CN112250443A - Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating - Google Patents

Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating Download PDF

Info

Publication number
CN112250443A
CN112250443A CN202011197952.9A CN202011197952A CN112250443A CN 112250443 A CN112250443 A CN 112250443A CN 202011197952 A CN202011197952 A CN 202011197952A CN 112250443 A CN112250443 A CN 112250443A
Authority
CN
China
Prior art keywords
ceramic
temperature
precursor
coating
ultrahigh
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.)
Pending
Application number
CN202011197952.9A
Other languages
Chinese (zh)
Inventor
栾新刚
李敏
成来飞
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.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
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 Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN202011197952.9A priority Critical patent/CN112250443A/en
Publication of CN112250443A publication Critical patent/CN112250443A/en
Pending legal-status Critical Current

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
    • C04B35/584—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 silicon nitride
    • 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
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • 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
    • C04B2235/3821—Boron 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
    • C04B2235/02—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
    • C04B2235/02—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
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • 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
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to a multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating, which is characterized in that a ceramic precursor is used as a raw material, a precursor pyrolysis product and the precursor are mixed to prepare slurry, and the precursor in the slurry is cracked in the temperature rise process (namely, in a low-pressure state) of deposition by combining a CVD (chemical vapor deposition) process, so that a compact film capable of being used at high temperature is prepared. The volume of the pyrolysis product in the slurry can not shrink at high temperature, so that the volume shrinkage of the slurry can be reduced to a certain extent, and cracking is reduced; when the ceramic precursor is cracked under low pressure, the micromolecular gas-phase products can escape more quickly without accumulating in the ceramic, so that the occurrence of internal holes can be reduced; the CVD process can seal microcracks generated in the cracking process of the precursor, and the integrity of the coating is ensured.

Description

Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating
Technical Field
The invention belongs to the technical field of preparation of surface coatings, and relates to a multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating, in particular to design and a preparation method of a compact high-temperature resistant ceramic coating based on the surface of an ultrahigh-temperature material.
Background
The Environmental Barrier Coatings (EBCs) can establish a protective barrier for high thrust-weight ratio aircraft engines, gas turbines, advanced rocket engines and the like in a high-temperature gas environment, effectively prevent or weaken corrosion of corrosive media such as water oxygen, molten salt and the like in the gas environment on hot end parts, enable the hot end parts to be safely and reliably in service in complex environments such as high-temperature high-speed airflow, water oxygen, molten salt and the like, and prolong the service time of devices.
SiBCN ceramics are generally amorphous or nanocrystalline structures and have good high temperature stability, strong creep resistance, low density (about 1.8g/cm3), and low thermal expansion coefficient (3 x 10)-6The amorphous structure has excellent performances of low thermal conductivity (about 3W/m.K) and the like, and the amorphous structure can be maintained at 1700-1800 ℃. And the SiBCN ceramic has good oxidation resistance, is one of non-oxide ceramic materials with the lowest oxidation rate, Weinmann [2 ]]TG analysis on SiBCN ceramic shows that the SiBCN ceramic has almost no quality change under oxygen environment at 1700 ℃, and SiC and Si3N4The ceramic has obvious weight gain, and the SiBCN ceramic is considered to have more excellent oxidation resistance. The SiBCN blocky ceramic is prepared at a lower temperature (about 1000 ℃) by a polymer-converted ceramic method. Feng [3 ]]And preparing a compact SiBCN coating at 1300 ℃ by using PBSZ as a precursor.
SiOC precursor ceramics are the earliest silicon-based ceramics, have wide raw material sources, low price, high yield, simple preparation, easy storage, and can prepare large and complex parts, and have been studied for many years and widely used. However, the yield of SiOC precursor ceramic is low, carbothermic reduction reaction starts to occur at around 1300 ℃, and the durability at high temperature is insufficient, limiting its application in severe environment. The high-temperature stability of the SiOC-based precursor ceramic can be effectively improved by doping elements such as boron, nitrogen, zirconium, hafnium and the like into the SiOC precursor ceramic, wherein the high-temperature oxidation resistance of the SiOC-based precursor ceramic can be remarkably improved by introducing the boron element. Numerous studies have shown that2The addition of a silicon-based second phase can significantly improve the silicon-free HfC or HfB2Including SiC/HfC, SiC/HfB2, or SiC/HfC/HfB2A composite material. Therefore, we consider new SiHfBCN amorphous ceramics and their nanocomposites as promising candidates in ultra-high temperature applications. Electrically insulating and optically transparent prepared by pulsed reactive magnetron sputteringAmorphous Hf of7B23Si17C4N45Film(s)[1]Since the nanocomposite protective oxide layer (containing HfO) can be formed on the surface at 1000 ℃ or higher2SiO of nanoparticles2Amorphous matrix) that exhibits excellent oxidation resistance in air up to 1600 c and is useful as a temperature protective coating for electronic and optical components at high temperatures.
The preparation method of the EBCs coating mainly comprises the following steps: plasma Spray Deposition (PSD), Electron Beam Physical Vapor Deposition (EB-PVD), Sol-Gel (Sol-Gel), Slurry impregnation (Slurry and Dipping), Chemical Vapor Deposition (CVD), and Polymer-modified Ceramics (PDCs), among others.
The polymer-converted ceramic method has the advantages of simple process equipment, low coating sintering temperature, capability of preparing coatings on the surfaces of substrates in various shapes and the like, and the method has the main defect that the polymer generates larger volume shrinkage due to volatilization of small molecular gases and increase of product density in the process of curing and cracking, so that a more compact coating is difficult to obtain. The chemical vapor deposition method has the advantages of uniform and compact coating, firm combination with the matrix, easy control of film components, stable film quality and high deposition rate. However, the method has high requirements on equipment, long preparation period, high production cost and long common period.
[1]P.Zeman,S.Zuzjakova,P.Mares,et al.Superior high-temperature oxidation resistance of magnetron sputtered Hf-B-Si-C-N film[J].Ceramics International,2016,42(4): 4853-4859.
[2]Weinmann M,
Figure BDA0002754535710000021
Schuhmacher,Kummer H,et al.Synthesis and Thermal Behavior of Novel Si-B-C-N Ceramic Precursors[J].Chemistry of Materials,2000,12(3).
[3]Feng Z L,Guo Z M,Lu B,et al.Preparation and Thermal Cycling Resistance of SiBCN(O)Coating[J].Key Engineering Materials,2014,602-603:393-396.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating.
Technical scheme
A multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating is characterized by comprising the following steps:
step 1: preparing a ceramic precursor, a precursor pyrolysis product and tetrahydrofuran into slurry according to the mass ratio of 1: 0.01-5: 0-5, coating the slurry on a substrate, heating to 100-200 ℃ at the heating rate of 2-10 ℃/min, and curing in argon for 2-5h to preliminarily prepare a ceramic coating;
step 2: in the temperature rising process of the CVD process, the deposition is carried out according to the deposition parameters of the ceramic; and (3) cracking the pyrolysis product of the ceramic precursor, and finishing additive cracking and ceramic formation of the ceramic precursor while depositing the ceramic coating so as to inhibit the shrinkage of the self-healing layer, finally finishing the preparation of the compact ceramic coating and reducing cracks and holes in the coating prepared at low temperature.
The ceramic precursor includes, but is not limited to, PSNB, PCS, or PBSZ.
Advantageous effects
The invention provides a multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating, which is characterized in that a ceramic precursor is used as a raw material of the coating, a precursor pyrolysis product and the precursor are mixed to prepare slurry, and the precursor in the slurry is cracked in the temperature rise process (namely, in a low-pressure state) of deposition by combining a CVD (chemical vapor deposition) process, so that a compact film capable of being used at high temperature is prepared. The volume of the pyrolysis product in the slurry can not shrink at high temperature, so that the volume shrinkage of the slurry can be reduced to a certain extent, and cracking is reduced; when the ceramic precursor is cracked under low pressure, the micromolecular gas-phase products can escape more quickly without accumulating in the ceramic, so that the occurrence of internal holes can be reduced; the CVD process can seal microcracks generated in the cracking process of the precursor, and the integrity of the coating is ensured.
The multiphase coupling low-temperature preparation method of the ultrahigh-temperature ceramic coating provided by the invention has the main advantages that: the prepared ceramic coating has excellent high temperature resistance, a compact coating can be prepared at a lower temperature, the high temperature resistance of the substrate is improved, the service life of the substrate is prolonged, the process is simple, and the repeatability is good.
The PDC and the CVD are combined together, solidified precursor powder is mixed in slurry of the PDC, and a coating which can be used at an ultrahigh temperature is prepared by adopting the effect of inhibiting ceramic shrinkage through gas-liquid-solid multiphase coupling. Selecting proper pyrolysis atmosphere, pressure and time according to the characteristics of the PDC and CVI processes; selecting a pyrolysis temperature range according to a thermogravimetric curve of the precursor; after cross-linking for 2 hours at 170 ℃ in a drying oven, pyrolyzing the precursor for different times by using a high-temperature tube furnace at different temperatures, different atmospheres and different pressures, and then determining the element proportion, the component distribution and the microstructure characteristics of the pyrolysis product by using EDS, NMR, XPS, XRD, SEM and other means for analysis and test, and determining the process parameter range of complete pyrolysis of different precursors. And (3) comparing contact angles of different precursor stock solutions and the solution mixed and diluted with tetrahydrofuran according to different proportions on the surface of the CVD SiC ceramic, and controlling the proportion of gas phase and solid phase.
The SiHfBCN coating is prepared on the surface of the C/SiC composite material by the method, as shown in figure 1(a), the coating weight loss is not obvious at 1200 ℃, the weight loss is maintained at a better degree at 1300 ℃, and the coating shows a continuous weight loss trend along with the extension of time when oxidized in air at 1400 ℃. As shown in FIG. 1(b), after oxidation in air at 1300 ℃ for 10h, a relatively dense oxide film is formed on the surface of the ceramic, which is beneficial to improving the oxidation resistance of the ceramic, and the prepared SiHfBCN coating can be used at 1300 ℃.
Drawings
FIG. 1: mass change curves in air at different temperatures for (a) preparation of SiHfBCN coatings by PDC in combination with CVD; (b) the appearance of the composite material after being oxidized for 10 hours in air at 1300 ℃;
FIG. 2: the surface appearance and the section appearance of the SiBCN ceramic coating prepared on the YCOB surface by combining PDC with CVD;
FIG. 3: the surface appearance of the SiHfBCN ceramic coating prepared on the SiC surface by combining the PDC with the CVD;
FIG. 4: surface morphology of SiHfBCN ceramic coating prepared on SiC surface by combining PDC with CVD
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example one
The method comprises the following steps: sequentially placing the YCOB substrate in acetone, alcohol and distilled water, respectively carrying out ultrasonic cleaning for about ten minutes, and then drying at normal temperature;
step two: pyrolysis products of PSNB0, tetrahydrofuran and PSNB0 were purified as PSNB 0: tetrahydrofuran: PSNB0 pyrolysis product (mass ratio) 1: 2: 3, diluting, stirring uniformly, dispersing uniformly by ultrasonic, and storing in a dark and sealed manner;
step three: uniformly brushing the slurry on a substrate by using a superfine pappus brush, standing for half an hour in vacuum, and waiting for the surface to be uniformly spread;
step four: placing the coated YCOB substrate in a graphite crucible, and placing the graphite crucible in a SiBCN deposition furnace in an atmosphere of MTS-BCl3-NH3-H2And Ar, carrying out pyrolysis of PSNB while carrying out chemical vapor deposition of SiBCN to obtain a SiBCN coating, wherein the temperature is 950 ℃ and the time is 2 h.
The thickness of the SiBCN coating prepared in the example 1 is 1um, and the YCOB/BN/SiBCN composite material prepared by combining the PDC and the CVD has a smooth surface and does not have obvious cracks and holes. Wherein the morphology of the cauliflower-like spherical particles on the surface is the morphology of a SiBCN coating deposited by a typical CVD method.
Example two
The method comprises the following steps: sequentially placing the SiC ceramic substrate in acetone, alcohol and distilled water, respectively carrying out ultrasonic cleaning for about ten minutes, and then drying at normal temperature;
step two: the pyrolysis products of PSNBHf, tetrahydrofuran and PSNBHf were mixed at PSNBHf: tetrahydrofuran: psnbbf pyrolysis product (mass ratio) 1: 1: diluting at a ratio of 0.1, stirring uniformly, dispersing uniformly by ultrasonic, and storing in a dark and sealed manner;
step three: uniformly brushing the slurry on a substrate by using a superfine pappus brush, standing for half an hour in vacuum, and waiting for the surface to be uniformly spread;
step four: and (3) placing the coated SiC ceramic substrate in a graphite crucible, placing the graphite crucible in a SiC deposition furnace in the atmosphere of MTS-H2-Ar, and performing pyrolysis of PSNBHF while performing chemical vapor deposition on SiC to obtain a SiHfBCN coating, wherein the temperature is 1000 ℃ and the time is 2H.
FIG. 3 is a surface topography of a complex phase ceramic coating prepared using the above process. It can also be seen in fig. 3 that the smaller size cracks have been encapsulated by CVD SiC (as shown by the black boxes in fig. 3), indicating that the CVI process encapsulates small pores in the material, enabling gas-liquid-solid multiphase coupled densification. It can also be seen in fig. 3 that the CVD SiC completely encapsulated the surface of the PDC SiHfBCN ceramic, demonstrating the good permeability of the chemical vapor deposition process employed in this patent.
EXAMPLE III
The method comprises the following steps: sequentially placing the SiC ceramic substrate in acetone, alcohol and distilled water, respectively carrying out ultrasonic cleaning for about ten minutes, and then drying at normal temperature;
step two: the pyrolysis products of PSNBHf, tetrahydrofuran and PSNBHf were mixed at PSNBHf: tetrahydrofuran: psnbbf pyrolysis product (mass ratio) 1: 1: diluting at a ratio of 0.15, stirring, ultrasonically dispersing, and storing in dark and sealed condition;
step three: uniformly brushing the slurry on a substrate by using a superfine pappus brush, standing for half an hour in vacuum, and waiting for the surface to be uniformly spread;
step four: and (3) placing the coated SiC ceramic substrate in a graphite crucible, placing the graphite crucible in a SiC deposition furnace in the atmosphere of MTS-H2-Ar, and performing pyrolysis of PSNBHF while performing chemical vapor deposition on SiC to obtain a SiHfBCN coating, wherein the temperature is 1000 ℃ and the time is 2H.
Fig. 4 shows the surface morphology of the complex phase ceramic coating prepared by the above process, and it can be found that the volume shrinkage of the precursor is greatly reduced, and the PDC SiHfBCN ceramic powder can be found on the surface of the pyrolysis product, which fully illustrates that the introduction of the PDC SiHfBCN ceramic powder improves the degree of densification of the ceramic layer.

Claims (4)

1. A multiphase coupling low-temperature preparation method of an ultrahigh-temperature ceramic coating is characterized by comprising the following steps:
step 1: preparing a ceramic precursor, a precursor pyrolysis product and tetrahydrofuran into slurry according to the mass ratio of 1: 0.01-5: 0-5, coating the slurry on a substrate, heating to 100-200 ℃ at the heating rate of 2-10 ℃/min, and curing in argon for 2-5h to preliminarily prepare a ceramic coating;
step 2: in the temperature rising process of the CVD process, the deposition is carried out according to the deposition parameters of the ceramic; and (3) cracking the pyrolysis product of the ceramic precursor, and finishing additive cracking and ceramic formation of the ceramic precursor while depositing the ceramic coating so as to inhibit the shrinkage of the self-healing layer, finally finishing the preparation of the compact ceramic coating and reducing cracks and holes in the coating prepared at low temperature.
2. The multiphase coupling low-temperature preparation method of the ultrahigh-temperature ceramic coating according to claim 1, characterized by comprising the following steps of: the ceramic precursor includes, but is not limited to, PSNB, PCS, or PBSZ.
3. The multiphase coupling low-temperature preparation method of the ultrahigh-temperature ceramic coating according to claim 1, characterized by comprising the following steps of: and (2) when the ceramic precursor adopts PSNB and precursor pyrolysis products thereof and the substrate is YCOB, carrying out the CVD process in the step 2: placing the ceramic coating substrate in a graphite crucible, and placing the graphite crucible in a SiBCN deposition furnace in an atmosphere of MTS-BCl3-NH3-H2And Ar, carrying out pyrolysis of PSNB while carrying out chemical vapor deposition of SiBCN to obtain a SiBCN coating, wherein the temperature is 950 ℃ and the time is 2 h.
4. The multiphase coupling low-temperature preparation method of the ultrahigh-temperature ceramic coating according to claim 1, characterized by comprising the following steps of: the ceramic precursor adopts PSNBHF and precursor pyrolysis products thereof, and when the substrate is SiC ceramic, the CVD process of the step 2 comprises the following steps: performing pyrolysis of PSNBHF (hydrogen sulfide Bronsted boron hydride) and chemical vapor deposition of SiC under the atmosphere of MTS-H2-Ar to obtain a SiHfBCN coating at the temperature of 1000 ℃ for 2 hours.
CN202011197952.9A 2020-10-30 2020-10-30 Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating Pending CN112250443A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011197952.9A CN112250443A (en) 2020-10-30 2020-10-30 Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011197952.9A CN112250443A (en) 2020-10-30 2020-10-30 Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating

Publications (1)

Publication Number Publication Date
CN112250443A true CN112250443A (en) 2021-01-22

Family

ID=74268114

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011197952.9A Pending CN112250443A (en) 2020-10-30 2020-10-30 Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating

Country Status (1)

Country Link
CN (1) CN112250443A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441762A (en) * 1991-03-22 1995-08-15 E. I. Du Pont De Nemours And Company Coating a composite article by applying a porous particulate layer and densifying the layer by subsequently applying a ceramic layer
CN103253938A (en) * 2013-05-15 2013-08-21 西北工业大学 Chemical vapor deposition method of Si-B-C-N amorphous ceramic
CN103898499A (en) * 2014-03-17 2014-07-02 中国人民解放军装甲兵工程学院 Method for preparing SiC/Al2O3 coating by using precursor conversion method
CN105399452A (en) * 2015-10-29 2016-03-16 西北工业大学 Rapid preparation method of ceramic matrix composite material
CN106977217A (en) * 2016-06-03 2017-07-25 北京航空航天大学 A kind of preparation method of high-strength and high-ductility silicon carbide fiber reinforced silicon carbide ceramic matric composite
CN110627514A (en) * 2019-10-30 2019-12-31 航天特种材料及工艺技术研究所 C/SiC-HfB2Composite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441762A (en) * 1991-03-22 1995-08-15 E. I. Du Pont De Nemours And Company Coating a composite article by applying a porous particulate layer and densifying the layer by subsequently applying a ceramic layer
CN103253938A (en) * 2013-05-15 2013-08-21 西北工业大学 Chemical vapor deposition method of Si-B-C-N amorphous ceramic
CN103898499A (en) * 2014-03-17 2014-07-02 中国人民解放军装甲兵工程学院 Method for preparing SiC/Al2O3 coating by using precursor conversion method
CN105399452A (en) * 2015-10-29 2016-03-16 西北工业大学 Rapid preparation method of ceramic matrix composite material
CN106977217A (en) * 2016-06-03 2017-07-25 北京航空航天大学 A kind of preparation method of high-strength and high-ductility silicon carbide fiber reinforced silicon carbide ceramic matric composite
CN110627514A (en) * 2019-10-30 2019-12-31 航天特种材料及工艺技术研究所 C/SiC-HfB2Composite material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XINGANG LUAN ET AL.: "Oxidation behavior of C/SiC-SiBCN composites at high temperature", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *
XINGANG LUAN ET AL.: "Wet oxidation behavior of C/SiC–SiHf(B)CN composites at high temperature", 《ADVANCED COMPOSITES AND HYBRID MATERIALS》 *
XINGANG LUAN ET AL.: "Wet oxidation behavior of SiC/(SiC‐ SiBCN)x composites", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 *

Similar Documents

Publication Publication Date Title
CN107814591B (en) Preparation method of boride modified silicon-based antioxidant coating on surface of carbon material
CN101503305B (en) Process for preparing self-sealing silicon carbide ceramic based composite material
CN107353025B (en) Preparation method of 1200-DEG C-resistant and oxidation-resistant ceramic matrix composite
CN107540400A (en) A kind of SiC with compound interfacef/ SiC ceramic based composites
Jiang et al. Oxidation and ablation protection of double layer HfB2-SiC-Si/SiC-Si coating for graphite materials
CN113845367B (en) Preparation method of high-temperature oxidation-resistant carbon fiber toughened zirconia ceramic material and high-temperature oxidation-resistant carbon fiber toughened zirconia ceramic material
CN104529498A (en) One-step preparation method of multi-layer environmental barrier coatings through spark plasma sintering (SPS)
Feng et al. Effect of tantalum carbide on the ablation behaviors of hafnium carbide coating for C/C composites under single and cyclic oxyacetylene torch environments
US20080193674A1 (en) Production of a Gas-Tight, Crystalline Mullite Layer by Using a Thermal Spraying Method
CN113860920B (en) Environmental barrier coating with excellent CMAS corrosion resistance and preparation method thereof
CN108947588A (en) A kind of C/SiC composite material and the antioxidant coating for the material and preparation method thereof
CN112409025A (en) Has SiC-HfB2Preparation method of carbon/carbon composite material of-Si single-layer composite coating
CN105481477A (en) Preparation method of graphite/SiC composite material
CN109265189A (en) Microwave-absorbing ceramic based composites fast preparation method with electromagnetic resistivity gradual change matrix
Qian et al. Corrosion behavior of Y2O3-doped mullite-ZrSiO4 coatings applied on C/C–SiC composites in the presence of moisture at temperatures of 1373–1773 K
CN115948721B (en) Method for preparing tantalum carbide coating by CVD method
CN112250443A (en) Multiphase coupling low-temperature preparation method of ultrahigh-temperature ceramic coating
CN115894085B (en) Composite ceramic coating material and preparation method and application thereof
CN115259903B (en) High-precision high-temperature ablation resistant coating formed on substrate material, preparation method thereof and composite material comprising coating
CN111848222A (en) Gradient environmental barrier coating formed on base material and preparation method thereof
CN112299883B (en) High-temperature-resistant protective coating of silicon carbide heating element and preparation method thereof
CN114380612A (en) Preparation method of low-loss high-oxidation-resistance silicon carbide fiber reinforced zirconia-zirconium tungstate ceramic composite material
KR20040069837A (en) Method for Making Oxidation Protective Double Coating for Carbon/Carbon Composite
CN105503270A (en) Method for preparing SiC coating
CN112174685A (en) Unidirectional fiber bundle reinforced ZrB2Preparation method of-SiC composite material

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20210122

RJ01 Rejection of invention patent application after publication