CN115724664A - Method for rapidly preparing MCMBs/SiC composite material by two-step sintering - Google Patents
Method for rapidly preparing MCMBs/SiC composite material by two-step sintering Download PDFInfo
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Abstract
The invention relates to a method for rapidly preparing MCMBs/SiC composite material by two-step sintering, which comprises the following steps: (1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesocarbon microbeads MCMBs and boron carbide powder into an organic solvent, performing ball milling and 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 (semi-solid solution sintering) mould, and performing discharge plasma sintering by adopting a two-step sintering method to prepare an MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to heat from room temperature to 1400 ℃, and the second step is to heat from 1400 ℃ to sintering temperature.
Description
Technical Field
The invention relates to a method for rapidly preparing MCMBs/SiC composite material by two-step sintering, belonging to the technical field of composite materials.
Background
With the increasingly prominent environmental and energy problems, high-tech industries such as nuclear power and the like are rapidly developed. The mechanical seal is one of three key components of the main pump of the shaft seal type nuclear reactor, is an important device for preventing the coolant of a reactor loop 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 harsh application environments such as high temperature, high pv value and vacuum due to excellent performances such as high hardness, high strength, wear resistance, corrosion resistance, high thermal conductivity and oxidation resistance, but under the dry friction condition, the friction coefficient and the wear rate of a pure silicon carbide material are high, so that the material has the risk of failure damage in the working process, and in order to ensure the safe operation and longer service life of a sealing part, the sealing material is required to have a low and stable friction coefficient and a low wear rate under the dry friction working condition, namely the material is required to have good self-lubricating performance. Wherein, the second phase mesocarbon microbeads are added into the silicon carbide matrix material, so that the friction coefficient under the dry friction condition can be obviously reduced, and the SiC/MCMBs composite material with good self-lubricating performance is obtained.
Disclosure of Invention
Therefore, the invention provides a method for rapidly preparing MCMBs/SiC composite material by two-step sintering, which comprises the following steps:
(1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesocarbon microbeads MCMBs and boron carbide powder into an organic solvent, performing ball milling and 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 (semi-solid phase sintering) mould, and performing spark plasma sintering by adopting a two-step sintering method to prepare an MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to heat from room temperature to 1400 ℃, and the second step is to heat from 1400 ℃ to sintering temperature.
In the previous research process, the inventors firstly thought to prepare the MCMBs/SiC composite (or called MCMBs/SiC self-lubricating composite) by hot press sintering. Although the hot-pressing sintering is simultaneously heated and pressurized, the mass transfer processes such as contact, diffusion, flow and the like of powder particles in the sintering process are facilitated, and the obtained sintered body has higher density. However, the method is limited by process conditions, has high requirements on the die, high production cost and low production efficiency, and limits the wide application of the self-lubricating composite material in practical production. The inventor considers that the MCMBs sintered ball has better conductivity after graphitization treatment in production and manufacture, creatively adopts a discharge plasma sintering technology, and prepares the MCMBs/SiC composite material with higher density and excellent performance at lower temperature and pressure through an electric field auxiliary and two-step sintering method. In the invention, the mesocarbon microbeads in the MCMBs/SiC composite material are also modified by the silicon carbide polymer precursor so as to crack at the interface of SiC and the mesocarbon microbeads to form silicon carbide microcrystals and free carbon, thereby improving the strength of the two-phase interface of SiC and MCMBs.
Preferably, the adding amount of the liquid polycarbosilane is 1 to 9 weight percent of the total mass of the raw material powder;
the content of the silicon carbide accounts for 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, and is preferably 30wt%;
the adding amount of the boron carbide is 0-1 wt% of the total mass of the raw material powder. The invention aims at the SiC/C self-lubricating composite material with high carbon content (the density is easy to be lower due to the sintering inertia of SiC and C when the carbon content is higher).
Preferably, the granularity of the silicon carbide powder is 0.5-2 mu m, and the purity is more than 99%.
Preferably, the mesocarbon microbeads MCMBs are mesocarbon microbead cooked spheres (graphitized spheres of MCMBs raw spheres after heat treatment at 2400-3000 ℃), the particle size is 5-15 μm, and the purity is more than 99%. Commercially MCMBs are generally divided into three grades: the raw material mesophase carbon microspheres separated from the matrix are called green spheres, the green spheres are called carbonized spheres after heat treatment at about 1000 ℃, and the graphitized spheres are called as instant balls when the treatment temperature reaches 2400-3000 ℃.
Preferably, the granularity of the boron carbide powder is 1.5 mu m, and the purity is more than 99 percent.
Preferably, the organic solvent includes 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.
Preferably, the ball milling and mixing is planetary ball milling, the ball material ratio is 2.
Preferably, the heating rate of the pyrolysis treatment is 1-5 ℃/min.
Preferably, the sintering temperature is 1900-2000 ℃, and the holding time in the sintering temperature stage is 5-25 min (such as 15 min);
the heating rate of the spark plasma sintering is 100 ℃/min; cooling after sintering, wherein the cooling rate is 50 ℃/min;
wherein, the pressure applied in the first step is 20-30 MPa, the pressure applied in the second step is 30-40 MPa, and the pressure applied in the second step is larger than that applied in the first step. The first sintering step is favorable for fully shrinking the mesocarbon microbeads and discharging small organic molecules, and the second sintering step is used for fully densifying.
Preferably, the diameter of the SPS die is 40mm.
Has the beneficial effects that:
the invention adopts the spark plasma sintering technology, accelerates the process of sintering densification of the composite material due to the electric field-force field coupling effect, reduces the sintering temperature by about 100-200 ℃ compared with the hot-pressing sintering mode, shortens the sintering time by about 4-5 h, and has the advantages of simple operation, energy saving and high efficiency.
In the invention, the MCMBs/SiC composite material is prepared by a SPS two-step sintering process, the density of the MCMBs/SiC composite material can be close to or even exceed that of the composite material prepared by hot-pressing sintering, and the mechanical property of the MCMBs/SiC composite material meets the actual application standard of a 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 density of the MCMBs/SiC composite material is more than or equal to 85 percent, and the bending strength of the MCMBs/SiC composite material is 200-350 MPa. The elastic modulus is 100-180 GPa. The preparation method is simple to operate, high in efficiency, low in cost, energy-saving, capable of preparing the MCMBs/SiC composite material with self-lubricating performance at a lower temperature in a shorter time, and has an important application prospect in the aspect of nuclear power mechanical sealing parts.
Drawings
FIG. 1 is a microstructure diagram of the MCMBs/SiC composite material prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive. The endpoints of the disclosed ranges and any values are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The following is an exemplary description of a two-step sintering process for the rapid preparation of MCMBs/SiC composites.
Sequentially adding liquid polycarbosilane, silicon carbide powder, MCMBs and boron carbide into cyclohexane, and performing ball milling and uniform mixing to obtain slurry. In an alternative embodiment, it is preferred that the silicon carbide powder be of the alpha-SiC crystalline form. In an alternative embodiment, it is preferable that the MCMBs are intermediate-phase carbon microsphere boiled balls, and the MCMBs raw balls are subjected to graphitization treatment (the MCMBs graphitized balls with the treatment temperature of 2400 ℃ to 3000 ℃ or higher, namely, the MCMBs boiled balls, and the graphitization treatment is a process in industrial production and is a boiled ball selected by a manufacturer). In an alternative embodiment, the liquid polycarbosilane has more vinyl groups in its side chains and the pyrolysis product is primarily hydrogen, which is cleaner. In an optional embodiment, the addition amount of boron carbide is 0 to 1wt%, preferably 0.5 to 1wt%, of the total mass of the raw material powder.
The slurry is dried (for example, for 12 hours) and then sieved (for example, 100 mesh) to obtain a raw material powder.
Carrying out pyrolysis treatment on the raw material powder at a certain temperature in vacuum or protective atmosphere. Wherein, the pyrolysis treatment is beneficial to releasing small molecular gas, and avoids deformation and cracking of a blank body and pollution to a furnace chamber during subsequent sintering, thereby obtaining pyrolysis powder.
And putting the pyrolysis powder into an SPS (spark plasma sintering) die with the diameter of 40mm, and performing spark plasma sintering by adopting a two-step sintering method, wherein the first step is from room temperature to 1400 ℃, and the second step is from 1400 ℃ to the sintering temperature, so as to prepare the MCMBs/SiC composite material.
As an example of a preparation method of the MCMBs/SiC composite material, the method comprises the following steps: adding liquid polycarbosilane, intermediate phase carbon microsphere cooked balls, silicon carbide powder and boron carbide into cyclohexane in sequence, uniformly stirring, drying the fully mixed slurry for 12h after ball milling for 3-5 h, sieving the dried powder with a 100-mesh sieve, then carrying out thermal decomposition treatment at 900 ℃ for 0.5 h, then loading into an SPS high-purity graphite mould, and obtaining the MCMBs/SiC composite material by adopting a two-step sintering method.
As a detailed example of the preparation method of the MCMBs/SiC composite material, the method comprises the following steps: 1) The method comprises the following steps of uniformly mixing graphitized MCMBs cooked balls serving as a second phase with silicon carbide, liquid polycarbosilane, boron carbide and cyclohexane to obtain an original slurry, wherein the MCMBs content is 30wt%, the silicon carbide content is 60-68 wt%, the liquid polycarbosilane content is 1-9 wt% and the boron carbide content is 0-1 wt% based on 100% of the total mass of raw material powder; 2) Performing ball milling and drying on 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 the raw material powder into a graphite crucible for pyrolysis treatment at a certain temperature; 4) And (4) putting the pyrolyzed powder obtained in the step 3) into a graphite mould, and carrying out a two-step sintering process by using a spark plasma sintering technology to obtain the MCMBs/SiC composite material. In the step 1), MCMBs are the intermediate phase carbon microsphere cooked balls after graphitization treatment. In the step 2), cyclohexane is used as a mixed solvent, and raw materials are dried and sieved after being fully mixed to prepare raw material powder. In the step 3), directly putting the raw material powder 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 discharge plasma device by adopting a two-step sintering method, wherein the temperature of the first step is from room temperature to 1400 ℃, and the temperature of the second step is from 1400 ℃ to the sintering temperature.
In the disclosure, the density of the MCMBs/SiC composite material measured by an Archimedes method is more than or equal to 85%.
In the 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 disclosure, the elastic modulus of the MCMBs/SiC composite material measured by a static three-point bending method is more than or equal to 100GPa.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples and comparative examples, unless otherwise specified, the particle diameter of the silicon carbide powder was 0.5 μm; the mesocarbon microbead cooked ball is provided by Rong carbon technology, inc., and has a particle size of 10 μm; the liquid polycarbosilane is VHPCS-1 prepared by chemical research of Chinese academy of sciences.
Example 1
1) Adding raw materials of 5wt% of liquid polycarbosilane, 64.4wt% of silicon carbide powder, 30wt% of intermediate phase carbon microsphere cooked balls, 0.6wt% of boron carbide and the like into cyclohexane in sequence, and fully and uniformly mixing by a planetary ball mill. The rotating speed of the planetary ball mill is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12h, and sieving the dried slurry with a 100-mesh sieve;
3) And (3) putting the raw material powder obtained in the step (2) into a graphite crucible, and carrying out thermal decomposition treatment at 900 ℃ for 0.5 hour.
4) And (4) grinding the pyrolyzed powder obtained in the step (3) for the second time, placing the powder in an SPS die with the diameter of 40mm, heating the powder to 1400 ℃ from room temperature, applying 30MPa of pressure, continuously heating the powder to 1900 ℃, gradually increasing the pressure to 40MPa, and then preserving the heat for 15min to obtain the MCMBs/SiC composite material.
Tests show that the density of the MCMBs/SiC composite material in the embodiment 1 is 92.7 +/-0.3%, the bending strength is 273 +/-8 MPa, and the elastic modulus is 149 +/-2 GPa.
Example 2
1) Adding 9wt% of liquid polycarbosilane, 60.4wt% of silicon carbide powder, 30wt% of intermediate phase carbon microsphere cooked balls, 0.6wt% of boron carbide and the like into cyclohexane in sequence, and fully and uniformly mixing by a planetary ball mill. The rotating speed of the planetary ball mill is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12h, and sieving the dried slurry with a 100-mesh sieve;
3) And (3) putting the raw material powder obtained in the step (2) into a graphite crucible, and carrying out thermal decomposition treatment at 1200 ℃ for 0.5 hour.
4) And (4) grinding the pyrolyzed powder obtained in the step (3) for the second time, placing the powder in an SPS (semi-solid phase sintering) mold with the diameter of 40mm, heating the powder to 1400 ℃ from room temperature, applying 30MPa of pressure, continuously heating the powder to 2000 ℃, gradually increasing the pressure to 40MPa, and then carrying out heat preservation for 20min to obtain the MCMBs/SiC composite material.
Tests show that the density of the MCMBs/SiC composite material of the embodiment 2 is 95.8 +/-0.4%, the bending strength is 330 +/-17 MPa, and the elastic modulus is 172 +/-5 GPa.
Example 3
1) Adding 9wt% of liquid polycarbosilane, 60.4wt% of silicon carbide powder, 30wt% of intermediate phase carbon microsphere cooked balls, 0.6wt% of boron carbide and the like into cyclohexane in sequence, and fully and uniformly mixing by a planetary ball mill. The rotating speed of the planetary ball mill is 300r/h, and the material: ball: the mass ratio of cyclohexane is 1:2:1;
2) Drying the slurry obtained in the step (1) in an oven at 60 ℃ for 12h, and sieving the dried slurry with a 100-mesh sieve;
3) And (3) putting the raw material powder obtained in the step (2) into a graphite crucible, and carrying out thermal decomposition treatment at 900 ℃ for 0.5 hour.
4) And (4) grinding the pyrolyzed powder obtained in the step (3) for the second time, placing the powder in an SPS mold with the diameter of 40mm, heating the powder to 1400 ℃ from room temperature, applying 30MPa of pressure, continuously heating the powder to 1900 ℃, gradually increasing the pressure to 40MPa, and then carrying out heat preservation for 15min to obtain the MCMBs/SiC composite material.
Tests show that the density of the MCMBs/SiC composite material in the embodiment 3 is 98.9 +/-0.3%, the bending strength is 345 +/-8 MPa, and the elastic modulus is 146 +/-3 GPa.
Example 4
The preparation of the MCMBs/SiC composite material in example 4 is carried out in accordance with example 1, with the following differences: sequentially adding 1wt% of liquid polycarbosilane, 68.4wt% of silicon carbide powder, 30wt% of intermediate phase carbon microsphere cooked balls, 0.6wt% of boron carbide and the like into cyclohexane, and fully and uniformly mixing by using a planetary ball mill.
Comparative example 1
The preparation of the MCMBs/SiC composite material in comparative example 1 is carried out in accordance with example 1, with the only difference that: adding 0wt% of liquid polycarbosilane, 69.4wt% of silicon carbide powder, 30wt% of intermediate phase carbon microsphere cooked balls, 0.6wt% of boron carbide and the like into cyclohexane in sequence, and fully and uniformly mixing by a planetary ball mill.
Comparative example 2
The preparation of the MCMBs/SiC composite material of the comparative example 2 is carried out in accordance with example 1, with the only difference that: and (4) grinding the pyrolyzed powder obtained in the step (3) for the second time, placing the powder in an SPS (semi-solid phase sintering) mold with the diameter of 40mm, heating the powder to 1400 ℃ from room temperature, applying 30MPa of pressure, continuously heating the powder to 1900 ℃, keeping the pressure unchanged to 30MPa, and then keeping the temperature for 15min to obtain the MCMBs/SiC composite material.
Table 1 shows the preparation and properties of the prepared MCMBs/SiC composite:
Claims (10)
1. a method for rapidly preparing MCMBs/SiC composite material by two-step sintering is characterized by comprising the following steps:
(1) Sequentially adding liquid polycarbosilane, silicon carbide powder, mesocarbon microbeads MCMBs and boron carbide powder into an organic solvent, performing ball milling and mixing uniformly, drying and sieving to obtain raw material powder;
(2) Carrying out pyrolysis treatment on the obtained raw material powder in a vacuum or protective atmosphere at the temperature of 600-1200 ℃ for 0.5-2 hours to obtain pyrolysis powder;
(3) Placing the obtained pyrolysis powder in an SPS (semi-solid phase sintering) mould, and performing spark plasma sintering by adopting a two-step sintering method to prepare an MCMBs/SiC composite material; the two-step sintering method comprises the following steps: the first step is to heat from room temperature to 1400 ℃, and the second step is to heat from 1400 ℃ to sintering temperature.
2. The method according to claim 1, wherein the liquid polycarbosilane is added in an amount of 1-9 wt% based on the total mass of the raw powder;
the content of the silicon carbide accounts for 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, and is preferably 30wt%;
the adding amount of the boron carbide is 0 to 1 weight percent of the total mass of the raw material powder.
3. The method according to claim 1 or 2, wherein the silicon carbide powder has a particle size of 0.5 to 2 μm and a purity of > 99%.
4. The method according to any one of claims 1 to 3, wherein the MCMBs are cooked mesocarbon microbeads having a particle size of 5 to 15 μm and a purity of > 99%.
5. The method according to any one of claims 1 to 4, wherein the boron carbide powder has a particle size of 1.5 μm and a purity of > 99%.
6. The method according to any one of claims 1 to 5, 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 a planetary ball milling, the ball material ratio is 2.
8. The production method according to any one of claims 1 to 7, wherein the temperature increase rate of the pyrolysis treatment is 1 to 5 ℃/min.
9. The method according to any one of claims 1 to 8, wherein the sintering temperature is 1900 to 2000 ℃ and the holding time in the sintering temperature stage is 5 to 25min;
the heating rate of the spark plasma sintering is 100 ℃/min; cooling after sintering, wherein the cooling rate is 50 ℃/min;
wherein, the pressure applied in the first step is 20-30 MPa, the pressure applied in the second step is 30-40 MPa, and the pressure applied in the second step is larger than that applied in the first step.
10. A method as claimed in any one of claims 1 to 9, wherein the SPS die has a diameter of 40mm.
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