CN114804886B - Preparation method of carbon-modified nano silicon carbide composite material and application of carbon-modified nano silicon carbide composite material as radiation detector material - Google Patents
Preparation method of carbon-modified nano silicon carbide composite material and application of carbon-modified nano silicon carbide composite material as radiation detector material Download PDFInfo
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Abstract
The invention belongs to the field of silicon carbide composite materials, and particularly relates to a preparation method of a carbon modified nano silicon carbide composite material and application of the carbon modified nano silicon carbide composite material as an irradiation detector material. The preparation of the composite material comprises the following steps: 1) Ball-milling and mixing a silicon carbide precursor, a pretreated silicon carbide precursor and a nano carbon material to prepare mixed powder; the silicon carbide precursor is selected from polycarbosilane or a mixture of polycarbosilane and divinylbenzene; 2) Pressing the mixed powder into a green body, crosslinking and solidifying under vacuum or inert gas, and then cracking at 900-1600 ℃. According to the invention, the carbon modified nano silicon carbide composite material is prepared by a silicon carbide precursor conversion method, and compared with SiC monocrystal, the carbon modified nano silicon carbide composite material has better irradiation resistance; the obtained material can meet the requirements of a new generation of radiation detector in future nuclear application (high temperature and high dosage).
Description
Technical Field
The invention belongs to the field of silicon carbide composite materials, and particularly relates to a preparation method of a carbon modified nano silicon carbide composite material and application of the carbon modified nano silicon carbide composite material as an irradiation detector material.
Background
The development of nuclear radiation detectors is one of the marks of nuclear technology development and is also a mark of the national nuclear technology level. The working principle of the radiation detector is based on the interaction of particles with a substance. Compared with the common detector, the irradiation detector not only requires high material efficiency and high reliability, but also requires the characteristics of good irradiation resistance, large forbidden bandwidth, structural durability in irradiation environment and the like.
Conventional semiconductor radiation detector materials are made of germanium (Ge) and silicon (Si). In the 90 s of the 20 th century, high quality single crystal silicon carbide (SiC) wafers were commercialized, gradually replacing Ge and Si, and increasingly being used in radiation detectors. The SiC has the characteristics of good high-temperature mechanical property, oxidation resistance, corrosion resistance, high charge mobility, high saturation drift speed and high critical breakdown electric field, and has good irradiation tolerance, so that the SiC is a preferable irradiation-resistant material for fourth-generation reactors and fusion reactors, and is particularly suitable for manufacturing electronic devices used in high-power and extreme (high-pressure, high-temperature and irradiation) environments.
With the continuous development of nuclear reactors, higher irradiation temperature (800-1000 ℃) and larger irradiation dose have higher requirements on the materials of an irradiation detector, the service life of the detector is more than or equal to 15 years, and single crystal SiC is replaced by new generation materials. The degradation of material properties due to irradiation has become a critical issue affecting detector lifetime.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-modified nano silicon carbide composite material, which has good irradiation resistance and meets the higher requirements of an irradiation detector in a nuclear environment on the material.
The second object of the invention is to provide the application of the carbon modified nano silicon carbide composite material obtained by the method as an irradiation detector material.
In order to achieve the above purpose, the technical scheme of the preparation method of the carbon modified nano silicon carbide composite material of the invention is as follows:
the preparation method of the carbon modified nano silicon carbide composite material comprises the following steps that the molar ratio of C/Si in the carbon modified nano silicon carbide composite material is 1.3-2.0:
1) Ball-milling and mixing a silicon carbide precursor, a pretreated silicon carbide precursor and a nano carbon material to prepare mixed powder; the silicon carbide precursor is selected from polycarbosilane or a mixture of polycarbosilane and divinylbenzene, wherein the mass ratio of the divinylbenzene in the mixture is not more than 20%; the pretreatment of the silicon carbide precursor is to heat treat the silicon carbide precursor for 3-5 hours at 200-500 ℃ under vacuum or inert gas;
in the mixed powder, the mass ratio of the untreated silicon carbide precursor to the pretreated silicon carbide precursor is 1/5-1/3; the volume percentage of the nano carbon material in the carbon modified nano silicon carbide composite material is below 6.4%;
2) Pressing the mixed powder into a green body, crosslinking and solidifying under vacuum or inert gas, and then cracking at 900-1600 ℃.
According to the invention, the carbon modified nano silicon carbide composite material is prepared by a silicon carbide precursor conversion method, and compared with SiC monocrystal, the carbon modified nano silicon carbide composite material has better irradiation resistance; the obtained material can meet the requirements of a new generation of radiation detector in future nuclear application (high temperature and high dosage).
Compared with the traditional monocrystalline silicon carbide, the nano SiC has a large number of interfaces, the interfaces can change the migration path of defects, capture point defects generated in the irradiation process, release the point defects again, and improve the recombination with vacancies in the range of a few nanometers near the interfaces, so that the self-healing capacity of the material is improved, and excellent anti-irradiation performance is shown. In addition, the conductivity range of the carbon modified nano silicon carbide composite material accords with the room temperature semiconductor radiation detector material pairConductivity (1X 10) -10 S/cm～1×10 -1 S/cm).
Step 1) adopts the silicon carbide precursor and the pretreated silicon carbide precursor to mix, on one hand, the requirement of later blank making is met, on the other hand, the silicon carbide precursor is subjected to pretreatment to generate certain degree of crosslinking and organic substance decomposition, and the untreated precursor provides a bonding effect, so that the porosity in a final product can be effectively reduced. In order to better consider the molding and the compactness, the temperature rising speed during the heat treatment is preferably controlled to be 1-3 ℃/min.
In the step 1), the ball milling and mixing are carried out by ball milling and mixing the silicon carbide precursor and the pretreated silicon carbide precursor until the particle size is 1-2 mu m, and then adding the nano carbon material for secondary ball milling and mixing, wherein the nano carbon material is the nano carbon material. The ball-material ratio during ball milling can be controlled to be 2:1-10:1. Ball milling before adding the nano carbon material can adopt planetary ball milling or high-energy ball milling, the rotating speed of the planetary ball milling can be controlled to be 200-300 rpm, and the ball milling time is 18-36 h; the high-energy ball milling can be controlled at 1800rpm, and the ball milling time is 5-15 min. After ball milling, powder with average grain diameter of 1-2 μm is obtained. After adding the nano carbon material, the rotating speed can be controlled to be 80-150 rpm, and the ball milling time is 4-8 h. To reduce impurity incorporation, an agate milling pot and agate milling media should be preferred.
The nano carbon material belongs to a modified component, and the thermal conductivity, the electrical property, the irradiation resistance and the like of the material can be adjusted by doping a proper amount of the nano carbon material, so that the use requirement of an irradiation detector is met, and preferably, in the step 1), the volume percentage of the nano carbon material in the carbon modified nano silicon carbide composite material is 1.6-6.4%. Such as may be 1.6vol.%, 3.2vol.%, 4.8vol.%, 6.4vol.% unequal. Preferably, the nano carbon material is one or more selected from carbon nanotubes, nanodiamond, onion carbon and graphene.
In the step 2), in order to achieve better crosslinking and curing effects and promote the formation of compact products, preferably, the crosslinking and curing are carried out by firstly preserving heat for at least 6 hours at 150-200 ℃, then raising the temperature to 300-400 ℃ and preserving heat for 1-3 hours. The crosslinking curing is carried out under vacuum or inert gas to reduce the introduction of oxygen in the heat treatment process and avoid the decrease of the irradiation resistance of the product caused by the overlarge oxygen content. The time for heat preservation at 150 to 200 ℃ is more preferably 6 to 8 hours.
When in crosslinking and curing, the temperature is raised from 150 ℃ to 200 ℃ to 300 ℃ to 400 ℃ at a speed of 50 ℃ to 100 ℃/min. The temperature rising from 300-400 ℃ to 900-1600 ℃ is 100-200 ℃/min. In order to obtain nanocrystalline SiC ceramic, a certain mechanical property of the product is ensured, and the cracking temperature is preferably 1150-1400 ℃. The time of cleavage is preferably 2 to 4 hours. Preferably, the temperature is reduced to 300-500 ℃ at 1-3 ℃/min after cracking, and then the furnace is cooled.
Aiming at the scheme that the silicon carbide precursor is a mixture of polycarbosilane and divinylbenzene, the addition of the divinylbenzene can carry out carbon modification on polycarbosilane molecules at the precursor scale, so that the cracked nano SiC contains pyrolytic carbon with adjustable content. The mass ratio of the divinylbenzene in the silicon carbide precursor is not more than 20%. The adoption of the scheme of the mixture has the effect of improving the anti-radiation performance.
In order to further optimize the pressing effect, preferably, the pressing comprises uniaxial pressing and cold isostatic pressing, wherein the pressure of the uniaxial pressing is 100-200 MPa, and the pressure is maintained for 1-2 min; the pressure of the cold isostatic pressing is 200-300 MPa, and the pressure is maintained for 1-2 min. Through the pressing process, a regular green body with the diameter of 12-20 mm and the thickness of 1-3 mm can be obtained, and the regular green body is a wafer with a certain thickness.
The material obtained by the preparation method of the carbon modified nano silicon carbide composite material is applied to the radiation detector material.
The ceramic wafer obtained by the preparation method is polished on the surface, so that the roughness is less than or equal to 1 mu m, and the requirements of the detector on the optical cleanliness are met.
The carbon modified nano silicon carbide composite material has excellent structural stability and performance durability, and the detector prepared from the material has wide working range and is applicable to different irradiation temperatures and particle types (electrons, heavy ions and neutrons). The method can be applied to an extreme irradiation environment with irradiation damage dose of more than or equal to 0.1dpa, wherein the irradiation temperature ranges from room temperature to 1000 ℃, and the irradiation particles comprise neutrons, electrons and heavy ions.
Drawings
FIG. 1 is a graph showing the response of PL (Photoluminescence) peak shift change of the carbon-modified nano-silicon carbide composite material of example 1 of the present invention to material structure change in an irradiation environment;
FIG. 2 is a graph showing the response of the PL (Photoluminescence) peak intensity and peak area variation of the carbon-modified nano-silicon carbide composite material of example 1 of the present invention to the structural variation of the material in the irradiation environment;
FIG. 3 is a diagram showing a potential application of a metastable material structure at 1150 ℃ in a detector material; NC-G is the abbreviation of nanocrystalline graphite;
FIG. 4 shows I of the material before and after irradiation with different amounts of carbon nanotubes D /I G Rate of change;
FIG. 5 shows the conductivity variation of different carbon nanotube doping materials;
FIG. 6 shows the Vickers hardness variation of materials doped with different carbon nanotubes.
Detailed Description
Embodiments of the present invention will be further described with reference to the following specific examples.
In the following examples, polycarbosilane and nanocarbon materials are commercially available. The volume percentage is calculated by the theoretical volume obtained by converting the mass and the theoretical density value.
The polycarbosilane has the molecular formula (C) 2 H 6 Si) n In examples 1 to 5 below, solid polycarbosilanes having a molecular weight of 1400 to 1800 were purchased from Soxhlet group Co., ltd. In example 6, liquid polycarbosilane having a molecular weight of 1050 to 1600 was purchased from the institute of chemistry, national academy of sciences. However, the present invention is not limited to a particular type, nor is it limited to the state of polycarbosilane.
The specification of the multi-wall carbon nano tube is 10-30 nm in diameter, 5-20 nm in length and 99% in purity. The specification of onion carbon is particle size <10nm, and purity is 99%. The specification of the nano diamond is that the particle size is less than 10nm and the purity is 99 percent. The specification of the graphene is multi-layer graphene, the thickness of the layer is 1.5-3 nm, and the purity is 99%.
1. Specific examples of the method for preparing the carbon-modified nano silicon carbide composite material of the present invention
Example 1
The preparation method of the carbon-modified nano silicon carbide composite material of the embodiment comprises the following steps:
1) Taking Polycarbosilane (PCS) as a silicon carbide precursor, and heating to 400 ℃ at a heating rate of 1 ℃/min under argon atmosphere, and preserving heat for 3 hours to obtain a pretreated silicon carbide precursor; the pretreatment silicon carbide precursor and the silicon carbide precursor which is not subjected to heat treatment are mixed according to the mass ratio of 3:1, and then ball milling and mixing in a planetary ball mill, wherein the ball-to-material ratio is 5:1, the ball milling speed is 300rpm, the ball milling time is 18 hours, and the average granularity of PCS mixed powder after ball milling is 1 mu m; then adding multi-wall carbon nano tube (the adding amount is 3.2% of the total volume of PCS mixed powder), the ball milling speed is 100rpm, and the ball milling time is 6h. In the mixed powder, the molar ratio of C/Si is 1.8;
2) Sieving and granulating the powder obtained in the step 1), and performing uniaxial compression molding at 100MPa for 1min; and then carrying out cold isostatic pressing, wherein the pressure is 200MPa, the dwell time is 1min, and the wafer blank with the diameter of 16mm and the thickness of 2mm is obtained.
3) And (3) crosslinking and curing the blank for 6 hours at the temperature of 200 ℃ under vacuum, heating to 400 ℃ at the speed of 100 ℃/min under argon, preserving heat for 1 hour, continuously heating to 1400 ℃ at the speed of 200 ℃/min, preserving heat for 4 hours, cooling to 300 ℃ at the speed of 2 ℃/min, and cooling with a furnace.
The sample density prepared in this example was 2.28g/cm 3 The porosity was 2.1%.
On the basis of the embodiment, as a simple modification, the addition amounts of the multiwall carbon nanotubes were adjusted to 1.6vol.%, 4.8vol.%, 6.4vol.%, respectively, so as to obtain the corresponding carbon-modified nano silicon carbide composite material.
On the basis of the present example, the conditions of the heat treatment for preparing the pre-treated silicon carbide precursor may be adjusted accordingly, for example, it may be adjusted to 200 ℃ for 5 hours or 500 ℃ for 3 hours. The mass ratio of the pretreated silicon carbide precursor to the untreated silicon carbide precursor may be adjusted to be 4:1 or 5:1. The uniaxial pressing can be carried out for 2min under 200 MPa; the cold isostatic pressing conditions may be maintained at 300MPa for 2min.
When the cross-linking is cured, the temperature can be kept at 150 ℃ for 6 hours, and then the temperature is raised to 300 ℃ for 3 hours at the speed of 100 ℃/min. The thermal cracking conditions can be 1h at 1600 ℃ and 2h at 1500 ℃. After cleavage, the mixture may be cooled to 400℃at a rate of 1℃per minute.
Example 2
The preparation method of the carbon-modified nano silicon carbide composite material in this embodiment is different from that in embodiment 1 in that in step 3), the cracking temperature is 1150 ℃.
As a simple variant of the embodiment, the cracking temperature is respectively adjusted to 900 ℃, 1000 ℃, 1200 ℃, 1300 ℃,1500 ℃ and 1600 ℃, and the corresponding carbon-modified nano silicon carbide composite material can be obtained.
Example 3
The preparation method of the carbon-modified nano silicon carbide composite material of the present embodiment is different from that of embodiment 1 in that in step 1), the nano carbon material used is nano diamond.
As a simple modification of this example, the doping amounts of nanodiamond were 1.6vol.%, 4.8vol.%, 6.4vol.%, respectively.
Example 4
The preparation method of the carbon-modified nano silicon carbide composite material of the present embodiment is different from that of embodiment 1 in that in step 1), the nano carbon material used is onion carbon.
As a simple modification of this example, the doping amounts of onion carbon were adjusted to 1.6vol.%, 4.8vol.%, 6.4vol.%, respectively.
Example 5
The preparation method of the carbon-modified nano silicon carbide composite material of the present embodiment is different from that of embodiment 1 in that in step 1), the nano carbon material used is graphene.
As a simple modification of the present embodiment, the doping amounts of the adjustable graphene were 1.6vol.%, 4.8vol.%, 6.4vol.%, respectively.
Example 6
The preparation method of the carbon-modified nano silicon carbide composite material in this embodiment is different from that in embodiment 1) in that in step 1), a silicon carbide precursor is formed by mixing liquid Polycarbosilane (PCS) and Divinylbenzene (DVB), and the mass ratio of PCS to DVB is 80:20.
the product obtained in this example has a C/Si of 1.5 and a density of 2.4g/cm 3 The porosity was 13.6%.
As a simple variation of this embodiment, the mass ratio of PCS to DVB may be adjusted to 90:10.
2. specific examples of the application of the carbon-modified nano silicon carbide composite material of the present invention as a radiation detector material
Example 7
The application of the carbon modified nano silicon carbide composite material as the irradiation detector material in the embodiment polishes the surface of the ceramic wafer obtained in the step 3) of the embodiment 1 to 1 mu m and prepares the ceramic wafer into a certain size, thereby meeting the requirements of the detector on optical cleanliness and the like. Au with 2MeV at room temperature 2+ And irradiating the material to be detected, wherein the irradiation dose is 1dpa. Photoluminescence performance detection (PL) was then performed to test for signal characteristic changes before and after irradiation.
In other application cases, the irradiation particles can be replaced with He on the basis of example 7 + 、Ar + 、C 2+ Such as heavy ions, electrons, neutrons, etc.; the irradiation temperature can be changed to any temperature less than or equal to 1000 ℃.
3. Experimental example
Experimental example 1
The irradiation response function of the carbon-modified nano silicon carbide composite material obtained in example 1 is evaluated, photoluminescence performance test is carried out on the material, the excitation wavelength is 325nm, the characteristic peak appears at 441nm, the reduced energy is 2.81eV, the peak shift and the intensity change before and after irradiation are carried out, and the results are shown in fig. 1 and fig. 2.
As can be seen from fig. 1 and fig. 2, at 1200 ℃, the photoluminescence characteristics are greatly changed due to the fact that the structure tends to be metastable and sensitive to radiation-induced defects and disorder, and the luminescence characteristics have a radiation response function.
Fig. 3 shows a potential application of a metastable material structure at 1150 ℃ in a detector material. After the sample is irradiated, an ion spot (ionrack) structure exists, nanocrystalline graphite (NC-G) is arranged around the ion spot, the structure is sensitive to irradiation dose and temperature change, and the ion spot ion sensor has potential application in the aspect of an irradiation sensor.
Experimental example 2
To better illustrate the effect of cracking temperature on silicon carbide nanocrystalline size, the grain size of pure PCS at different cracking temperatures was analyzed without adding nanocarbon material on the basis of example 1, and the results are shown in table 1.
TABLE 1 grain size of pure PCS at different cracking temperatures
The results in Table 1 show that after cracking of pure PCS at 1150-1500 ℃, the grain size of the resulting silicon carbide grows slowly with increasing cracking temperature, and the grain size at 1500 ℃ is controlled within 13 nm.
Experimental example 3
Based on example 1, I of the material before and after irradiation under the condition of multi-wall carbon nanotubes with different doping amounts D /I G The rate of change and the results are shown in FIG. 4.
I D /I G The change rate means the damage degree of the sample before and after irradiation, and can be used for explaining the damage condition and the irradiation resistance of the sample. The results show that when the blending amount is 3.2 vol% D /I G The change is minimal, and the sample has the best irradiation resistance.
Experimental example 4
Based on the example 2 (cracking temperature: 1150 ℃ C.), the conductivity change of the obtained material was examined with different amounts of carbon nanotubes, and the results are shown in FIG. 5.
Fig. 5 shows that the conductivity increases significantly after carbon nanotube incorporation, and that the conductivity is maximized at an incorporation level of 3.2 vol.%. At this time, the carbon nanotubes are most uniformly dispersed, and the material density is the greatest.
Experimental example 5
Based on the example 1 (cracking temperature 1400 ℃), the change of the Vickers hardness of the obtained material at different carbon nanotube doping amounts was studied, and the result is shown in FIG. 6.
In fig. 6, the hardness after doping the carbon nanotubes increases and decreases, and the hardness is about 14GPa at the maximum when the doping amount is 3.2 vol.%. The addition of a small amount of carbon nanotubes increases the hardness of the sample, but the carbon nanotubes are agglomerated with the addition of an increased amount, resulting in a significant decrease in hardness.
By utilizing the method, the nano silicon carbide is prepared through the silicon carbide precursor, so that the interface volume fraction of the material is increased, the point defect generated by radiation is absorbed, then the point defect is released again and is compounded with vacancies in the range of a few nanometers near the interface, the self-healing capacity of the material is improved, the radiation resistance of the material is further improved, and the service life of the material is prolonged. In addition, by doping carbon nano-tubes and other nano-carbon materials, the thermal conductivity and the electrical conductivity of the material can be improved, the performance degradation of the irradiated material can be improved, and the performance stability can be improved.
Claims (8)
1. The preparation method of the carbon modified nano silicon carbide composite material is characterized in that the molar ratio of C/Si in the carbon modified nano silicon carbide composite material is 1.3-2.0, and the preparation method comprises the following steps:
1) Ball-milling and mixing a silicon carbide precursor, a pretreated silicon carbide precursor and a nano carbon material to prepare mixed powder; the silicon carbide precursor is selected from polycarbosilane or a mixture of polycarbosilane and divinylbenzene, wherein the mass ratio of the divinylbenzene in the mixture is not more than 20%; the pretreatment of the silicon carbide precursor is to heat treat the silicon carbide precursor for 3-5 hours at 200-500 ℃ under vacuum or inert gas;
in the mixed powder, the mass ratio of the untreated silicon carbide precursor to the pretreated silicon carbide precursor is 1/5-1/3; the volume percentage of the nano carbon material in the carbon modified nano silicon carbide composite material is 1.6-6.4%;
2) Pressing the mixed powder into a green body, crosslinking and solidifying under vacuum or inert gas, and then cracking at 900-1600 ℃.
2. The method for preparing a carbon-modified nano silicon carbide composite material according to claim 1, wherein in the step 1), the ball-milling mixing is performed by firstly ball-milling mixing a silicon carbide precursor and a pretreated silicon carbide precursor to a particle size of 1-2 μm, and then adding a nano carbon material for secondary ball-milling mixing.
3. The method for preparing a carbon-modified nano silicon carbide composite material according to claim 1, wherein the nano carbon material is one or more selected from the group consisting of carbon nanotubes, nanodiamonds, onion carbon and graphene.
4. The method for preparing a carbon-modified nano silicon carbide composite material according to claim 1, wherein the cross-linking and curing is performed by firstly preserving heat at 150-200 ℃ for at least 6 hours, then raising the temperature to 300-400 ℃ and preserving heat for 1-3 hours.
5. The method for preparing a carbon-modified nano silicon carbide composite material according to claim 1, wherein the cracking is performed at 900-1600 ℃ for 1-4 hours.
6. The method for preparing a carbon-modified nano silicon carbide composite material according to claim 1 or 5, wherein the temperature is reduced to 300-400 ℃ at 1-3 ℃/min after cracking, and then the carbon-modified nano silicon carbide composite material is cooled along with the furnace.
7. The method for preparing a carbon-modified nano silicon carbide composite material according to any one of claims 1 to 5, wherein the pressing comprises uniaxial pressing and cold isostatic pressing, the uniaxial pressing pressure is 100 to 200MPa, and the pressure is maintained for 1 to 2 minutes; the pressure of the cold isostatic pressing is 200-300 MPa, and the pressure is maintained for 1-2 min.
8. Use of a material obtained by the method for preparing a carbon-modified nano silicon carbide composite material according to any one of claims 1 to 7 as a radiation detector material.
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