CN113061037B - Core-shell structure SiC converted from polysilazanexNyOzPreparation method of micro-spheres - Google Patents
Core-shell structure SiC converted from polysilazanexNyOzPreparation method of micro-spheres Download PDFInfo
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Abstract
The invention discloses core-shell structure SiC converted from polysilazanexNyOzA method for preparing microspheres, the method comprising: preparing divinyl benzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid; heating the mixed liquid for reaction, washing, and then carrying out vacuum filtration and vacuum drying to obtain initial powder; thirdly, sintering the initial powder under the protection of inert atmosphere to obtain core-shell structure SiC converted from polysilazanexNyOzAnd (4) micro-spheres. The invention obviously improves the core-shell structure SiC by controlling the polymerization temperature, the solute proportion and the sintering treatment temperature of the heating reactionxNyOzYield and high-temperature stability of micro-spheres and core-shell structure SiCxNyOzThe micron spheres are not agglomerated and are easy to disperse, have excellent oxidation resistance and good wave absorbing performance, and have wide application prospect in the field of high-temperature wave absorbing agents.
Description
Technical Field
The invention belongs to the technical field of preparation of micron ceramic powder, and particularly relates to core-shell structure SiC converted from polysilazanexNyOzA preparation method of micro-spheres.
Background
Along with the rapid development of the electromagnetic compatibility technology, the electromagnetic anti-interference technology and the military stealth technology of the civil Internet of things, the importance of the electromagnetic shielding wave-absorbing material is increasingly highlighted, and particularly, the electromagnetic shielding wave-absorbing material is used as a high-temperature component of an advanced weapon to be applied to a high-temperature wave-absorbing coating and a structural wave-absorbing material of an aircraft engine, a fighter tail nozzle, a cruise missile end cap and the like, and is a key for improving the national advanced weapon stealth technology. The material has the advantages of light weight, thin thickness, high electromagnetic wave absorption rate and wide effective absorption spectrum, and simultaneously, the material with high temperature resistance and oxidation resistance is the development and pursuit direction of the high-temperature electromagnetic wave-absorbing material in the future.
Modified or doped optimized polymer conversion ceramics are reported to have good wave absorbing properties: wang peng et al reported that C-SiC/Si prepared based on modification of polyvinylpyrrolidone and polycarbosilane3N4The composite material has good wave-absorbing performance, and the Effective Absorption Bandwidth (EAB) corresponding to a sample with the thickness of 2.5mm reaches 6.4 GHz.Duan et al prepared porous composite materials by introducing SiC nanowires based on polysiloxane-converted SiCO ceramics, and achieved 3.5GHz EAB when the thickness of the material was 2.83 mm. The preparation process of the material is relatively complex, and in addition, the oxidation resistance of the material is not commented on.
In order to further promote the practical application of the wave absorbing agent or the wave absorbing coating in the civil or military field, the preparation method and the process of the material need to be further simplified, and the comprehensive wave absorbing performance of the material needs to be further optimized, including increasing the EAB of the wave absorbing agent, further reducing the thickness of the wave absorbing material, improving the high-temperature stability and the oxidation resistance of the wave absorbing agent and the like.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a core-shell structure SiC converted from polysilazane for overcoming the disadvantages of the prior artxNyOzA preparation method of micro-spheres. The method comprises the steps of preparing SiC with a core-shell structure by using divinylbenzene, carbon-carbon double bond-containing polysilazane and 2, 2' -azobisisobutyronitrile as solutes and acetonitrile as a solvent through a heating reaction and sintering process in sequencexNyOzThe micron spheres obviously improve the core-shell structure SiC by controlling the polymerization temperature, solute proportion and sintering treatment temperature of heating reactionxNyOzYield and high-temperature stability of micro-spheres and core-shell structure SiCxNyOzThe micron spheres are not agglomerated and are easy to disperse, and the oxidation resistance is excellent.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the micro-spheres is characterized by comprising the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid;
the mass of divinylbenzene in the mixed liquid is 10-30% of the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds, the mass of 2, 2' -azobisisobutyronitrile is 1-3% of the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds, and the ratio of the mass of acetonitrile to the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds is 3: 1-7: 1;
step two, heating the mixed liquid obtained in the step one for reaction, then repeatedly washing the mixed liquid by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying; the heating reaction is carried out in a closed reaction kettle, the temperature of the heating reaction is (75-90 ℃) plus or minus 5 ℃, and the time is 10-16 h;
step three, sintering the initial powder obtained in the step two under the protection of inert atmosphere, and cooling to room temperature to obtain core-shell structure SiC converted from polysilazanexNyOzThe micro-spheres comprise 0.67 to 10.31 of x, 0.04 to 0.53 of y and 0.25 to 1.51 of z; the sintering temperature is 1250-1350 ℃.
The preparation method comprises the steps of preparing SiC with a core-shell structure by using Divinylbenzene (DVB), carbon-carbon double bond-containing Polysilazane (PSN) and 2, 2' -Azobisisobutyronitrile (AIBN) as solutes and acetonitrile as a solvent through a heating reaction and a sintering process in sequencexNyOzAnd (4) micro-spheres. According to the molecular structure research of DVB and PSN, the DVB has higher polymerization reaction probability at low temperature than PSN, so that the temperature of the heating reaction is controlled, the self-polymerization probability of DVB is higher than the polymerization probability of DVB and PSN, the polymerization probability of DVB and PSN is higher than the self-polymerization or solidification probability of PSN, and all solutes are polymerized to form an inner core in a polymer with the shape of a core-shell structure through the heating reaction, wherein DVB is polymerized preferentially to form the inner core at higher polymerization probability and higher polymerization rate, the polymerization probabilities and rates of DVB and PSN are reduced in sequence, and the three kinds of polymerization are combined to form the core-shell structure, so that the carbon content in the core-shell structure is higher, and the carbon content outside the core-shell structure is lower; the polymer microsphere increases in size and specific surface area along with the heating reaction, and the nucleation speed of the free radical polymerization reaction is increased by controlling the higher solute proportion in the mixed solution and the heating reaction temperatureEnsuring that the core is fully nucleated on the core to finally form a core-shell structure, wherein in the subsequent sintering treatment process, carbon in the core-shell structure is easy to react with a small amount of polymerized PSN, so that Si-C bonds are generated after the reaction of Si-N bonds in the core-shell structure, and finally the core-shell structure with more core carbon and less nitrogen or no nitrogen and more shell carbon is formed; in addition, the redundant solute in the product of the heating reaction is washed away by the aid of methanol and tetrahydrofuran capable of dissolving the solute, and the residual solvent is slowly volatilized by the cooperation of mild drying and slow temperature rise of vacuum drying, so that the SiC with the core-shell structurexNyOzThe micron sphere powder is not agglomerated and is easy to disperse, and finally the core-shell structure SiC is realizedxNyOzAnd (4) preparing the microspheres. The invention obviously improves the core-shell structure SiC by controlling the polymerization temperature of the heating reaction and the higher solute proportionxNyOzThe yield of the micron balls is improved, and meanwhile, the temperature of sintering treatment is controlled, so that the SiC is further improvedxNyOzHigh temperature stability of the microspheres.
The core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the microspheres is characterized in that in the step one, the mass of the divinylbenzene in the mixed liquid is 20% of the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 2% of the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane containing carbon-carbon double bonds is 4.8: 1. The preferred solute-solvent ratio is favorable for ensuring full nucleation on the inner core in the later polymerization stage in the heating reaction and is favorable for SiCxNyOzAnd (3) fully nucleating and growing the microspheres to form a core-shell structure.
The core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the microspheres is characterized in that the heating reaction in the step two is carried out in a closed reaction kettle, the temperature of the heating reaction is 90 +/-5 ℃, and the time is 16 h. The preferred temperature for the heating reaction is favorable to increase the nucleation rate and thus the polymerization rate, while the preferred reaction timeIs beneficial to shortening the process flow on the premise of ensuring the full reaction of all solutes.
The core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the microspheres is characterized in that the inert atmosphere in the third step is nitrogen.
The core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the micro-spheres is characterized in that the sintering temperature in the third step is 1300 ℃. The optimized sintering treatment temperature is favorable for further improving the core-shell structure SiCxNyOzThe stability of the micron sphere, and the excellent conductivity and dielectric parameter of the micron sphere are beneficial to the loss and absorption of electromagnetic waves, so that the micron sphere has good wave-absorbing performance.
Compared with the prior art, the invention has the following advantages:
1. the method takes divinylbenzene, polysilazane containing carbon-carbon double bonds and 2, 2' -azobisisobutyronitrile as solutes and acetonitrile as solvents to prepare SiC with a core-shell structure sequentially through a heating reaction and a sintering processxNyOzThe micron sphere obviously improves the core-shell structure SiC by controlling the polymerization temperature, the solute proportion and the sintering treatment temperature of the heating reactionxNyOzYield and high-temperature stability of micro-spheres and core-shell structure SiCxNyOzThe micron spheres are not agglomerated and are easy to disperse, and the oxidation resistance is excellent.
2. Core-shell structure SiC converted from polysilazane prepared by the inventionxNyOzThe yield of the micro-spheres can reach 7 percent, and the mass loss rate after the micro-spheres are treated in the inert atmosphere at 1000 ℃ is only 1 to 4 percent, so the micro-spheres have good wave absorbing performance and wide application prospect in the field of high-temperature wave absorbing agents.
3. The preparation method is simple, the technological parameters are easy to adjust, the requirement on equipment is low, and the large-scale production and engineering application are easy.
4. Core-shell structure SiC of the inventionxNyOzOf micro-spheresThe designability is high, the structure of the product can be conveniently adjusted through process parameters, the yield is high, the dispersibility is good, and the comprehensive wave-absorbing performance is excellent.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 shows SiC with core-shell structure prepared in example 1 of the present invention5.53N0.08O1.33TEM images of the microspheres.
FIG. 2 shows SiC with core-shell structure prepared in example 1 of the present invention5.53N0.08O1.33EDS elemental profile at the shell of the microsphere.
FIG. 3 shows SiC with core-shell structure prepared in example 1 of the present invention5.53N0.08O1.33EDS elemental profiles at the shell and core of the microspheres.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid; the mass of the divinylbenzene in the mixed liquid is 20% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 2% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 4.8: 1;
step two, placing the mixed liquid obtained in the step one in a closed reaction kettle, heating to 90 +/-5 ℃, reacting for 16 hours, then repeatedly washing by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying;
step three, heating the initial powder obtained in the step two to 1300 ℃ under the protection of nitrogen atmosphere for sintering treatment, and cooling to room temperature to obtain core-shell structure SiC converted from polysilazane5.53N0.08O1.33And (4) micro-spheres.
Through detection, the bookPolysilazane-converted core-shell structure SiC prepared in examples5.53N0.08O1.33The yield of the micron ball is 7.2 percent, and the core-shell structure SiC is obtained5.53N0.08O1.33The weight loss rate of the micron ball after being sintered to 1000 ℃ in the argon environment and then cooled to room temperature is only 3.4%.
FIG. 1 shows SiC with core-shell structure prepared in this example5.53N0.08O1.33TEM image of the microspheres, as can be seen from FIG. 1, the SiC5.53N0.08O1.33The micron ball is a core-shell mechanism, and the thickness of the shell is about 100 nm.
The core-shell structure SiC prepared in this example was subjected to EDS (in TEM test mode)5.53N0.08O1.33The shell, shell and core of the microsphere are analyzed respectively, and the obtained spectrograms are shown in fig. 2 and 3.
FIG. 2 shows SiC with core-shell structure prepared in this example5.53N0.08O1.33EDS element distribution diagram at shell of microsphere, FIG. 3 is SiC of core-shell structure prepared in this example5.53N0.08O1.33EDS element distribution diagram at the shell and core of the micron sphere, as can be seen from FIGS. 2 and 3, the SiC5.53N0.08O1.33The content of N element at the shell of the microsphere is obviously larger than that of N element at the shell and the core.
The core-shell structure SiC prepared in this example was subjected to XPS (electron spectroscopy) and EDS (X-ray spectroscopy in scanning electron microscopy, in SEM test mode) respectively5.53N0.08O1.33The microspheres were tested, and the results are shown in table 1.
TABLE 1
| Detection method | C(at％) | N(at％) | O(at％) | Si(at％) |
| XPS | 42.49 | 9.98 | 28.61 | 18.91 |
| EDS | 72.64 | 0 | 15.47 | 11.88 |
As can be seen from table 1, the XPS detection result contained N, and the EDS detection result contained no N; based on the detection depths of EDS and XPS, it can be seen from fig. 2 and 3 that the core-shell SiC prepared in this example has a core-shell structure5.53N0.08O1.33The shell of the micron sphere is a compound containing four elements of Si, C, N and O, and the core mainly contains the elements of Si, C and O, namely SiC5.53N0.08O1.33SiC with a shell2.25N0.53O1.51Cladding core SiC6.11O1.30The core-shell structure of (1).
Core-shell structure SiC based on EDS analysis under TEM and TEM5.53N0.08O1.33The structure of the microsphere is verified, and the detection difference of XPS and EDS (under SEM) is considered to indicate that the core-shell structure SiC can be shown by combining the analysis results of XPS and EDS5.53N0.08O1.33The core-shell structure of the microsphere can characterize the core-shell structure SiC based on the detection results of XPS and EDSxNyOzCore-shell structure of the microsphere.
Comparative example 1
The preparation method of this comparative example comprises the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid; the mass of the divinylbenzene in the mixed liquid is 20% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 2% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 16: 1;
step two, placing the mixed liquid obtained in the step one in a closed reaction kettle, heating to 90 +/-5 ℃, reacting for 16 hours, then repeatedly washing by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying;
step three, heating the initial powder obtained in the step two to 1300 ℃ under the protection of nitrogen atmosphere for sintering treatment, and cooling to room temperature to obtain the SiC converted from polysilazane12.22N0.25O1.40And (4) micro-spheres.
Upon examination, polysilazane-converted SiC prepared in this comparative example12.22N0.25O1.40The yield of the micro-spheres is 2.3 percent, and SiC is added12.22N0.25O1.40The weight loss rate of the micron ball after being sintered to 1000 ℃ in the argon environment and then cooled to room temperature is only 2.1%.
The SiC prepared in this comparative example was subjected to XPS (Electron Spectroscopy) and EDS (X-ray Spectroscopy in scanning Electron microscope, in SEM test mode) separately12.22N0.25O1.40The microspheres were tested, and the results are shown in Table 2.
TABLE 2
| Detection method | C(at％) | N(at％) | O(at％) | Si(at％) |
| XPS | 70.25 | 11.80 | 10.74 | 7.21 |
| EDS | 73.63 | 12.48 | 8.07 | 5.82 |
As can be seen from Table 2, the XPS and EDS detection results both contain N, and the detection difference of each element in the XPS and EDS detection results is small, and the side surface reflects SiC12.22N0.25O1.40The element difference gradient in the micron spheres is very small, which shows that the SiC prepared by the comparative example12.22N0.25O1.40The core-shell structure in the microspheres disappeared.
Comparing example 1 with comparative example 1, it can be seen that the solute-solvent ratio has a great influence on the structure of the powder, and only by controlling the proper solute-solvent ratio, the SiC having the core-shell structure can be obtained by sinteringxNyOzAnd (4) micro-spheres.
Example 2
The preparation method of this example includes the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid; the mass of the divinylbenzene in the mixed liquid is 10% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 1% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 3: 1;
step two, placing the mixed liquid obtained in the step one in a closed reaction kettle, heating to 75 +/-5 ℃, reacting for 10 hours, then repeatedly washing by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying;
step three, heating the initial powder obtained in the step two to 1250 ℃ under the protection of nitrogen atmosphere for sintering treatment, and cooling to room temperature to obtain core-shell structure SiC converted from polysilazane2.19N0.04O0.28And (4) micro-spheres.
Through detection, the polysilazane prepared in the embodiment is converted into core-shell structure SiC2.19N0.04O0.28The yield of the micron spheres is 2.3 percent, and the core-shell structure SiC is obtained2.19N0.04O0.28The weight loss rate of the micron ball after being sintered to 1000 ℃ in the argon environment and then cooled to room temperature is only 1.7%.
The core-shell structure SiC prepared in this example was subjected to XPS (electron spectroscopy) and EDS (X-ray spectroscopy in scanning electron microscopy, in SEM test mode) respectively2.19N0.04O0.28The microspheres were tested, and the results are shown in Table 3.
TABLE 3
SiC incorporating the core-shell structure of the present embodiment2.19N0.04O0.28XPS element of microsphereThe results of the distribution and the EDS element distribution showed that the SiC was obtained2.19N0.04O0.28The micron ball has a shell SiC0.67N0.25O0.45Cladding core SiC2.45O0.25The core-shell structure of (1).
Example 3
The preparation method of this example includes the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid; the mass of the divinylbenzene in the mixed liquid is 30% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 3% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 7: 1;
step two, placing the mixed liquid obtained in the step one in a closed reaction kettle, heating to 85 +/-5 ℃, reacting for 12 hours, then repeatedly washing by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying;
step three, heating the initial powder obtained in the step two to 1350 ℃ under the protection of nitrogen atmosphere for sintering treatment, and cooling to room temperature to obtain core-shell structure SiC converted from polysilazane8.94N0.06O1.10And (4) micro-spheres.
Through detection, the polysilazane prepared in the embodiment is converted into core-shell structure SiC8.94N0.06O1.10The yield of the micron spheres is 4.3 percent, and the core-shell structure SiC is obtained8.94N0.06O1.10The weight loss rate of the micron ball after being sintered to 1000 ℃ in the argon environment and then cooled to room temperature is only 2.6%.
The core-shell structure SiC prepared in this example was subjected to XPS (electron spectroscopy) and EDS (X-ray spectroscopy in scanning electron microscopy, in SEM test mode) respectively8.94N0.06O1.10The microspheres were tested and the results are shown in table 4.
TABLE 4
SiC incorporating the core-shell structure of the present embodiment8.94N0.06O1.10The XPS element distribution results and the EDS element distribution results of the micro spheres revealed that the SiC8.94N0.06O1.10The micron ball has a shell SiC1.15N0.38O0.79Cladding core SiC10.31O1.16The core-shell structure of (1).
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (4)
1. Core-shell structure SiC converted from polysilazanexNyOzThe preparation method of the micro-spheres is characterized by comprising the following steps:
preparing divinylbenzene, carbon-carbon double bond-containing polysilazane, 2' -azobisisobutyronitrile and acetonitrile into mixed liquid;
the mass of the divinylbenzene in the mixed liquid is 10-30% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 1-3% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 3: 1-7: 1;
step two, heating the mixed liquid obtained in the step one for reaction, then repeatedly washing the mixed liquid by adopting methanol and tetrahydrofuran, and obtaining initial powder after vacuum filtration and vacuum drying; the heating reaction is carried out in a closed reaction kettle, the temperature of the heating reaction is (75-90 ℃) plus or minus 5 ℃, and the time is 10-16 h;
step three, sintering the initial powder obtained in the step two under the protection of inert atmosphere, and cooling to room temperature to obtain core-shell structure SiC converted from polysilazanexNyOzMicrospheres, wherein x = 0.67-10.31, y = 0.04-0.53, and z = 0.25-1.51; the sintering treatment temperature is 1250-1350 ℃; the inert atmosphere is nitrogen.
2. The polysilazane-converted core-shell structure SiC according to claim 1xNyOzThe preparation method of the microspheres is characterized in that in the step one, the mass of the divinylbenzene in the mixed liquid is 20% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, the mass of the 2, 2' -azobisisobutyronitrile is 2% of the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds, and the ratio of the mass of the acetonitrile to the total mass of the divinylbenzene and the polysilazane with carbon-carbon double bonds is 4.8: 1.
3. The polysilazane-converted core-shell structure SiC according to claim 1xNyOzThe preparation method of the microspheres is characterized in that the heating reaction in the step two is carried out in a closed reaction kettle, the temperature of the heating reaction is 90 +/-5 ℃, and the time is 16 h.
4. The polysilazane-converted core-shell structure SiC according to claim 1xNyOzThe preparation method of the micro-spheres is characterized in that the sintering temperature in the third step is 1300 ℃.
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