and the formed TiSiO is discovered by the invention 4 The layer is difficult to react with the water vapor, and has better stability in the high-temperature gas environment, thereby improving the protective property of the material in the high-temperature gas environment and effectively improving the protective capability of an oxide layer in the ultra-high-temperature ceramic material to the high-temperature water vapor.
(2) The high-temperature water-containing steam flow field verification shows that: by TiB 2 Doping modification to ensure ZrB 2 -TiB 2 the-SiC material can keep 600s stable at 2300 ℃, and the microscopic morphology analysis further discovers that a compact oxide layer is formed on the surface of the material and effectively slows down ablation, the oxide layer is composed of four elements of Zr-Ti-Si-O, visible doping element Ti enters the oxide layer, and the oxide layer plays a certain role in high-temperature stability of the oxide layer; and undoped ZrB 2 SiC material which is destroyed after 489s ablation, the surface oxidation layer is porous and consists of Zr-Si-O, and the oxidation atmosphere can pass through the holes to the materialThe ablation of the matrix occurs, so that the material is damaged; it can be seen that ZrB in the present invention 2 -TiB 2 the-SiC material has better high-temperature water vapor protection capability and is expected to become a thermal protection material of a next-generation high thrust-weight ratio engine.
Drawings
FIG. 1 shows ZrB of example 1 of the present invention 2 -TiB 2 -SiC Material and ZrB of comparative example 1 2 -ablation temperature response map of SiC material.
FIG. 2 shows ZrB in example 1 of the present invention 2 -TiB 2 -SiC Material with ZrB in comparative example 1 2 -a micro-topography of the oxide layer of the SiC material after ablation.
FIG. 3 is the corresponding ZrB of FIG. 2 2 -TiB 2 -surface element distribution of the oxide layer of SiC material.
FIG. 4 shows ZrB in example 1 of the present invention 2 -TiB 2 -ternary phase diagram of oxide layer of SiC material after 600s ablation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides in a first aspect a high temperature steam corrosion resistant ultra high temperature ceramic material (also denoted as ZrB) 2 -TiB 2 -SiC material or ZrB 2 -TiB 2 -SiC ultra high temperature ceramic material) is formed from 70 to 81% (e.g. 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, 80.5% or 81%) ZrB by volume 2 4-6% (e.g. 4%, 4.5%, 5%, 5.5% or6%) of TiB 2 And 15-25% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25%) SiC.
Compared with the prior art with TiB 2 The invention is firstly realized by adopting ZrB as the base material (main component) and is different from the titanium boride-zirconium boride-silicon carbide self-lubricating composite ceramic material (see CN103387392A) 2 The method is characterized in that a nucleation component TiB with the volume percentage content of only 4-6% is added into the ultrahigh-temperature ceramic material serving as the main phase 2 Modifying the material to form TiSiO in a high-temperature oxidation process (such as a high-temperature oxidation process at about 2300℃) 4 Oxide layer, SiO of improved material 2 The oxide layer is easy to react with water vapor, so that the problem of ablation damage is solved, and the protective performance of the material in a high-temperature gas environment can be improved. The invention discovers that TiB 2 The ablation characteristic of the material is not directly changed by doping, a new method is adopted, and the water vapor protection capability of the material is improved by improving the stability of an oxide layer of the material; and the invention discovers that in the ultrahigh-temperature ceramic material resisting high-temperature steam corrosion, TiB 2 Is particularly important only if the TiB is present 2 The volume percentage of (A) is 4-6%, the high temperature steam corrosion resistant ultra-high temperature ceramic material can be ensured to have excellent high temperature steam corrosion resistance, and if the TiB is used, the TiB 2 Too small a volume percentage of (a) would not have a significant effect of improving the water vapor barrier capability of the material, whereas if the TiB is used as the binder, the effect of improving the water vapor barrier capability of the material would not be significant 2 If the volume percentage of (b) is too large, the high-temperature ablation resistance of the main body material can be affected, and the improvement of the high-temperature water vapor corrosion resistance can be affected.
According to some preferred embodiments, the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion is prepared by a hot-pressing sintering process;
in the hot-pressing sintering process, the temperature of the hot-pressing sintering is 1800-2000 ℃ (such as 1800 ℃, 1850 ℃, 1900 ℃, 1950 ℃ or 2000 ℃), and the pressure of the hot-pressing sintering is 25-35 MPa (such as 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35M)Pa) is preferably 30MPa, and the time for hot-pressing sintering is 0.5-2 h (such as 0.5, 1, 1.5 or 2h), preferably 1 h; in the invention, the temperature of the hot-pressing sintering is preferably 1800-2000 ℃, and the pressure of the hot-pressing sintering is 25-35 MPa, so that the obtained more compact ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion is ensured, and TiSiO formed after ablation (high-temperature oxidation) is enabled to be 4 The oxide layer is more compact, TiSiO 4 The oxide layer has better protection, thereby having stronger high-temperature water vapor protection capability on the material and being beneficial to the improvement of the high-temperature water vapor corrosion resistance of the material; the invention discovers that if the temperature and the pressure of the hot-pressing sintering are too low, the obtained high-temperature water vapor corrosion resistant ultrahigh-temperature ceramic material becomes loose, which is not beneficial to improving the high-temperature water vapor corrosion resistant performance of the material; if the temperature and the pressure are too high, the mechanical property of the material is deteriorated, the strength is reduced, and the high-temperature steam corrosion resistance of the material is influenced to a certain extent.
According to some preferred embodiments, the ramp rate up to the temperature of the hot press sintering is from 5 to 15 ℃/min (e.g., 5, 8, 10, 12, or 15 ℃/min); more preferably, in the hot-pressing sintering process, after the hot-pressing sintering is performed, the cooling procedure adopted is as follows: reducing the temperature of the hot-pressing sintering to 1300 ℃ at a cooling rate of 5-15 ℃/min (for example, 5, 8, 10, 12 or 15 ℃/min), and then cooling to room temperature along with the furnace; the invention preferably carries out the cooling under the cooling program, and the invention finds that compared with a mode of directly adopting furnace cooling, the ultrahigh-temperature ceramic material resisting high-temperature water vapor corrosion can be more compact, and the TiSiO formed after ablation (high-temperature oxidation) of the obtained ultrahigh-temperature ceramic material resisting high-temperature water vapor corrosion is more favorable for 4 The oxide layer is more compact, thereby being beneficial to improving the high-temperature steam corrosion resistance of the material.
According to some preferred embodiments, ZrB is contained in the high temperature steam corrosion resistant ultra high temperature ceramic material 2 The volume ratio of the SiC to the SiC is (3-4.5): 1 (e.g., 3:1, 3.5:1, 4:1, or 4.5:1), more preferably ZrB 2 The volume ratio to SiC was 4:1,thus being more beneficial to the improvement of the high-temperature water vapor corrosion resistance of the material.
According to some preferred embodiments, the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion forms TiSiO after field oxidation of high-temperature water-containing vapor flow 4 And oxidizing the layer, thereby improving the high-temperature water vapor corrosion resistance of the ultrahigh-temperature ceramic material.
According to some preferred embodiments, the superhigh temperature ceramic material resisting high temperature steam corrosion consists of 76% ZrB by volume percentage 2 5% of TiB 2 And 19% SiC.
According to some preferred embodiments, the high temperature water vapor corrosion resistant ultra high temperature ceramic material is compounded from a first ultra high temperature ceramic material and a second ultra high temperature ceramic material; preferably, in the first ultra high temperature ceramic material, ZrB 2 The volume ratio of the SiC to the SiC is 3.5: 1; in the second ultra-high temperature ceramic material, ZrB 2 The volume ratio to SiC was 4: 1.
According to some preferred embodiments, said first ultrahigh-temperature ceramic material consists of 73.5% by volume of ZrB 2 5.5% of TiB 2 And 21% SiC; the second ultrahigh-temperature ceramic material consists of 76 percent of ZrB by volume percentage 2 5% of TiB 2 And 19% SiC; the thicknesses of the first and second ultra-high temperature ceramic materials are not particularly limited, and may be adjusted according to the required thicknesses of the materials, and it is preferable that the thickness ratio of the first and second ultra-high temperature ceramic materials is, for example, 1: (0.5 to 2); the invention discovers that when the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by compounding the first ultrahigh-temperature ceramic material and the second ultrahigh-temperature ceramic material, the high-temperature steam corrosion resistance of the ultrahigh-temperature ceramic material can be effectively ensured.
In a second aspect, the present invention provides a method for preparing the superhigh temperature ceramic material resisting high temperature steam corrosion, which includes the following steps:
(1) reacting ZrB 2 Powder, TiB 2 Uniformly mixing the powder and the SiC powder by ball milling to obtain a mixture; in the present invention, ZrB is subjected to, for example, a wet ball milling process 2 Powder, TiB 2 Ball-milling the powder and the SiC powder for 6-10 hours to obtain a uniformly mixed mixture; invention pair ZrB 2 Powder, TiB 2 The particle size of the powder and the SiC powder is not particularly limited, and the conventional particle size can be adopted, and for example, the particle size can be 1-3 micrometers; the wet ball milling process conditions are not particularly limited, and the ball milling can be carried out by adopting the conventional conditions, for example, the ball milling can be carried out by taking absolute ethyl alcohol as a medium, carrying out ball milling, then carrying out rotary drying at 50-60 ℃ for 30min, and then sieving to obtain uniformly mixed powder, namely the mixture;
(2) carrying out hot-pressing sintering on the mixture, and then cooling to prepare the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion; wherein the temperature of the hot-pressing sintering is 1800-2000 ℃ (such as 1800 ℃, 1850 ℃, 1900 ℃, 1950 ℃ or 2000 ℃) and is preferably 1900 ℃, the pressure of the hot-pressing sintering is 25-35 MPa (such as 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35MPa) and is preferably 30MPa, and the time of the hot-pressing sintering is 0.5-2 h (such as 0.5, 1, 1.5 or 2h) and is preferably 1 h; in the present invention, the hot press sintering is performed in an argon atmosphere.
According to some preferred embodiments, the rate of temperature increase to the temperature of the hot press sintering is 5 to 15 ℃/min (e.g., 5, 8, 10, 12, or 15 ℃/min); and/or the cooling is: the temperature of the hot-pressing sintering is reduced to 1300 ℃ at the cooling rate of 5-15 ℃/min (for example, 5, 8, 10, 12 or 15 ℃/min), and then the temperature is cooled to room temperature along with the furnace.
According to some specific embodiments, the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion prepared by the hot-pressing sintering method comprises: firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder in proportion, and ball-milling for 8 hours to obtain uniformly mixed powder; sintering the mixed powder by adopting a hot pressing process, wherein the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation is carried out for 1 hour, and the heating rate is 10 ℃/minThe temperature reduction rate of 1900 ℃ -1300 ℃ is 10 ℃/min, the ceramic material is cooled along with the furnace below 1300 ℃, and finally the compact ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion is obtained.
According to some preferred embodiments, when the high temperature steam corrosion resistant ultra high temperature ceramic material is compounded of a first ultra high temperature ceramic material and a second ultra high temperature ceramic material, in step (1), a first mixture material and a second mixture material are obtained, corresponding to the components of the first ultra high temperature ceramic material and the second ultra high temperature ceramic material, respectively; in the step (2), the first mixture is prepared into slurry and then is subjected to tape casting to obtain a first epitaxial layer, then the slurry prepared from the second mixture is adopted to carry out tape casting on the basis of the first epitaxial layer to obtain a second epitaxial layer on the basis of the first epitaxial layer, and then hot-pressing sintering is carried out, and finally the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion is prepared through cooling; the invention has no special limit on the technical conditions for carrying out the casting, and the casting is carried out by adopting the conventional parameters, so that the slurry of the first mixture and the slurry of the second mixture can be cast into sheets.
In a third aspect, the invention provides an application of the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion in the first aspect or the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion in the second aspect as a heat protection material for an engine with a high thrust-weight ratio.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples. The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
An ultrahigh-temp ceramic material able to resist high-temp steam corrosion is prepared from the components in percentage by volumeCalculated as 76% ZrB 2 5% of TiB 2 And 19% SiC.
The preparation method of the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 76:5:19, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the temperature rise rate is 10 ℃/min when the temperature rises to 1900 ℃, the temperature drop rate is 10 ℃/min when the temperature is 1900-1300 ℃, the temperature is cooled to room temperature when the temperature is below 1300 ℃ along with the furnace, and finally the compact ultrahigh-temperature ceramic material (ZrB) resisting high-temperature steam corrosion is obtained 2 -TiB 2 -SiC material).
The high-temperature water vapor-containing flow field generated by the high-frequency plasma wind tunnel simulates the high-temperature water vapor-containing oxidation flow field environment of the material, and the high-temperature water vapor protective performance of the ultrahigh-temperature ceramic material in the embodiment is examined as follows:
mixing high-temperature water vapor with a high-enthalpy plasma flow field (high-enthalpy air plasma flow field) on a high-frequency plasma wind tunnel to obtain a high-temperature water vapor-containing flow field, simulating the high-temperature water vapor-containing flow field (the high-temperature water vapor-containing flow field is close to the actual service environment of the material) in the combustion environment of an engine, and examining the oxidation resistance and the high-temperature water vapor corrosion resistance of the material; the examination conditions are as follows: the high-temperature water-containing steam flow field contains 10 mass percent of water steam, so that the surface heat flow density of the material is 3.4MW/m 2 The surface pressure was 8.7kPa, and the surface temperature was 2300 ℃. In the examination, ZrB in this example 2 -TiB 2 Model surface temperature (ZrB) of SiC material in ablation examination process of 600s 2 -TiB 2 Surface temperature of-SiC material) is stabilized around 2300 ℃, as shown in fig. 1, the temperature of the material is always stable, indicating that ZrB is present 2 -TiB 2 the-SiC material has stable ablation, good ablation resistance and good high-temperature water vapor corrosion resistance; and the ablation profile of the model remains substantially stable, as shown in FIG. 2As shown, an oxide layer formed after the material is ablated for 600s is compact and has good protection.
In the further examination of this example, ZrB 2 -TiB 2 Surface element distribution analysis is carried out on an oxide layer formed by ablating 600s of the-SiC material, as shown in figure 3, four element groups of O-Zr-Ti-Si are distributed in the oxide layer in sequence, which shows that the doping component Ti enters the oxide layer, and the (ZrO) is obtained by further calculation 2 ) 0.6 /(SiO 2 ) 0.4 -TiO 2 Ternary phase diagrams, as shown in fig. 4; the results show that at 5 vol% TiB 2 At the doping content, TiSiO formed by the system 4 +ZrO 2 The melting point of the co-solution is about 2300 ℃ which is equivalent to that of the model (ZrB) in the test 2 -TiB 2 -SiC material) has a uniform surface temperature, visible TiSiO 4 The introduction of the compound enables a new liquid phase protective layer to be formed on the surface of the material, and the original SiO is replaced 2 The protective layer improves the high-temperature water vapor protection capability (high-temperature water vapor corrosion resistance) of the material, so that the material is kept stable in the ablation process of 600 s.
Example 2
An ultrahigh-temperature ceramic material resisting high-temperature steam corrosion is prepared from (by volume) 76.8% ZrB 2 4% of TiB 2 And 19.2% SiC.
The preparation method of the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 76.8:4:19.2, and carrying out ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the temperature rising rate is 10 ℃/min when the temperature rises to 1900 ℃, the temperature falling rate is 10 ℃/min when the temperature is 1900-1300 ℃, the temperature is cooled to room temperature along with the furnace below 1300 ℃, and finally the compact ultrahigh-temperature ceramic material (ZrB) resisting high-temperature steam corrosion is obtained 2 -TiB 2 -SiC material).
Example 3
High-temperature-resistant water vaporCorrosive ultrahigh-temperature ceramic material consisting of 75.2 percent by volume of ZrB 2 6% of TiB 2 And 18.8% SiC.
The preparation of the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 75.2:6:18.8, and carrying out ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the temperature rise rate is 10 ℃/min when the temperature rises to 1900 ℃, the temperature drop rate is 10 ℃/min when the temperature is 1900-1300 ℃, the temperature is cooled to room temperature when the temperature is below 1300 ℃ along with the furnace, and finally the compact ultrahigh-temperature ceramic material (ZrB) resisting high-temperature steam corrosion is obtained 2 -TiB 2 -SiC material).
Example 4
The high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by compounding a first ultrahigh-temperature ceramic material and a second ultrahigh-temperature ceramic material; the first ultrahigh-temperature ceramic material consists of 73.5 percent of ZrB by volume percentage 2 5.5% of TiB 2 And 21% SiC; the second ultrahigh-temperature ceramic material consists of 76 percent of ZrB by volume percentage 2 5% of TiB 2 And 19% SiC.
The preparation of the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material comprises the following steps:
ZrB is subjected to ball milling by adopting a wet method 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 73.5:5.5:21, and performing ball milling for 8 hours to obtain uniformly mixed powder (a first mixture); ZrB is subjected to ball milling by adopting a wet method 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 76:5:19, and performing ball milling for 8 hours to obtain uniformly mixed powder (a second mixture); then preparing the first mixture into slurry, carrying out casting to obtain a first epitaxial layer, and carrying out casting by adopting the slurry prepared by the second mixture on the basis of the first epitaxial layer to obtain a second epitaxial layer on the basis of the first epitaxial layerThen carrying out hot-pressing sintering, and finally cooling to prepare the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material; wherein the hot-pressing sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate of the temperature rise to 1900 ℃ is 10 ℃/min, the cooling rate of the temperature rise to 1900 ℃ to 1300 ℃ is 10 ℃/min, and the temperature is cooled to the room temperature along with the furnace below 1300 ℃.
Example 5
An ultrahigh-temperature ceramic material resisting high-temperature steam corrosion is prepared from 70.4 vol% of ZrB 2 5% of TiB 2 And 24.6% SiC.
The preparation method of the ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 70.4:5:24.6, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the temperature rising rate is 10 ℃/min when the temperature rises to 1900 ℃, the temperature falling rate is 10 ℃/min when the temperature is 1900 ℃ -1300 ℃, the temperature is cooled to room temperature along with the furnace below 1300 ℃, and finally the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material (ZrB) 2 -TiB 2 -SiC material).
Example 6
An ultrahigh-temperature ceramic material resisting high-temperature water vapor corrosion is prepared from 78.5 vol% of ZrB 2 5% of TiB 2 And 16.5% SiC.
The preparation method of the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 78.5:5:16.5, and carrying out ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate of the temperature to 1900 ℃ is 10 ℃/min, the cooling rate of the temperature to 1900 ℃ is 10 ℃/min, the temperature to the temperature of the temperature to the temperature of the temperature is 130 ℃/minCooling to room temperature with the furnace below 0 ℃ to finally obtain the high temperature steam corrosion resistant ultrahigh temperature ceramic material (ZrB) 2 -TiB 2 -SiC material).
Example 7
Example 7 is essentially the same as example 1, except that:
the temperature of the hot-pressing sintering is 1700 ℃.
Example 8
Example 8 is essentially the same as example 1, except that:
the temperature of the hot-pressing sintering is 2100 ℃.
Example 9
Example 9 is essentially the same as example 1, except that:
keeping the temperature for 1h at the hot-pressing sintering temperature of 1900 ℃, and directly cooling to the room temperature along with the furnace.
Comparative example 1
An ultrahigh-temperature ceramic material is prepared from 80 vol% of ZrB 2 And 20% SiC.
The preparation method of the ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 Mixing the SiC powder and the SiC powder according to the volume ratio of 4:1, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (the sintering time) is 1 hour, the heating rate of the mixed powder is 10 ℃/min when the mixed powder is heated to 1900 ℃, the cooling rate of the mixed powder is 10 ℃/min when the mixed powder is cooled to 1300 ℃, the mixed powder is cooled to room temperature along with the furnace below 1300 ℃, and finally the ultrahigh-temperature ceramic material (ZrB) is obtained 2 -SiC material).
This comparative example applied the same method as in example 1 to ZrB of this comparative example 2 the-SiC material is subjected to the examination of the high-temperature water vapor protective performance; the results show that ZrB is present in comparative example 2 After the SiC material is ablated for 489s, the temperature of the model surface rapidly rises, as shown in FIG. 1, which is the expression of ablation damage of the material, and the ablation topography of the material well indicates the phenomenon that the surface of the material is ablatedAnd as shown in FIG. 2, an oxide layer on the surface of the material is porous and consists of three elements Zr-Si-O, and an oxidation atmosphere can ablate the material matrix through the pores and cannot effectively protect the matrix, so that temperature jump and ablation damage are caused.
Comparative example 2
An ultrahigh-temperature ceramic material is prepared from (by volume) 74.4% ZrB 2 7% of TiB 2 And 18.6% SiC.
The preparation method of the ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 74.4:7:18.6, and carrying out ball milling for 8 hours to obtain uniformly mixed powder (mixture); and sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate of the mixed powder is 10 ℃/min when the mixed powder is heated to 1900 ℃, the cooling rate of the mixed powder is 10 ℃/min when the mixed powder is cooled to 1300 ℃, and the mixed powder is cooled to room temperature along with a furnace below 1300 ℃, so that the ultrahigh-temperature ceramic material is finally obtained.
Comparative example 3
An ultrahigh-temperature ceramic material is prepared from (by volume) 77.6% ZrB 2 3% of TiB 2 And 19.4% SiC.
The preparation method of the ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 77.6:3:19.4, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); and sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate of the mixed powder is 10 ℃/min when the mixed powder is heated to 1900 ℃, the cooling rate of the mixed powder is 10 ℃/min when the mixed powder is cooled to 1300 ℃, and the mixed powder is cooled to room temperature along with a furnace below 1300 ℃, so that the ultrahigh-temperature ceramic material is finally obtained.
Comparative example 4
A titanium boride-zirconium boride-silicon carbide ceramic material which is composed of 30 percent by volumeZrB 2 65.0% of TiB 2 And 5.0% SiC.
The titanium boride-zirconium boride-silicon carbide ceramic material is prepared by the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、TiB 2 Mixing the powder with SiC powder according to the volume ratio of 30:65:5, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); and sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate is 10 ℃/min when the temperature is raised to 1900 ℃, the cooling rate is 10 ℃/min when the temperature is lowered to 1900-1300 ℃, and the temperature is cooled to room temperature along with the furnace below 1300 ℃, so that the titanium boride-zirconium boride-silicon carbide ceramic material is finally obtained.
Comparative example 5
A titanium boride-zirconium boride-silicon carbide self-lubricating composite ceramic material was prepared by the same method as in example 1 in CN 103387392A.
Comparative example 6
An ultrahigh-temperature ceramic material is prepared from 70% ZrB 2 5% of HfC, 10% of SiC and 7% of TiB 2 And 8% SC 2 O 3 The components of the composition are as follows,
the preparation method of the ultrahigh-temperature ceramic material comprises the following steps:
firstly, ZrB is subjected to a wet ball milling process 2 、HfC、SiC、TiB 2 And SC 2 O 3 Mixing the powder materials according to the volume ratio of 70:5:10:7:8, and performing ball milling for 8 hours to obtain uniformly mixed powder (mixture); and sintering the mixed powder by adopting a hot pressing process, wherein the sintering atmosphere is argon, the sintering temperature is 1900 ℃, the sintering pressure is 30MPa, the heat preservation (sintering time) is 1 hour, the heating rate of the mixed powder is 10 ℃/min when the mixed powder is heated to 1900 ℃, the cooling rate of the mixed powder is 10 ℃/min when the mixed powder is cooled to 1300 ℃, and the mixed powder is cooled to room temperature along with a furnace below 1300 ℃, so that the ultrahigh-temperature ceramic material is finally obtained.
The materials in examples 2 to 9 and comparative examples 1 to 6 were examined for high-temperature steam protective performance by the same method as in example 1, and the time results of the high-temperature steam corrosion resistance of each material are shown in table 1.
Particularly, the material is ablated during examination, and along with the prolonging of ablation time, when the surface temperature of the material rapidly rises, the ablation damage of the material at the time point is shown, and the time for the material to resist the high-temperature water vapor corrosion is the longest at the time point; taking comparative example 1 as an example, ZrB in the comparative example 1 is adopted 2 The SiC material is subjected to the examination of the high-temperature water vapor protective performance; the results show that ZrB in this comparative example 2 The rapid increase in the temperature of the surface of the model after ablation of the SiC material for 489s, i.e. ZrB in comparative example 1 2 The time of the-SiC material for resisting high-temperature water vapor corrosion is 489 s.
Table 1: the performance indexes of the materials in examples 1-9 and comparative examples 1-6.
Figure BDA0003680055500000171
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the embodiments can still be modified, or some technical features can be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention in its aspects.

Claims (10)

1. The high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is characterized in that:
the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by 70-81% of ZrB in percentage by volume 2 4-6% of TiB 2 And 15-25% of SiC.
2. The hyperthermal ceramic material resistant to high temperature steam corrosion according to claim 1, characterized in that:
the ultrahigh-temperature ceramic material resistant to high-temperature steam corrosion is prepared by a hot-pressing sintering process;
in the hot-pressing sintering process, the temperature of the hot-pressing sintering is 1800-2000 ℃, preferably 1900 ℃, the pressure of the hot-pressing sintering is 25-35 MPa, preferably 30MPa, and the time of the hot-pressing sintering is 0.5-2 h, preferably 1 h;
preferably, the heating rate of the temperature raised to the hot-pressing sintering temperature is 5-15 ℃/min;
more preferably, in the hot-pressing sintering process, after the hot-pressing sintering is performed, the cooling procedure adopted is as follows: and reducing the temperature of the hot-pressing sintering to 1300 ℃ at a cooling rate of 5-15 ℃/min, and then cooling to room temperature along with the furnace.
3. The ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion according to claim 1, characterized in that:
the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion forms TiSiO after being subjected to high-temperature water-containing vapor flow field oxidation 4 And oxidizing the layer, thereby improving the high-temperature water vapor corrosion resistance of the ultrahigh-temperature ceramic material.
4. The high temperature water vapor corrosion resistant ultra high temperature ceramic material according to any one of claims 1 to 3, characterized in that:
the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material consists of 76 percent of ZrB in percentage by volume 2 5% of TiB 2 And 19% SiC.
5. The high temperature water vapor corrosion resistant ultra high temperature ceramic material according to any one of claims 1 to 3, characterized in that:
the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by compounding a first ultrahigh-temperature ceramic material and a second ultrahigh-temperature ceramic material.
6. The ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion according to claim 5, characterized in that:
the first ultrahigh-temperature ceramic material consists of 73.5 percent of ZrB by volume percentage 2 5.5% of TiB 2 And 21% SiC;
the second ultrahigh-temperature ceramic material consists of 76 percent of ZrB by volume percentage 2 5% of TiB 2 And 19% SiC.
7. The method for preparing a hyperthermal ceramic material resistant to high temperature water vapor corrosion according to any of claims 1 to 6, characterized in that it comprises the following steps:
(1) reacting ZrB 2 Powder, TiB 2 Uniformly mixing the powder and the SiC powder by ball milling to obtain a mixture;
(2) carrying out hot-pressing sintering on the mixture, and then cooling to prepare the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material;
the hot-pressing sintering temperature is 1800-2000 ℃, the hot-pressing sintering pressure is 25-35 MPa, and the hot-pressing sintering time is 0.5-2 h.
8. The method for producing according to claim 7, characterized in that:
the heating rate of the temperature raised to the hot-pressing sintering temperature is 5-15 ℃/min; and/or
The cooling is as follows: and reducing the temperature of the hot-pressing sintering to 1300 ℃ at a cooling rate of 5-15 ℃/min, and then cooling to room temperature along with the furnace.
9. The production method according to claim 7 or 8, characterized in that:
when the high-temperature steam corrosion resistant ultrahigh-temperature ceramic material is formed by compounding a first ultrahigh-temperature ceramic material and a second ultrahigh-temperature ceramic material, respectively obtaining a first mixed material and a second mixed material corresponding to the components of the first ultrahigh-temperature ceramic material and the second ultrahigh-temperature ceramic material in step (1); in the step (2), the first mixture is prepared into slurry and then is subjected to tape casting to obtain a first epitaxial layer, then the slurry prepared from the second mixture is adopted to carry out tape casting on the basis of the first epitaxial layer to obtain a second epitaxial layer on the basis of the first epitaxial layer, and then hot-pressing sintering and cooling are carried out to obtain the ultrahigh-temperature ceramic material resistant to high-temperature water vapor corrosion.
10. Use of the hyperthermal ceramic material resistant to high temperature steam corrosion according to any of claims 1 to 6 or the hyperthermal ceramic material resistant to high temperature steam corrosion prepared according to the preparation method of any of claims 7 to 9 as a thermal protection material for high thrust-weight ratio engines.
CN202210631409.8A 2022-06-06 2022-06-06 High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof Active CN115124349B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210631409.8A CN115124349B (en) 2022-06-06 2022-06-06 High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210631409.8A CN115124349B (en) 2022-06-06 2022-06-06 High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115124349A true CN115124349A (en) 2022-09-30
CN115124349B CN115124349B (en) 2023-03-31

Family

ID=83378708

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210631409.8A Active CN115124349B (en) 2022-06-06 2022-06-06 High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115124349B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102126860A (en) * 2010-01-14 2011-07-20 中国科学院上海硅酸盐研究所 Method for preparing boride-based ceramic by slip casting
CN103387392A (en) * 2013-07-25 2013-11-13 洛阳理工学院 Titanium boride-zirconium boride-silicon carbide self-lubricating composite ceramic material and preparation method thereof
CN107235731A (en) * 2017-05-12 2017-10-10 西南交通大学 Eutectic structure superhigh temperature ZrB2SiC complex phase ceramics and preparation method
CN108911757A (en) * 2018-06-25 2018-11-30 广东工业大学 A kind of high-performance zirconium boride-carborundum complex phase ceramic and its preparation method and application
CN114394837A (en) * 2022-02-08 2022-04-26 哈尔滨工业大学 Preparation method and application of antioxidant diboride-carbide solid solution ceramic

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102126860A (en) * 2010-01-14 2011-07-20 中国科学院上海硅酸盐研究所 Method for preparing boride-based ceramic by slip casting
CN103387392A (en) * 2013-07-25 2013-11-13 洛阳理工学院 Titanium boride-zirconium boride-silicon carbide self-lubricating composite ceramic material and preparation method thereof
CN107235731A (en) * 2017-05-12 2017-10-10 西南交通大学 Eutectic structure superhigh temperature ZrB2SiC complex phase ceramics and preparation method
CN108911757A (en) * 2018-06-25 2018-11-30 广东工业大学 A kind of high-performance zirconium boride-carborundum complex phase ceramic and its preparation method and application
CN114394837A (en) * 2022-02-08 2022-04-26 哈尔滨工业大学 Preparation method and application of antioxidant diboride-carbide solid solution ceramic

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHANG XING-HONG等: "Microstructure and Mechanical Properties of ZrB2-based Ceramics", 《KEY ENGINEERING MATERIALS》 *
尹嘉琦等: "《难熔超硬耐高温硼化物材料及其应用》", 31 July 2017, 冶金工业出版社 *

Also Published As

Publication number Publication date
CN115124349B (en) 2023-03-31

Similar Documents

Publication Publication Date Title
Aparicio et al. Yttrium silicate coatings for oxidation protection of carbon–silicon carbide composites
CA2647453C (en) Thermal barrier coating member, method for producing the same, thermal barrier coating material, gas turbine, and sintered body
JP4969094B2 (en) Thermal barrier coating member and production thereof, and gas turbine
JP2000248961A (en) Method for preventing receding loss of silica and silicon- containing material in combustion gas atmosphere
JP4031631B2 (en) Thermal barrier coating material, gas turbine member and gas turbine
CN113045332A (en) Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof
CN112341197B (en) CMAS corrosion resistant high-entropy ceramic material, preparation method and application thereof
CN107119251A (en) It is a kind of for self-healing ceramic thermal barrier coating material of metal surface and preparation method thereof
CN110387148B (en) Anti-ablation coating material for resin-based composite material and preparation method thereof
CN112142486A (en) Preparation method of ablation-resistant silicon carbide fiber reinforced ceramic matrix composite
CN111534796B (en) Nano mullite powder for plasma physical vapor deposition and preparation method thereof
CN115124339B (en) Multielement high entropy doped zirconia-based ceramic material and preparation method and application thereof
Jiang et al. Oxidation and ablation behaviour of multiphase ultra-high-temperature ceramic Ta0· 5Zr0· 5B2–Si–SiC protective coating for graphite
CN110198920B (en) Component comprising a substrate and an environmental barrier
Zhu et al. Ablation properties and mechanisms of BN-coated Cf-reinforced SiBCNZr ceramic composites under an oxyacetylene combustion torch
Jiang et al. Multiphase composite Hf0. 8Ti0· 2B2–SiC–Si coating providing oxidation and ablation protection for graphite under different high temperature oxygen-containing environments
Wang et al. Effect of ablative angles on the ablation behaviors of ZrB2-SiC modified carbon/carbon composites
US6537617B2 (en) Manufacturing method of ceramic matrix composite
Zhang et al. A thick SiC-Si coating prepared by one-step pack cementation for long-term protection of carbon/carbon composites against oxidation at 1773 K
CN110373628A (en) Spontaneous High temperature diffusion barrier of a kind of refractory metal surfaces reaction in-situ and preparation method thereof
CN115124349B (en) High-temperature steam corrosion resistant ultrahigh-temperature ceramic material and preparation method and application thereof
CN104087806B (en) Thermal protection SiC-Cu complex phase transpiration cooling material and preparation method thereof
CN105908043B (en) A kind of Mo ZrB2SiC AlN composites and preparation method thereof
CN112250476A (en) YSZ-RETaO with high-temperature ceramic coating4SiC-based composite material and preparation method thereof
Wang et al. Oxidation ablation resistance of ZrB2-HfB2-SiC-TaSi2 coating prepared on C/C composite surface

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant