CN114213664B - Synthesis method of five-component SiBCNZr ceramic precursor - Google Patents

Synthesis method of five-component SiBCNZr ceramic precursor Download PDF

Info

Publication number
CN114213664B
CN114213664B CN202111583211.9A CN202111583211A CN114213664B CN 114213664 B CN114213664 B CN 114213664B CN 202111583211 A CN202111583211 A CN 202111583211A CN 114213664 B CN114213664 B CN 114213664B
Authority
CN
China
Prior art keywords
sibcnzr
precursor
temperature
ceramic
precursor solution
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.)
Active
Application number
CN202111583211.9A
Other languages
Chinese (zh)
Other versions
CN114213664A (en
Inventor
韩文波
吕杨
赵广东
周善宝
汪梦宇
张幸红
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.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
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 Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN202111583211.9A priority Critical patent/CN114213664B/en
Publication of CN114213664A publication Critical patent/CN114213664A/en
Application granted granted Critical
Publication of CN114213664B publication Critical patent/CN114213664B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes

Abstract

The invention discloses a synthesis method of a five-component SiBCNZr ceramic precursor, belongs to the technical field of high polymer materials, and particularly relates to a synthesis method of a five-component SiBCNZr ceramic precursor. The invention aims to solve the problem that the SiBCN ceramic precursor prepared by the existing method has poor oxidation resistance. In the curing process, elements such as Zr are crosslinked in the SiBCN-based precursor, namely Si, N, B, C and Zr are connected through covalent bonds to form a precursor polymer containing a large amount of Si, B, N, C and Zr elements. The structure of the SiBCNZr ceramic precursor can be effectively adjusted, and the uniformity of element distribution in the precursor is ensured. And then removing small molecules from the precursor through a curing reaction to form a high polymer, and finally obtaining the SiBCNZr ceramic material with stable covalent bond connection at a high yield through pyrolysis. The invention is used for the five-component SiBCNZr ceramic precursor.

Description

Synthesis method of five-component SiBCNZr ceramic precursor
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a synthesis method of a five-component SiBCNZr ceramic precursor.
Background
With the development of science and technology, the performance requirements on high-temperature materials are higher and higher. Silicon-based ceramics (e.g. SiC, si) have been found 3 N 4 Etc.) has the advantages of high strength, high hardness, excellent oxidation resistance, thermal stability, chemical stability, etc., and is an important advanced high-temperature material. Silicon-based ceramic parts are manufactured using powder processing techniques including powder synthesis, powder processing (e.g., milling and mixing), molding, and sintering. Due to the intrinsic brittleness of ceramic materials and the rise of ceramic fibers, the preparation process of the traditional ceramics is gradually changed, and the development of ceramic precursors is advanced.
The key phenomenon of conversion of polymers to ceramics during pyrolysis provides an important avenue for the development of novel silicon-based ceramics, including coatings/films, small diameter fibers, ceramic matrix composites, dense monolithic bodies obtained at relatively low temperatures (1000-1300 ℃) and non-oxide ceramics that are stable up to 2000 ℃. Silicon-based ternary ceramics (e.g., siCN and SiOC), quaternary ceramics (e.g., siBCN, siBCO, siCNO, siAlCN, and SiAlCO), and even quinary ceramics (e.g., sifhbcn and siffcno) can also be conveniently produced using PDCs processes, and have heretofore been difficult to produce by other methods. Because PDCs have good structural and functional properties, as well as good machine-shaping capabilities, their application in many critical areas has received widespread attention.
Currently, there are research institutions for preparing ceramic precursors such as SiBOC, siHfOC, and SiZrBOC, but there are still few specific methods for preparing non-oxide SiBCNZr ceramic precursors. And the prepared SiBCN ceramic has the problem of poor oxidation resistance, and the research on the modified SiBCN ceramic is less.
Disclosure of Invention
The invention provides a synthesis method of a five-component SiBCNZr ceramic precursor, aiming at solving the problem of poor oxidation resistance of the SiBCN ceramic precursor prepared by the existing method.
A method for synthesizing a five-component SiBCNZr ceramic precursor comprises the following steps:
1. mixing methyl trichlorosilane and boron trichloride, and stirring for 0.5-1 h under an oil bath at the temperature of 1-3 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1 (3-5);
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Continuously stirring for 0.5-1 h under the oil bath with the temperature of 1-3 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 h at the temperature of 150-170 ℃ to obtain a precursor solution C;
4. reducing the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, increasing the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 h at the temperature of 150-180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the precursor solution C is 1 (10-20);
5. and putting the precursor D solution into an oven for curing to obtain the SiBCNZr ceramic precursor.
The invention has the beneficial effects that: the SiBCN-based precursor is prepared by crosslinking Zr and other elements in a SiBCN-based precursor, namely, si, N, B, C and Zr are connected through covalent bonds to form a precursor polymer containing a large amount of Si, B, N, C and Zr elements. In the process, the structure of the SiBCNZr ceramic precursor can be effectively adjusted through the molecular level design of the precursor, and the uniformity of element distribution in the precursor is ensured. And then removing small molecules from the precursor through a curing reaction to form a high polymer, and finally forming the SiBCNZr ceramic material with stable covalent bond connection through pyrolysis. The invention introduces Zr element into SiBCN precursor for modification and improves the oxidation resistance, and the oxidation product of SiBCNZr ceramic after high-temperature oxidation test mainly comprises ZrSiO 4 、ZrO 2 、SiO 2 Etc., and the products of SiBCN ceramics after high-temperature oxidation are mainly SiO 2 High temperature oxidation products ZrSiO of SiBCNZr ceramics in general terms 4 、ZrO 2 Has a specific SiO ratio 2 The melting point and the oxidation resistance are more excellent; therefore, the oxidation resistance can be effectively improved.
Drawings
FIG. 1 is an XRD pattern of the SiBCNZr ceramic precursor obtained in example 1 after cracking;
FIG. 2 is an XPS summary plot of the SiBCNZr ceramic precursor obtained in example 1 after cracking;
FIG. 3 is an XPS spectrum of Si after cracking of the SiBCNZr ceramic precursor obtained in example 1;
FIG. 4 is an XPS spectrum of B after cracking of the SiBCNZr ceramic precursor obtained in example 1;
FIG. 5 is an XPS spectrum of C after cleavage of the SiBCNZr ceramic precursor obtained in example 1;
FIG. 6 is an XPS spectrum of N after cracking of the SiBCNZr ceramic precursor obtained in example 1;
FIG. 7 is an XPS plot of Zr after cracking of the SiBCNZr ceramic precursor obtained in example 1;
FIG. 8 is an SEM image of the SiBCNZr ceramic precursor obtained in example 2 after cracking;
FIG. 9 is a TEM image of the SiBCNZr ceramic precursor obtained in example 3 after pyrolysis;
FIG. 10 is a graph of TG after cracking of the SiBCNZr ceramic precursor obtained in example 2;
FIG. 11 is a comparison of the XRD patterns of the SiBCNZr ceramic material and the SiBCN ceramic material of example 3 after high temperature oxidation; wherein 1 is SiBCNZr ceramic material, and 2 is SiBCN ceramic.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, but includes any combination of the specific embodiments.
The first embodiment is as follows: the synthesis method of the five-component SiBCNZr ceramic precursor in the embodiment is completed according to the following steps:
1. mixing methyl trichlorosilane and boron trichloride, and stirring for 0.5-1 h under an oil bath at the temperature of 1-3 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1 (3-5);
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Continuously stirring for 0.5-1 h under the oil bath with the temperature of 1-3 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 h at the temperature of 150-170 ℃ to obtain a precursor solution C;
4. reducing the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, increasing the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 h at the temperature of 150-180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the C is 1 (10-20);
5. and (4) putting the precursor D solution into an oven for curing to obtain the SiBCNZr ceramic precursor.
In this embodiment, si, N, B, C, and Zr are linked by covalent bonds to form a polymer precursor structure stabilized by the covalent bonds. Precursor polymers with different ceramic yields can be obtained according to different mass ratios of the added reagents.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and the low-temperature control of the oil bath in the step one is realized by adding ice blocks into the water bath kettle and arranging a circulating cooling device in the condensing pipe. The rest is the same as the first embodiment.
The present embodiment realizes low-temperature control by the cooperation of the ice cubes and the circulation cooling device.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the mass ratio of the methyltrichlorosilane to the boron trichloride is 1. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment mode and one of the first to third embodiment modes is: the rate of temperature rise in the third step is 20 ℃/h. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: in the third step, the reaction temperature of the precursor solution B is raised from 1-3 ℃ to 160 ℃, and the crosslinking is carried out for 5 hours under the condition that the temperature is 160 ℃. The rest is the same as one of the first to third embodiments.
The sixth specific implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the fourth step, the reaction temperature of the precursor solution C is reduced from 160 ℃ to 80 ℃. The rest is the same as one of the first to third embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to third embodiments is: in the fourth step, the reaction temperature is increased from 80 ℃ to 160 ℃, and crosslinking is carried out for 5 hours at the temperature of 160 ℃. The rest is the same as one of the first to third embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to third embodiments is: in the fourth step, the temperature reduction rate is 20 ℃/h, and the temperature rise rate is 20 ℃/h. The rest is the same as one of the first to third embodiments.
The specific implementation method nine: the difference between this embodiment mode and one of the first to third embodiment modes is: and in the fifth step, the curing temperature is 190-210 ℃, and the curing time is 8-12 h. The rest is the same as one of the first to third embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to third embodiments is: pyrolyzing the SiBCNZr ceramic precursor obtained in the fifth step to obtain a SiBCNZr ceramic material; the pyrolysis is to heat up to 1200-1400 ℃ at a heating rate of 5 ℃/min, preserve heat for 1h at the temperature of 1200-1400 ℃, and then cool down to room temperature at a cooling rate of 5 ℃/min; the yield of the SiBCNZr ceramic material is 50-58%. The rest is the same as one of the first to third embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the synthesis method of the five-component SiBCNZr ceramic precursor is completed according to the following steps:
1. mixing methyltrichlorosilane and boron trichloride, and stirring for 0.5h under an oil bath at the temperature of 3 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1;
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Stirring for 1h under the condition of oil bath with the temperature of 3 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 3 ℃ to 160 ℃ at a heating rate of 20 ℃/h, and crosslinking for 5h at the temperature of 160 ℃ to obtain a precursor solution C;
4. cooling the reaction temperature of the precursor solution C from 160 ℃ to 80 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 80 ℃ to 180 ℃, and crosslinking for 6 hours at the temperature of 180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the precursor solution C is 1;
5. putting the precursor D solution into an oven for curing to obtain a SiBCNZr ceramic precursor; the curing temperature is 190 ℃, and the curing time is 12h;
6. pyrolyzing the SiBCNZr ceramic precursor, heating to 1200 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h, then cooling to room temperature at a cooling rate of 5 ℃/min, wherein the yield is about 52 percent, and finally obtaining the SiBCNZr ceramic material.
Example 2: the synthesis method of the five-component SiBCNZr ceramic precursor is completed according to the following steps:
1. mixing methyltrichlorosilane and boron trichloride, and stirring for 0.5h under an oil bath at the temperature of 2 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1;
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Stirring for 1h under an oil bath at the temperature of 2 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 2 ℃ to 160 ℃ at a heating rate of 20 ℃/h, and crosslinking for 4h at the temperature of 160 ℃ to obtain a precursor solution C;
4. cooling the reaction temperature of the precursor solution C from 160 ℃ to 80 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 80 ℃ to 180 ℃, and crosslinking for 6 hours at the temperature of 180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the precursor solution C is 1.5;
5. putting the precursor D solution into an oven for curing to obtain a SiBCNZr ceramic precursor; the curing temperature is 200 ℃, and the curing time is 10h;
6. and (3) pyrolyzing the SiBCNZr ceramic precursor, heating to 1300 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h, and then cooling to room temperature at a cooling rate of 5 ℃/min, wherein the yield is about 58 percent, and finally obtaining the SiBCNZr ceramic material.
Example 3: the synthesis method of the five-component SiBCNZr ceramic precursor is completed according to the following steps:
1. mixing methyltrichlorosilane and boron trichloride, and stirring for 0.5h under an oil bath at the temperature of 3 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1;
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Stirring for 1h under the condition of oil bath with the temperature of 3 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 3 ℃ to 160 ℃ at a heating rate of 20 ℃/h, and crosslinking for 5h at the temperature of 160 ℃ to obtain a precursor solution C;
4. cooling the reaction temperature of the precursor solution C from 160 ℃ to 80 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 80 ℃ to 180 ℃, and crosslinking for 6 hours at the temperature of 180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the precursor solution C is 1;
5. putting the precursor D solution into an oven for curing to obtain a SiBCNZr ceramic precursor; the curing temperature is 210 ℃, and the curing time is 12h;
6. and (3) pyrolyzing the SiBCNZr ceramic precursor, heating to 1400 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h, and then cooling to room temperature at a cooling rate of 5 ℃/min, wherein the yield is about 54 percent, and finally the SiBCNZr ceramic material is obtained.
Experimental results show that the novel SiBCNZr five-component high-resistance alloy synthesized by the inventionThe main product of the warm ceramic precursor material after high-temperature pyrolysis, namely SiBCNZr ceramic, is mainly ZrSiO after a high-temperature oxidation test 4 、ZrO 2 、SiO 2 Etc. and the products of SiBCN ceramics of similar systems after high-temperature oxidation are mainly SiO 2 High temperature oxidation products ZrSiO of SiBCNZr ceramics in general terms 4 、ZrO 2 Compared with SiO 2 Has higher stability and oxidation resistance. Therefore, the oxidation resistance of the material can be effectively improved.

Claims (9)

1. A method for synthesizing a five-component SiBCNZr ceramic precursor is characterized in that the method for synthesizing the five-component SiBCNZr ceramic precursor is completed according to the following steps:
1. mixing methyl trichlorosilane and boron trichloride, and stirring for 0.5-1 h under an oil bath at the temperature of 1-3 ℃ to obtain a precursor solution A; the mass ratio of the methyl trichlorosilane to the boron trichloride is 1 (3-5);
2. adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N 2 Continuously stirring for 0.5-1 h under the oil bath with the temperature of 1-3 ℃ to obtain a precursor solution B; the mass of the hexamethyldisilazane is the same as that of the boron trichloride in the step one;
3. heating the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 h at the temperature of 150-170 ℃ to obtain a precursor solution C;
4. reducing the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, increasing the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 h at the temperature of 150-180 ℃ to obtain a precursor solution D; the mass ratio of the zirconocene dichloride to the C is 1 (10-20);
5. putting the precursor D solution into an oven for curing to obtain a SiBCNZr ceramic precursor, and pyrolyzing the SiBCNZr ceramic precursor to obtain a SiBCNZr ceramic material; the pyrolysis is to heat up to 1200-1400 ℃ at a heating rate of 5 ℃/min, preserve the temperature for 1h at 1200-1400 ℃, and then cool down to room temperature at a cooling rate of 5 ℃/min; the yield of the SiBCNZr ceramic material is 50-58%.
2. The method as claimed in claim 1, wherein the low temperature control of the oil bath in step one is achieved by adding ice blocks into the water bath and installing a cooling circulation device in the condenser tube.
3. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 1, wherein the mass ratio of said methyltrichlorosilane to boron trichloride in step one is 1.
4. The method of claim 1 wherein the temperature is raised at a rate of 20 ℃/hr.
5. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 4, wherein the reaction temperature of precursor solution B is raised from 1-3 ℃ to 160 ℃ in step three, and the precursor solution B is cross-linked for 5h at 160 ℃.
6. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 5, wherein the reaction temperature of the precursor solution C in the fourth step is decreased from 160 ℃ to 80 ℃.
7. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 6, wherein in the fourth step, the reaction temperature is raised from 80 ℃ to 160 ℃, and the cross-linking is carried out for 5h under the condition of 160 ℃.
8. The method as claimed in claim 1, wherein the temperature reduction rate is 20 ℃/h and the temperature increase rate is 20 ℃/h.
9. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 1, wherein the temperature of said solidifying in step five is 190-210 ℃ and the solidifying time is 8-12 h.
CN202111583211.9A 2021-12-22 2021-12-22 Synthesis method of five-component SiBCNZr ceramic precursor Active CN114213664B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111583211.9A CN114213664B (en) 2021-12-22 2021-12-22 Synthesis method of five-component SiBCNZr ceramic precursor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111583211.9A CN114213664B (en) 2021-12-22 2021-12-22 Synthesis method of five-component SiBCNZr ceramic precursor

Publications (2)

Publication Number Publication Date
CN114213664A CN114213664A (en) 2022-03-22
CN114213664B true CN114213664B (en) 2023-01-24

Family

ID=80705203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111583211.9A Active CN114213664B (en) 2021-12-22 2021-12-22 Synthesis method of five-component SiBCNZr ceramic precursor

Country Status (1)

Country Link
CN (1) CN114213664B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114804862B (en) * 2022-05-07 2023-05-05 中山大学 SiBCNMO nano-particles and preparation method thereof
CN115959911B (en) * 2022-12-30 2023-10-31 长安大学 Divinylbenzene cross-linked polymer converted amorphous SiBCN wave-absorbing ceramic and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050026769A1 (en) * 2003-08-01 2005-02-03 Jongsang Lee Process for SiBCN based preceramic polymers and products derivable therefrom
CN103333343A (en) * 2013-07-18 2013-10-02 中国人民解放军国防科学技术大学 Preparation method of poly-zirconium-boron-silazane precursor
CN105418071B (en) * 2015-07-28 2018-01-16 山东合创明业精细陶瓷有限公司 The synthetic method of high pure and ultra-fine ZrC SiC composite granules
CN107500766B (en) * 2017-09-19 2021-03-19 东华大学 Preparation method of amorphous silicon boron carbon nitrogen zirconium ceramic fiber
CN112174671B (en) * 2020-10-10 2022-07-29 黑龙江大学 Preparation method of high-temperature-resistant SiZrBOC quinary ceramic

Also Published As

Publication number Publication date
CN114213664A (en) 2022-03-22

Similar Documents

Publication Publication Date Title
CN114213664B (en) Synthesis method of five-component SiBCNZr ceramic precursor
CN110423119B (en) Preparation method of ablation-resistant C/SiC ceramic matrix composite
CN111454061B (en) Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic
CN101240070B (en) Method for synthesizing supercritical fluid of ceramic precursor polycarbosilane
CN111848172B (en) Molybdenum disilicide/silicon carbide three-dimensional polymer precursor ceramic and preparation method thereof
CN101186504B (en) Method for synthesizing tantalum-containing SiC ceramic precursor
CN101318821A (en) Method for manufacturing hafnium containing SiC ceramic precursor
CN104230345A (en) Preparation method of porous silicon nitride ceramic material
CN113149686B (en) Carbon/carbon composite material crucible with composite ceramic layer and preparation method thereof
CN109467450A (en) One kind containing Ti3SiC2The SiC of boundary layerfThe preparation method of/SiC ceramic matrix composite material
CN103613365A (en) Method for synthesizing silicon-oxygen-carbon ceramic material by utilizing polysiloxane resin
CN101734925B (en) Silicon nitride porous ceramics with controllable porosity and preparation method thereof
CN101219788A (en) Silicon carbide thin film forming device and silicon carbide thin film producing method
US5545687A (en) Preparation of high density boron carbide ceramics with preceramic polymer binders
CN115894041A (en) Preparation method of powder extrusion 3D printing molding reaction sintering silicon carbide ceramic
CN109133986B (en) Foaming-method-based AlN-SiC porous composite ceramic and preparation method thereof
CN109608235A (en) Gel infiltration ceramic modification method for C/C composite material special-shaped part
CN107057071A (en) The preparation method of polycarbosilane precusor
CN113880581B (en) Preparation method and application of four-component SiHfBC polymer ceramic precursor
CN114196019B (en) Preparation method of shape-plastic high-molecular ceramic precursor
CN103396125B (en) Preparation method for boron-carbon-nitrogen porous ceramic
CN112174671B (en) Preparation method of high-temperature-resistant SiZrBOC quinary ceramic
CN113788697A (en) Ceramic precursor slurry applicable to winding process and preparation method thereof
JP2931824B2 (en) Manufacturing method of silicon carbide ceramics
CN106187263A (en) The manufacture method of C/C SiC ceramic matrix composite material parts and C/C SiC ceramic matrix composite material parts

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