CN114213664A - Synthesis method of five-component SiBCNZr ceramic precursor - Google Patents
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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
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 found3N4Etc.) 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 promoted.
The key phenomenon of conversion of polymers to ceramics during pyrolysis provides an important concept 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-. Silicon-based ternary ceramics (e.g., SiCN and SiOC), quaternary ceramics (e.g., SiBCN, SiBCO, SiCNO, siacn, and siaco), and even quinary ceramics (e.g., SiHfBCN and SiHfCNO) can also be conveniently produced using PDCs processes, which 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:
firstly, mixing methyltrichlorosilane 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);
secondly, adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N2Continuously 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;
thirdly, raising the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 hours at the temperature of 150-170 ℃ to obtain a precursor solution C;
fourthly, cooling the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 hours 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);
and fifthly, 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. Followed by de-miniaturization of the precursor by a curing reactionMolecules form high polymers, and finally the SiBCNZr ceramic material with stable covalent bond connection is formed 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 ZrSiO4、ZrO2、SiO2Etc., and the products of SiBCN ceramics after high-temperature oxidation are mainly SiO2High temperature oxidation product ZrSiO of SiBCNZr ceramics in general4、ZrO2Has a specific SiO ratio2The 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 cracking 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 cracking;
FIG. 10 is a graph of TG after cracking of the SiBCNZr ceramic precursor obtained in example 2;
FIG. 11 is a comparison of XRD patterns for SiBCNZr and SiBCN ceramic materials 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 between 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:
firstly, mixing methyltrichlorosilane 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);
secondly, adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N2Continuously 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;
thirdly, raising the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 hours at the temperature of 150-170 ℃ to obtain a precursor solution C;
fourthly, cooling the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 hours 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);
and fifthly, 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. The precursor polymer with different ceramic yield can be obtained according to the 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: 4. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: 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 mode and one of the first to third embodiment modes 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 mode and one of the first to third embodiment modes 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 mode and one of the first to third embodiment modes 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 mode and one of the first to third embodiment modes is: pyrolyzing the SiBCNZr ceramic precursor obtained in the fifth step to obtain a SiBCNZr ceramic material; the pyrolysis is carried out by heating to 1200-1400 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h at 1200-1400 ℃, and then cooling 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:
firstly, 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: 4;
secondly, adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N2Stirring 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;
thirdly, raising the reaction temperature of the precursor solution B from 3 ℃ to 160 ℃ at a rate of 20 ℃/h, and crosslinking for 5h at the temperature of 160 ℃ to obtain a precursor solution C;
fourthly, 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: 20;
fifthly, 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 12 h;
and sixthly, pyrolyzing the SiBCNZr ceramic precursor, heating to 1200 ℃ 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 52 percent, and finally the SiBCNZr ceramic material is obtained.
Example 2: the synthesis method of the five-component SiBCNZr ceramic precursor is completed according to the following steps:
firstly, 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: 4;
secondly, adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N2Stirring 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;
thirdly, raising the reaction temperature of the precursor solution B from 2 ℃ to 160 ℃ at a rate of 20 ℃/h, and crosslinking for 4h at the temperature of 160 ℃ to obtain a precursor solution C;
fourthly, 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: 12.5;
fifthly, 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 10 hours;
and sixthly, pyrolyzing the SiBCNZr ceramic precursor, heating to 1300 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, and then cooling to room temperature at the 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:
firstly, 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: 4;
secondly, adding hexamethyldisilazane into the precursor solution A dropwise through a constant-pressure separating funnel, and introducing N2Stirring 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;
thirdly, raising the reaction temperature of the precursor solution B from 3 ℃ to 160 ℃ at a rate of 20 ℃/h, and crosslinking for 5h at the temperature of 160 ℃ to obtain a precursor solution C;
fourthly, 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: 20;
fifthly, 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 12 hours;
and sixthly, 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 obtaining the SiBCNZr ceramic material.
Experimental results show that the invention synthesizes a novel five-component SiBCNZr high-temperature resistant ceramic precursor material, and the main product of the SiBCNZr ceramic after high-temperature cracking is ZrSiO4、ZrO2、SiO2Etc. and the products of SiBCN ceramics of similar systems after high-temperature oxidation are mainly SiO2High temperature oxidation product ZrSiO of SiBCNZr ceramics in general4、ZrO2Compared with SiO2Has higher stability and oxidation resistance. Therefore, the oxidation resistance of the material can be effectively improved.
Claims (10)
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:
firstly, mixing methyltrichlorosilane 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);
II, hexamethyl bisSilazane was added dropwise to the precursor solution A via a constant pressure separatory funnel, while N was added2Continuously 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;
thirdly, raising the reaction temperature of the precursor solution B from 1-3 ℃ to 150-170 ℃, and crosslinking for 4-6 hours at the temperature of 150-170 ℃ to obtain a precursor solution C;
fourthly, cooling the reaction temperature of the precursor solution C from 150-170 ℃ to 70-90 ℃, adding zirconocene dichloride into the precursor solution C, uniformly stirring, heating the reaction temperature from 70-90 ℃ to 150-180 ℃, and crosslinking for 4-6 hours 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);
and fifthly, putting the precursor D solution into an oven for curing to obtain the SiBCNZr ceramic precursor.
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 disposing a circulating cooling device in the condenser tube.
3. The method as claimed in claim 1, wherein the mass ratio of methyltrichlorosilane to boron trichloride in step one is 1: 4.
4. The method of claim 1 wherein the temperature is raised at a rate of 20 ℃/hr.
5. The method for synthesizing the five-component SiBCNZr ceramic precursor according to claim 4, wherein the reaction temperature of the precursor solution B in the third step is raised from 1-3 ℃ to 160 ℃, and the precursor solution B is crosslinked for 5 hours at the temperature of 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 the reaction temperature in step four is raised from 80 ℃ to 160 ℃ and the cross-linking is carried out for 5h at 160 ℃.
8. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 1, wherein the temperature decreasing rate in the fourth step is 20 ℃/h and the temperature increasing rate is 20 ℃/h.
9. The method for synthesizing a five-component SiBCNZr ceramic precursor as claimed in claim 1, wherein the curing temperature in step five is 190-210 ℃ and the curing time is 8-12 h.
10. The method for synthesizing a five-component SiBCNZr ceramic precursor according to claim 1, wherein the SiBCNZr ceramic precursor obtained in the step five is pyrolyzed to obtain a SiBCNZr ceramic material; the pyrolysis is carried out by heating to 1200-1400 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 1h at 1200-1400 ℃, and then cooling to room temperature at a cooling rate of 5 ℃/min; the yield of the SiBCNZr ceramic material is 50-58%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114804862A (en) * | 2022-05-07 | 2022-07-29 | 中山大学 | SiBCNMO nano-particles and preparation method thereof |
| CN115959911A (en) * | 2022-12-30 | 2023-04-14 | 长安大学 | Divinylbenzene crosslinked polymer converted amorphous SiBCN wave-absorbing ceramic and preparation method thereof |
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| CN114804862A (en) * | 2022-05-07 | 2022-07-29 | 中山大学 | SiBCNMO nano-particles and preparation method thereof |
| CN115959911A (en) * | 2022-12-30 | 2023-04-14 | 长安大学 | Divinylbenzene crosslinked polymer converted amorphous SiBCN wave-absorbing ceramic 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 |
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