CN115724664B - Method for rapidly preparing MCMBs/SiC composite material through two-step sintering - Google Patents
Method for rapidly preparing MCMBs/SiC composite material through two-step sintering Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 64
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Abstract
The invention relates to a method for rapidly preparing an MCMBs/SiC composite material by two-step sintering, which comprises the following steps: (1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesophase carbon microsphere MCMBs and boron carbide powder into an organic solvent, performing ball milling, mixing uniformly, drying and sieving to obtain raw material powder; (2) Carrying out pyrolysis treatment on the obtained raw material powder for 0.5-2 hours at 600-1200 ℃ in vacuum or protective atmosphere to obtain pyrolysis powder; (3) Placing the obtained pyrolysis powder in an SPS mold, and performing spark plasma sintering by adopting a two-step sintering method to obtain the MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to raise the temperature from room temperature to 1400 deg.c and the second step is to raise the sintering temperature from 1400 deg.c to 1400 deg.c.
Description
Technical Field
The invention relates to a method for rapidly preparing an MCMBs/SiC composite material by two-step sintering, and belongs to the technical field of composite materials.
Background
With the increasing prominence of environmental and energy problems, the high and new technology industries such as nuclear power and the like develop rapidly. The mechanical seal is one of three key components of a main pump of a shaft seal type nuclear reactor, is important equipment for preventing a reactor loop coolant from leaking to the atmosphere through a rotating pump shaft, and has the characteristics of high manufacturing precision requirement, high technical content, high material performance requirement and the like.
The silicon carbide ceramic wear-resistant sealing element is suitable for severe application environments such as high temperature, high pv value and vacuum due to the excellent performances such as high hardness, high strength, wear resistance, corrosion resistance, high thermal conductivity, oxidation resistance and the like, but under the dry friction condition, the friction coefficient and the wear rate of a pure silicon carbide material are higher, so that the material has the risk of damage failure in the working process, and in order to ensure the safe operation of the sealing element and have longer service life, the sealing material is required to have a low and stable friction coefficient under the dry friction working condition, and the lower wear rate is required to have good self-lubricating performance. The second-phase mesophase carbon microspheres are added into the silicon carbide matrix material, so that the friction coefficient under the dry friction condition can be remarkably reduced, and the SiC/MCMBs composite material with good self-lubricating performance can be obtained.
Disclosure of Invention
To this end, the invention provides a method for rapidly preparing MCMBs/SiC composite material by two-step sintering, comprising the following steps:
(1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesophase carbon microsphere MCMBs and boron carbide powder into an organic solvent, performing ball milling, mixing uniformly, drying and sieving to obtain raw material powder;
(2) Carrying out pyrolysis treatment on the obtained raw material powder for 0.5-2 hours at 600-1200 ℃ in vacuum or protective atmosphere to obtain pyrolysis powder;
(3) Placing the obtained pyrolysis powder in an SPS mold, and performing spark plasma sintering by adopting a two-step sintering method to obtain the MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to raise the temperature from room temperature to 1400 deg.c and the second step is to raise the sintering temperature from 1400 deg.c to 1400 deg.c.
In the previous investigation, the inventors first thought that the MCMBs/SiC composite (or MCMBs/SiC self-lubricating composite) was prepared by hot-pressed sintering. Although hot-pressed sintering is beneficial to mass transfer processes such as contact, diffusion, flow and the like of powder particles in the sintering process due to simultaneous heating and pressurizing, the obtained sintered body has higher density. However, the method has high requirements on the die and high production cost and low production efficiency, and is limited by process conditions, so that the wide application of the self-lubricating composite material in actual production is limited. The inventor considers that the MCMBs cooked spheres have better conductivity after graphitization treatment in production and manufacture, creatively adopts a spark plasma sintering technology, and prepares the MCMBs/SiC composite material with higher density and excellent performance at lower temperature and pressure by an electric field assisted and two-step sintering method. In the invention, the intermediate phase carbon microspheres in the MCMBs/SiC composite material are modified by the silicon carbide polymer precursor so as to crack at the interface of the SiC and the intermediate phase carbon microspheres to form silicon carbide microcrystals and free carbon, thereby improving the two-phase interface strength of the SiC and the MCMBs.
Preferably, the addition amount of the liquid polycarbosilane is 1-9 wt% of the total mass of the raw material powder;
the silicon carbide content is 60-68wt% of the total mass of the raw material powder;
the MCMBs content is 15-30wt%, preferably 30wt% of the total mass of the raw material powder;
the adding amount of the boron carbide is 0-1 wt% of the total mass of the raw material powder. The invention aims at SiC/C self-lubricating composite materials with high carbon content (the density is low easily due to the existence of sintering inertia of SiC and C when the carbon content is high).
Preferably, the granularity of the silicon carbide powder is 0.5-2 mu m, and the purity is more than 99%.
Preferably, the intermediate phase carbon microsphere MCMBs are intermediate phase carbon microsphere mature spheres (graphitized spheres of MCMBs green spheres after heat treatment at 2400-3000 ℃), the granularity is 5-15 mu m, and the purity is more than 99%. Commercial MCMBs are generally classified into three grades: the intermediate phase carbon microsphere separated from the matrix is called green pellet, and is called carbonized pellet after heat treatment at about 1000 deg.c, and graphitized pellet is called cooked pellet after the treatment temperature reaches 2400-3000 deg.c.
Preferably, the granularity of the boron carbide powder is 1.5 mu m, and the purity is more than 99%.
Preferably, the organic solvent includes at least one of cyclic hydrocarbon solvents, ether solvents and aromatic solvents; the cyclic hydrocarbon solvent is at least one selected from cyclopentane, cyclohexane, cycloheptane and cyclodecane, the ether solvent is tetrahydrofuran, and the aromatic solvent is at least one selected from benzene, toluene and xylene.
Preferably, the ball milling and mixing are planetary ball milling, the ball-material ratio is 2:1, the rotating speed is 200-300 r/min, and the time is 3-5 hours.
Preferably, the heating rate of the pyrolysis treatment is 1-5 ℃/min.
Preferably, the sintering temperature is 1900-2000 ℃, and the heat preservation time in the sintering temperature stage is 5-25 min (for example, 15 min);
the heating rate of the spark plasma sintering is 100 ℃/min; cooling after sintering is completed, wherein the cooling rate is 50 ℃/min;
wherein, in the two-step sintering mode, the pressure is applied at 20-30 MPa in the first step, the pressure is applied at 30-40 MPa in the second step, and the pressure of the second step is larger than the pressure of the first step. The first sintering step is favorable for fully shrinking the mesophase carbon microspheres and discharging small organic molecules, and the second sintering step aims at fully densification.
Preferably, the diameter of the SPS mold is 40mm.
The beneficial effects are that:
the invention adopts the spark plasma sintering technology, accelerates the sintering densification process of the composite material due to the coupling effect of an electric field and a force field, reduces the sintering temperature by about 100-200 ℃ compared with a hot-pressing sintering mode, shortens the sintering time by about 4-5 hours, and has the advantages of simple operation, energy conservation and high efficiency.
In the invention, the MCMBs/SiC composite material is prepared by SPS two-step sintering process, the density of the composite material can be close to or even exceed that of the composite material prepared by hot-pressed sintering, and the mechanical property of the composite material meets the practical application standard of the sealing element. Specifically, the method adopts a Spark Plasma Sintering (SPS) technology, and prepares the MCMBs/SiC composite material by a two-step sintering method under a proper sintering system, wherein the compactness is more than or equal to 85 percent, and the bending strength is 200-350 MPa. The elastic modulus is 100-180 GPa. The preparation method is simple to operate, high in efficiency, low in cost and energy-saving, can prepare the MCMBs/SiC composite material with self-lubricating performance at a lower temperature in a shorter time, and has important application prospects in the aspect of nuclear power mechanical sealing parts.
Drawings
FIG. 1 is a microstructure of the MCMBs/SiC composite material prepared in example 2.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. In the present invention, endpoints of the disclosed ranges and any values are not limited to the precise range or value, and such range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following illustrates a method for two-step sintering to rapidly prepare MCMBs/SiC composites.
Sequentially adding liquid polycarbosilane, silicon carbide powder, MCMBs and boron carbide into cyclohexane, and ball-milling and uniformly mixing to obtain slurry. In an alternative embodiment, it is preferred that the silicon carbide powder is in the alpha-SiC crystal form. In an alternative embodiment, preferably mcms are mesocarbon microbeads, and the mcms green balls are subjected to graphitization treatment (the graphitized balls of the mcms with the treatment temperature reaching 2400-3000 ℃ or higher, namely the mcms cooked balls, the graphitization treatment is a process in industrial production, and the cooked balls purchased from manufacturers are selected by themselves) to achieve good electric conduction. In an alternative embodiment, the liquid polycarbosilane side chains contain more vinyl groups and the pyrolysis product is predominantly hydrogen, which is cleaner. In an alternative embodiment, the boron carbide is added in an amount of 0 to 1wt%, preferably 0.5 to 1wt%, based on the total mass of the raw material powder.
The slurry is dried (for example, 12 hours) and then screened (for example, 100 meshes) to obtain raw material powder.
And (3) carrying out pyrolysis treatment on the raw material powder in vacuum or protective atmosphere at a certain temperature. Wherein, pyrolysis treatment is favorable to releasing the micromolecular gas, avoids the blank to appear warping, fracture and cause the pollution to the furnace chamber when following sintering, obtains pyrolysis powder.
And placing the pyrolysis powder in an SPS mold with the diameter of 40mm, and adopting a two-step sintering method to perform spark plasma sintering, wherein the first step is from room temperature to 1400 ℃, and the second step is from 1400 ℃ to sintering temperature, so as to prepare the MCMBs/SiC composite material.
As an example of a method for preparing an MCMBs/SiC composite, it comprises: sequentially adding liquid polycarbosilane, mesocarbon microbead cooked spheres, silicon carbide powder and boron carbide into cyclohexane, uniformly stirring, ball-milling for 3-5 hours, drying the fully mixed slurry for 12 hours, sieving the dried powder through a 100-mesh sieve, preserving heat for 0.5 hour at 900 ℃ for pyrolysis treatment, then filling the powder into an SPS high-purity graphite mold, and obtaining the MCMBs/SiC composite material by adopting a two-step sintering method.
As a detailed example of a method of preparing MCMBs/SiC composites, it includes: 1) Uniformly mixing the graphitized MCMBs cooked spheres serving as a second phase with silicon carbide, liquid polycarbosilane, boron carbide and cyclohexane to obtain original slurry, wherein the content of the MCMBs is 30wt%, the content of the silicon carbide is 60-68%, the content of the liquid polycarbosilane is 1-9 wt% and the content of the boron carbide is 0-1 wt% based on 100% of the total mass of raw material powder; 2) Ball milling and drying the raw materials obtained in the step 1) for 12 hours, and sieving the raw materials with a 100-mesh sieve to obtain raw material powder; 3) Putting raw material powder into a graphite crucible for pyrolysis treatment at a certain temperature; 4) And 3) placing the pyrolyzed powder obtained in the step 3) into a graphite die, and obtaining the MCMBs/SiC composite material through a two-step sintering process of a spark plasma sintering technology. In the step 1), MCMBs are mesocarbon microbeads cooked spheres after graphitization treatment. In the step 2), cyclohexane is adopted as a mixed solvent, and raw materials are fully mixed, dried and sieved to prepare raw material powder. In the step 3), the raw material powder is directly put into a graphite crucible for pyrolysis at 900 ℃; in the step 4), the raw material powder is directly filled into a graphite die and is rapidly sintered by a two-step sintering method through discharge plasma equipment, wherein the first step is from room temperature to 1400 ℃, and the second step is from 1400 ℃ to sintering temperature.
In the present disclosure, the density of the MCMBs/SiC composite material measured by the Archimedes method is more than or equal to 85 percent.
In the present disclosure, the bending strength of the MCMBs/SiC composite material measured by a three-point bending method is more than or equal to 200MPa.
In the present disclosure, the elastic modulus of the MCMBs/SiC composite material is more than or equal to 100GPa measured by a static three-point bending method.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below. The particle size of the silicon carbide powder was 0.5 μm unless otherwise specified in the following examples and comparative examples; the mesophase carbon microsphere cooked sphere is provided by Rongcarbon technology Co., ltd, and has the particle diameter of 10 μm; the liquid polycarbosilane is VHPCS-1 prepared by China academy of sciences chemistry research.
Example 1
1) Sequentially adding raw materials such as 5 weight percent of liquid polycarbosilane, 64.4 weight percent of silicon carbide powder, 30 weight percent of intermediate phase carbon microsphere cooked spheres, 0.6 weight percent of boron carbide and the like into cyclohexane, and fully and uniformly mixing by a planetary ball mill. The rotating speed of planetary ball milling is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1, a step of;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12 hours, and sieving with a 100-mesh sieve;
3) And (3) loading the raw material powder obtained in the step (2) into a graphite crucible, and carrying out pyrolysis treatment at 900 ℃ for 0.5 hour.
4) And (3) carrying out secondary grinding on the pyrolyzed powder obtained in the step (3), placing the pyrolyzed powder in an SPS mold with the diameter of 40mm, heating to 1400 ℃ from room temperature, applying 30MPa pressure, continuously heating to 1900 ℃, gradually increasing the pressure to 40MPa, and then carrying out heat preservation for 15min to obtain the MCMBs/SiC composite material.
The MCMBs/SiC composite material of the example 1 has the compactness of 92.7+/-0.3%, the bending strength of 273+/-8 MPa and the elastic modulus of 149+/-2 GPa.
Example 2
1) 9 weight percent of liquid polycarbosilane, 60.4 weight percent of silicon carbide powder, 30 weight percent of intermediate phase carbon microsphere cooked spheres, 0.6 weight percent of boron carbide and other raw materials are sequentially added into cyclohexane and fully and uniformly mixed by a planetary ball mill. The rotating speed of planetary ball milling is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1, a step of;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12 hours, and sieving with a 100-mesh sieve;
3) And (3) loading the raw material powder obtained in the step (2) into a graphite crucible, and carrying out pyrolysis treatment at 1200 ℃ for 0.5 hour.
4) And (3) carrying out secondary grinding on the pyrolyzed powder obtained in the step (3), placing the pyrolyzed powder in an SPS mold with the diameter of 40mm, heating to 1400 ℃ from room temperature, applying 30MPa pressure, continuously heating to 2000 ℃, gradually increasing the pressure to 40MPa, and then carrying out heat preservation for 20min to obtain the MCMBs/SiC composite material.
The MCMBs/SiC composite material of the example 2 has the compactness of 95.8+/-0.4%, the bending strength of 330+/-17 MPa and the elastic modulus of 172+/-5 GPa.
Example 3
1) 9 weight percent of liquid polycarbosilane, 60.4 weight percent of silicon carbide powder, 30 weight percent of intermediate phase carbon microsphere cooked spheres, 0.6 weight percent of boron carbide and other raw materials are sequentially added into cyclohexane and fully and uniformly mixed by a planetary ball mill. The rotating speed of planetary ball milling is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1, a step of;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12 hours, and sieving with a 100-mesh sieve;
3) And (3) loading the raw material powder obtained in the step (2) into a graphite crucible, and carrying out pyrolysis treatment at 900 ℃ for 0.5 hour.
4) And (3) carrying out secondary grinding on the pyrolyzed powder obtained in the step (3), placing the pyrolyzed powder in an SPS mold with the diameter of 40mm, heating to 1400 ℃ from room temperature, applying 30MPa pressure, continuously heating to 1900 ℃, gradually increasing the pressure to 40MPa, and then carrying out heat preservation for 15min to obtain the MCMBs/SiC composite material.
The MCMBs/SiC composite material of the example 3 has the compactness of 98.9+/-0.3%, the bending strength of 345+/-8 MPa and the elastic modulus of 146+/-3 GPa.
Example 4
The preparation of the MCMBs/SiC composite material of this example 4 is described with reference to example 1, with the only difference that: raw materials such as 1 weight percent of liquid polycarbosilane, 68.4 weight percent of silicon carbide powder, 30 weight percent of intermediate phase carbon microsphere cooked spheres, 0.6 weight percent of boron carbide and the like are sequentially added into cyclohexane, and fully and uniformly mixed by a planetary ball mill.
Comparative example 1
The preparation of the MCMBs/SiC composite material of this comparative example 1 is described with reference to example 1, with the only difference: raw materials such as 0 weight percent of liquid polycarbosilane, 69.4 weight percent of silicon carbide powder, 30 weight percent of intermediate phase carbon microsphere cooked spheres, 0.6 weight percent of boron carbide and the like are sequentially added into cyclohexane, and fully and uniformly mixed by a planetary ball mill.
Comparative example 2
The preparation of the MCMBs/SiC composite material of this comparative example 2 is described with reference to example 1, with the only difference: and (3) carrying out secondary grinding on the pyrolyzed powder obtained in the step (3), placing the pyrolyzed powder in an SPS mold with the diameter of 40mm, heating to 1400 ℃ from room temperature, applying 30MPa pressure, continuously heating to 1900 ℃ with the pressure still being 30MPa, and then carrying out heat preservation for 15min to obtain the MCMBs/SiC composite material.
Table 1 shows the preparation and properties of the prepared MCMBs/SiC composite materials:
Claims (10)
1. a method for rapidly preparing an mcms/SiC composite material by two-step sintering, comprising:
(1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesophase carbon microsphere MCMBs and boron carbide powder into an organic solvent, performing ball milling, mixing uniformly, drying and sieving to obtain raw material powder; the liquid polycarbosilane is added in an amount of 1-9 wt% of the total mass of the raw material powder, the silicon carbide content is 60-68 wt% of the total mass of the raw material powder, the MCMBs content is 15-30 wt% of the total mass of the raw material powder, the boron carbide is added in an amount of 0-1 wt% of the total mass of the raw material powder, and the sum of the four components is 100wt%;
(2) Carrying out pyrolysis treatment on the obtained raw material powder for 0.5-2 hours at 600-1200 ℃ in vacuum or protective atmosphere to obtain pyrolysis powder;
(3) Placing the obtained pyrolysis powder in an SPS mold, and performing spark plasma sintering by adopting a two-step sintering method to obtain the MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to raise the temperature from room temperature to 1400 ℃, and the second step is to raise the sintering temperature from 1400 ℃; the sintering temperature is 1900-2000 ℃, and the heat preservation time in the sintering temperature stage is 5-25 min; wherein, in the two-step sintering mode, the pressure is applied at 20-30 MPa in the first step, the pressure is applied at 30-40 MPa in the second step, and the pressure of the second step is larger than the pressure of the first step.
2. The method according to claim 1, wherein the mcms content is 30wt% of the total mass of the raw powder.
3. A method according to claim 1, wherein the silicon carbide powder has a particle size of 0.5-2 μm and a purity of > 99%.
4. The method according to claim 1, wherein the mesophase carbon microbeads MCMBs are mesophase carbon microbeads having a particle size of 5-15 μm and a purity of > 99%.
5. The method of claim 1, wherein the boron carbide powder has a particle size of 1.5 μm and a purity of > 99%.
6. The method of claim 1, wherein the organic solvent comprises at least one of a cyclic hydrocarbon solvent, an ether solvent, and an aromatic solvent; the cyclic hydrocarbon solvent is at least one selected from cyclopentane, cyclohexane, cycloheptane and cyclodecane, the ether solvent is tetrahydrofuran, and the aromatic solvent is at least one selected from benzene, toluene and xylene.
7. The method according to any one of claims 1 to 6, wherein the ball milling mixing is planetary ball milling, the ball-to-material ratio is 2:1, the rotational speed is 200-300 r/min, and the time is 3-5 hours.
8. The method of any one of claims 1-6, wherein the pyrolysis treatment has a ramp rate of 1-5 ℃/min.
9. The method of any one of claims 1-6, wherein the spark plasma sintering is at a ramp rate of 100 ℃/min; cooling after sintering, wherein the cooling rate is 50 ℃/min.
10. The method of any one of claims 1-6, wherein the SPS die has a diameter of 40mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211333384 | 2022-10-28 | ||
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