CN112266251A - Preparation method of silicon nitride/titanium carbide ceramic material based on spark plasma sintering - Google Patents
Preparation method of silicon nitride/titanium carbide ceramic material based on spark plasma sintering Download PDFInfo
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Abstract
The invention particularly relates to a preparation method of a silicon nitride/titanium carbide ceramic material based on spark plasma sintering. The silicon nitride-based ceramic material has good mechanical property and stability, and the high-performance Si is prepared3N4The SiC ceramic material is expected to be widely applied in the industrial field. The invention provides Si based on spark plasma sintering3N4Preparation method of/TiC ceramic material using alpha-Si3N4As matrix, TiC as reinforcing phase, Al2O3And Y2O3The sintering aid is prepared by ball milling, mixing, drying, and performing spark plasma sintering at 1650-1750 deg.C for 20-35 min. Si prepared by the invention3N4the/TiC ceramic material has good sintering compactness, and the bending strength, the fracture toughness and the hardness of the ceramic material are not lower than 700MPa and 6.1 MPa.m1/2，13GPa。
Description
Technical Field
The invention belongs to the technical field of ceramic material preparation, and particularly relates to silicon nitride/titanium carbide (Si) based on spark plasma sintering3N4TiC) ceramic material preparation method and Si prepared by method3N4A TiC ceramic material and application.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
As the most popular ultra-fast sintering technology at present, Spark Plasma Sintering (SPS) is mainly used for preparing nano-structure materials, amorphous materials, intermetallic compounds, metal matrixes and ceramic matrix composite materials. Compared with the traditional sintering mode, the Spark Plasma Sintering (SPS) technology has higher heating speed and can achieve the same sintering effect in shorter sintering time. The rapid temperature rise of the discharge plasma sintering (SPS) preparation material is caused by the skin effect of a direct current component and an alternating current component in the pulse current and the smaller heat capacity of a heating system. During sintering, most of heat is generated from the inner edge of the die, and the higher the temperature of the die, the higher the temperature of the surface of the powder. In Spark Plasma Sintering (SPS), a powder is placed in a graphite mold and an electric current is passed through the mold and sample (if the latter is a conductive material) while applying pressure to the powder to heat the powder green body, and if the powder is a non-conductive material, the electric current flows primarily through the mold to generate heat. Besides the fact that the nano-material without obvious grain growth can be successfully prepared due to the lower sintering temperature and the shorter sintering time, the SPS process has the following advantages in preparing the ceramic material due to the unique heating system: the method can clean the grain boundary, can obviously increase superplasticity, reduce grain boundary segregation, enhance bonding quality, improve thermoelectric performance and improve the ductility of the alloy ceramic.
The silicon nitride-based ceramic material has higher fracture toughness and strength and excellent thermal shock resistance, corrosion resistance and wear resistance, and is applied to the industrial fieldHas wide application. Therefore, many researchers have focused their eyes on how to prepare high-performance Si by a suitable sintering method3N4A base ceramic material. The conventional sintering methods for sintering the silicon nitride ceramic material comprise the following steps: pressureless sintering, reactive sintering, Gas Pressure Sintering (GPS), hot isostatic pressing sintering (HIP), and Hot Pressing (HP) sintering. Chinese patent CN 109516814A discloses Si3N4a/SiC complex phase ceramic material and a preparation method thereof, wherein Si is3N4the/SiC complex phase ceramic material is Si3N4And SiC as a raw material powder, Tm2O3And MgO is used as a sintering aid and is prepared by hot-pressing sintering. The method can obtain Si with high density3N4The SiC ceramic material has longer sintering time.
Disclosure of Invention
Against the background of the above research, the inventors believe that providing a preparation method with higher sintering efficiency is beneficial to increasing Si3N4The production of the SiC ceramic material, the spark plasma sintering is characterized by sintering in the pressurizing process, and the plasma generated by the pulse current and the pressurizing in the sintering process are beneficial to reducing the sintering temperature of the powder. Meanwhile, the powder can be rapidly sintered and compacted due to the characteristics of low voltage and high current. The invention applies it to Si3N4The sintering time of the SiC ceramic material is successfully shortened to half of the pressure sintering time, and in addition, the Si prepared by sintering by adopting the method provided by the invention3N4The SiC ceramic material also has excellent mechanical property.
Based on the technical effects, the invention provides the following technical scheme:
in a first aspect of the invention, Si based on spark plasma sintering is provided3N4The preparation method of the/TiC ceramic material comprises the following steps: with Si3N4As matrix, TiC as reinforcing phase, Al2O3And Y2O3The sintering aid is prepared by performing wet ball milling mixing and spark plasma sintering on the raw materials.
After sintering by spark plasma, the Si3N4The preparation time of the TiC ceramic material is obviously shortened, the invention provides a corresponding temperature-rising sintering procedure aiming at spark plasma sintering, and the detection result shows that the sintering method provided by the invention can inhibit beta-Si3N4Increase the proportion of alpha crystal phase in the sintered product due to the excessive growth of alpha-Si3N4The crystalline phase has higher strength, and the ceramic material prepared by the method is more suitable for preparing cutting tools, in particular for preparing ceramic cutters. And the introduction of TiC can better improve Si3N4Conductivity and electric spark processing performance.
The beneficial effects of one or more technical schemes are as follows:
the preparation process is simple, the sintering time is short, and Si can be finished in a short time3N4And sintering the TiC ceramic material. Compared with hot-press sintering, the time for spark plasma sintering is only 1/2 of hot-press sintering. And Si prepared by the present invention3N4The TiC ceramic material has excellent mechanical property, bending strength, fracture toughness and Vickers hardness, and inhibits beta-Si due to the unique sintering mechanism of SPS3N4Avoiding large beta-Si3N4This pair of Si3N4The properties of the/TiC ceramic material are beneficial.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows Si prepared in example 13N4A graph of the sintering temperature and the displacement of the upper pressure head in the spark plasma sintering process of the TiC ceramic material;
FIG. 2 shows Si prepared in example 13N4XRD detection diagram of the/TiC ceramic material;
FIG. 3 shows Si prepared in example 13N4SEM image of fracture surface of/TiC ceramic material.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background section, high density Si is aimed at3N4The SiC ceramic material has longer sintering time and low production efficiency. In order to solve the technical problems, the invention provides Si based on spark plasma sintering3N4Compared with the existing hot-pressing sintering method, the preparation method of the/TiC ceramic material shortens 1/2 time, and the Si prepared by the method3N4the/TiC ceramic has good mechanical property.
In a first aspect of the invention, Si based on spark plasma sintering is provided3N4The preparation method of the/TiC ceramic material comprises the following steps: with Si3N4As matrix, TiC as reinforcing phase, Al2O3And Y2O3The sintering aid is prepared by performing wet ball milling mixing and spark plasma sintering on the raw materials.
Preferably, in the preparation method, the volume percentages of the raw materials are as follows: alpha-Si3N4 70-85％，TiC 5-15％，Al2O3 1-6％，Y2O3 3-7％。
Go toThe volume percentage of TiC is 7-10%, or Al2O3Is 2-4% by volume, or said Y2O3The volume percentage of the raw materials is 4-6%, the raw materials are adjusted within the volume percentage range, and the sum of the rest components is 100%.
In some embodiments of the above preferred embodiments, the raw materials are as follows: alpha-Si3N4 80％，TiC 10％，Al2O3 4％，Y2O3 6％。
In some embodiments of the above preferred embodiments, the raw materials are as follows: alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％。
In some embodiments of the above preferred embodiments, the raw materials are as follows: alpha-Si3N4 75％，TiC 15％，Al2O3 4％，Y2O3 6％。
Preferably, the alpha-Si is3N4The average particle diameter of the powder is 0.5-1 μm.
Preferably, the average grain diameter of the TiC powder is 0.5-1 μm.
Preferably, the Al is2O3The average particle diameter of the powder is 0.5-2 μm.
Preferably, said Y is2O3The average particle diameter of the powder is 0.1-0.5 μm.
Preferably, the preparation method specifically comprises the following steps:
(1) alpha-Si is mixed3N4Adding TiC powder into dispersion medium respectively to make it uniformly dispersed so as to obtain alpha-Si3N4Mixing the suspension and the TiC suspension to obtain a complex phase suspension;
(2) weighing alpha-Si3N4Dispersing agent with weight of 1-5 wt% is added into the dispersing medium to be dissolved, then dispersing agent solution is added into the multiphase suspension, and Al is added2O3And Y2O3Powder bodyDispersing the mixture evenly to obtain a mixed system;
(3) transferring the mixed system obtained in the step (2) to a ball milling tank for ball milling; drying the ball milling liquid and sieving to obtain mixed powder;
(4) and (4) filling the mixed powder in the step (3) into a mould for forming, and then performing spark plasma sintering.
Further, in the step (1) or (2), the dispersion medium includes, but is not limited to, absolute ethyl alcohol or absolute methyl alcohol.
Further, in the step (2), the dispersant includes, but is not limited to, polyethylene glycol, and specifically, polyethylene glycol 6000.
Further, in the step (3), ball milling is carried out for 40-50 h in a protective atmosphere by adding ball milling balls according to the ball material weight ratio of 10: 0.5-1.5; specifically, the protective atmosphere is nitrogen.
Further, in the step (3), the ball grinding balls are cemented carbide pellets YG6 or YG 8.
Further, in the step (3), the drying manner of the ball milling liquid includes, but is not limited to, one of atmospheric drying, vacuum drying, spray drying or freeze drying.
In a specific embodiment, the drying is vacuum drying and is carried out at the temperature of 80-120 ℃ for 12-24 hours.
Further, in the step (3), the ball milling liquid is dried and then sieved through a 100-mesh and 120-mesh sieve to obtain the mixed powder.
Further, in the step (4), the discharge plasma sintering parameters are: the heating rate is as follows: before 1300 ℃, 90-110 ℃/min, higher than 1300 ℃, 30-50 ℃/min; the sintering temperature is 1650-1750 ℃; the heat preservation time is 20-35min, and the heat preservation time is 10-17min after the temperature is 1600 ℃ and the sintering temperature is reached respectively; the axial pressure is 25-35 MPa.
In a specific embodiment of the above preferred technical solution, the preparation method comprises the following steps:
(1) weighing alpha-Si in proportion3N4Adding proper amount of absolute ethyl alcohol into TiC powder as dispersion medium, ultrasonic dispersing and mechanically stirring10-20min to obtain alpha-Si3N4Suspension liquid and TiC suspension liquid, and mixing the two suspension liquids to obtain complex phase suspension liquid;
(2) weighing alpha-Si3N4Dissolving 1-5 wt% of polyethylene glycol 6000 in anhydrous ethanol, adding into the multiphase suspension, and adding Al in proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 30-50 min;
(3) pouring the final suspension obtained in the step (2) into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, carrying out ball milling for 48 hours under a protective atmosphere, drying the ball milling liquid in a vacuum drying oven at 80-120 ℃ for 12-24 hours, sieving the ball milling liquid through a 100-sand-screening 120-mesh sieve to obtain mixed powder, and sealing and storing for later use;
(4) and (4) filling the mixed powder obtained in the step (3) into a graphite die, and putting the graphite die into a discharge plasma sintering furnace for sintering after cold press molding.
In a second aspect of the present invention, there is provided Si according to the first aspect based on spark plasma sintering3N4Si prepared by preparation method of TiC ceramic material3N4A TiC ceramic material.
In a third aspect of the present invention, there is provided Si as defined in the first aspect3N4The TiC ceramic material is applied to the fields of producing cutting tools, wear-resistant parts, inserts, products for the aviation industry and the like.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples, wherein the raw materials in the following examples are all commercially available products.
Example 1
Si based on Spark Plasma Sintering (SPS)3N4The preparation method of the/TiC ceramic material comprises the following steps of preparing raw material components by volume percentage of alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％。
Weighing alpha-Si in proportion3N4Adding appropriate amount of anhydrous alcohol into TiC powder respectivelyIs used as a dispersion medium, ultrasonically dispersed and mechanically stirred for 15min to prepare alpha-Si3N4Suspension, TiC suspension; mixing the two suspensions to obtain a complex phase suspension. Weighing Si3N4Dissolving 3 wt% of polyethylene glycol 6000 in anhydrous ethanol, adding into the multiphase suspension, and adding Al in proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 45 min; and pouring the obtained final suspension into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, and carrying out ball milling for 48 hours in a nitrogen atmosphere.
Drying the obtained ball milling liquid for 12 hours at 110 ℃ in a vacuum drying oven, sieving the ball milling liquid by a 100-mesh sieve to obtain mixed powder, filling the obtained mixed powder into a graphite mold, and putting the graphite mold into a discharge plasma sintering furnace for hot-pressing sintering after cold-press molding; discharge plasma sintering parameters: 100 ℃/min before 1300 ℃; 50 ℃/min at 1300-1450 ℃; 30 ℃/min at the temperature of 1450-1600 ℃; keeping the temperature at 1600 ℃ for 15 min; 30 ℃/min at 1600-1700 ℃; preserving heat at 1700 ℃ for 10 min; the pressure is 30 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 959MPa, the hardness is 15.21GPa, and the fracture toughness is 8.61 MPa.M1/2. From FIG. 1, it can be seen that spark plasma sintering of Si3N4Densification and crystal growth of the ceramic material. Before 1200 ℃, the powder expands under heat, the lower pressure head moves downwards, and the Z-axis displacement decreases. Densification takes place after 1200 c, at which time the lower ram moves up and the Z-axis displacement increases. When the temperature reaches 1700 ℃, the crystal begins to grow and the ceramic material begins to expand, and the Z-axis displacement is reduced. From FIG. 2, it can be found that Si is present after sintering3N4The phase composition of the/TiC ceramic material is beta-Si3N4、TiC0.3N0.7And a small amount of alpha-Si3N4Wherein TiC0.3N0.7 is mainly due to Si during sintering3N4And TiC. And from figure 2 it can be seen that the junctions in the ceramic materialThe crystallinity is good. FIG. 3 shows Si3N4SEM image of fracture surface of/TiC ceramic material can find that the crystal grains are uniform, and larger beta-Si is not found3N4And the compactness is good, and no obvious air hole is found, which is also the reason that the ceramic material has excellent mechanical property.
Example 2
Si based on Spark Plasma Sintering (SPS)3N4The preparation method of the/TiC ceramic material comprises the following steps of preparing raw material components by volume percentage of alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％。
Weighing alpha-Si in proportion3N4Adding proper amount of absolute ethyl alcohol into TiC powder as dispersion medium, ultrasonic dispersing and mechanically stirring for 15min to obtain alpha-Si3N4Suspension, TiC suspension; mixing the three suspensions to obtain a complex phase suspension. Weighing Si3N4Dispersing agent with the weight of 3 wt% of the powder is dissolved by absolute ethyl alcohol and then added into the multiphase suspension, and then Al is added according to the proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 45 min; and pouring the obtained final suspension into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, and carrying out ball milling for 48 hours in a nitrogen atmosphere.
Drying the obtained ball milling liquid for 12 hours at 110 ℃ in a vacuum drying oven, sieving the ball milling liquid by a 100-mesh sieve to obtain mixed powder, filling the obtained mixed powder into a graphite mold, and putting the graphite mold into a discharge plasma sintering furnace for hot-pressing sintering after cold-press molding; discharge plasma sintering parameters: 100 ℃/min before 1300 ℃; 50 ℃/min at 1300-1450 ℃; 30 ℃/min at the temperature of 1450-1600 ℃; keeping the temperature at 1600 ℃ for 15 min; 30 ℃/min at the temperature of 1600-1650 ℃; keeping the temperature at 1650 ℃ for 10 min; the pressure is 30 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test of the material shows that the bending strength of the material is 768MPa, the hardness is 15.81GPa, and the fracture toughness is6.19MPa·M1/2. And the introduction of TiC can better improve Si3N4Conductivity and electric spark processing performance.
Example 3
Si based on Spark Plasma Sintering (SPS)3N4The preparation method of the/TiC ceramic material comprises the following steps of preparing raw material components by volume percentage of alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％。
Weighing alpha-Si in proportion3N4Adding proper amount of absolute ethyl alcohol into TiC powder as dispersion medium, ultrasonic dispersing and mechanically stirring for 15min to obtain alpha-Si3N4Suspension, TiC suspension; mixing the three suspensions to obtain a complex phase suspension. Weighing Si3N4Dispersing agent with the weight of 3 wt% of the powder is dissolved by absolute ethyl alcohol and then added into the multiphase suspension, and then Al is added according to the proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 45 min; and pouring the obtained final suspension into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, and carrying out ball milling for 48 hours in a nitrogen atmosphere.
Drying the obtained ball milling liquid for 12 hours at 110 ℃ in a vacuum drying oven, sieving the ball milling liquid by a 100-mesh sieve to obtain mixed powder, filling the obtained mixed powder into a graphite mold, and putting the graphite mold into a discharge plasma sintering furnace for hot-pressing sintering after cold-press molding; discharge plasma sintering parameters: 100 ℃/min before 1300 ℃; 50 ℃/min at 1300-1450 ℃; 30 ℃/min at the temperature of 1450-1600 ℃; keeping the temperature at 1600 ℃ for 15 min; 30 ℃/min at 1600-1700 ℃; preserving the heat at 1700 ℃ for 15 min; the pressure is 30 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 886MPa, the hardness is 13.73GPa, and the fracture toughness is 7.85 MPa.M1/2。
Example 4
Si based on Spark Plasma Sintering (SPS)3N4The preparation method of the/TiC ceramic material comprises the following steps of preparing raw material components by volume percentage of alpha-Si3N4 82％，TiC 10％，Al2O3 4％，Y2O3 6％。
Weighing alpha-Si in proportion3N4Adding proper amount of absolute ethyl alcohol into TiC powder as dispersion medium, ultrasonic dispersing and mechanically stirring for 15min to obtain alpha-Si3N4Suspension, TiC suspension; mixing the three suspensions to obtain a complex phase suspension. Weighing Si3N4Dispersing agent with the weight of 3 wt% of the powder is dissolved by absolute ethyl alcohol and then added into the multiphase suspension, and then Al is added according to the proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 45 min; pouring the obtained final suspension into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, and carrying out ball milling for 48 hours in a nitrogen atmosphere;
drying the obtained ball milling liquid for 12 hours at 110 ℃ in a vacuum drying oven, sieving the ball milling liquid by a 100-mesh sieve to obtain mixed powder, filling the obtained mixed powder into a graphite mold, and putting the graphite mold into a discharge plasma sintering furnace for hot-pressing sintering after cold-press molding; discharge plasma sintering parameters: 100 ℃/min before 1300 ℃; 50 ℃/min at 1300-1450 ℃; 30 ℃/min at the temperature of 1450-1600 ℃; keeping the temperature at 1600 ℃ for 15 min; 30 ℃/min at 1600-1700 ℃; preserving heat at 1700 ℃ for 10 min; the pressure is 30 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 891MPa, the hardness is 13.21GPa, and the fracture toughness is 8.37 MPa.M1/2。
Example 5
Si based on Spark Plasma Sintering (SPS)3N4The preparation method of the/TiC ceramic material comprises the following steps of preparing raw material components by volume percentage of alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％。
Weighing alpha-Si in proportion3N4Adding proper amount of absolute ethyl alcohol into TiC powder as dispersion medium, ultrasonic dispersing and mechanically stirring for 15min to obtain alpha-Si3N4Suspension, TiC suspension; mixing the three suspensions to obtain a complex phase suspension. Weighing Si3N4Dispersing agent with the weight of 3 wt% of the powder is dissolved by absolute ethyl alcohol and then added into the multiphase suspension, and then Al is added according to the proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 45 min; and pouring the obtained final suspension into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, and carrying out ball milling for 48 hours in a nitrogen atmosphere.
Drying the obtained ball milling liquid for 12 hours at 110 ℃ in a vacuum drying oven, sieving the ball milling liquid by a 100-mesh sieve to obtain mixed powder, filling the obtained mixed powder into a graphite mold, and putting the graphite mold into a discharge plasma sintering furnace for hot-pressing sintering after cold-press molding; discharge plasma sintering parameters: 100 ℃/min before 1300 ℃; 50 ℃/min at 1300-1450 ℃; 30 ℃/min at the temperature of 1450-1600 ℃; keeping the temperature at 1600 ℃ for 15 min; 30 ℃/min at 1600-1700 ℃; preserving heat at 1700 ℃ for 10 min; the pressure is 40 MPa.
The ceramic material prepared in this example was cut into standard strip specimens of 3mm × 4mm × 35mm, and then the specimens were subjected to rough grinding, chamfering, and polishing. The mechanical property test shows that the bending strength of the material is 801MPa, the hardness is 14.63GPa, and the fracture toughness is 7.26 MPa.M1/2。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Si based on spark plasma sintering3N4The preparation method of the/TiC ceramic material is characterized by comprising the following steps: with Si3N4As matrix, TiC as reinforcing phase, Al2O3And Y2O3The sintering aid is prepared by performing wet ball milling mixing and spark plasma sintering on the raw materials.
2. Si based on spark plasma sintering according to claim 13N4The preparation method of the/TiC ceramic material is characterized in that in the preparation method, the volume percentages of the raw materials are as follows: alpha-Si3N4 70-85％，TiC 5-15％，Al2O3 1-6％，Y2O3 3-7％。
3. Si based on spark plasma sintering according to claim 23N4The preparation method of the/TiC ceramic material is characterized in that the volume percentage of TiC is 7-10%, or Al2O3Is 2-4% by volume, or said Y2O3Is 4-6% by volume.
4. Si based on spark plasma sintering according to claim 33N4The preparation method of the/TiC ceramic material is characterized in that the volume percentage of the raw materials is as follows: alpha-Si3N4 82％，TiC 10％，Al2O3 4％，Y2O36％；
Or, the volume percentage of the raw materials is as follows: alpha-Si3N4 82％，TiC 10％，Al2O3 3％，Y2O3 5％；
Or, the volume percentage of the raw materials is as follows: alpha-Si3N4 75％，TiC 15％，Al2O3 4％，Y2O3 6％。
5. Si based on spark plasma sintering according to claim 33N4The preparation method of the/TiC ceramic material is characterized in that the alpha-Si3N4The average particle size of the powder is 0.5-1 μm;
or the average grain diameter of the TiC powder is 0.5-1 mu m;
or, the Al2O3The average particle size of the powder is 0.5-2 μm;
or, said Y2O3The average particle diameter of the powder is 0.1-0.5 μm.
6. Si based on spark plasma sintering according to claim 13N4The preparation method of the/TiC ceramic material is characterized by comprising the following steps:
(1) alpha-Si is mixed3N4Adding TiC powder into dispersion medium respectively to make it uniformly dispersed so as to obtain alpha-Si3N4Mixing the suspension and the TiC suspension to obtain a complex phase suspension;
(2) weighing alpha-Si3N4Dispersing agent with weight of 1-5 wt% is added into the dispersing medium to be dissolved, then dispersing agent solution is added into the multiphase suspension, and Al is added2O3And Y2O3Uniformly dispersing the powder to obtain a mixed system;
(3) transferring the mixed system obtained in the step (2) to a ball milling tank for ball milling; drying the ball milling liquid and sieving to obtain mixed powder;
(4) and (4) filling the mixed powder in the step (3) into a mould for forming, and then performing spark plasma sintering.
7. Si based on spark plasma sintering according to claim 63N4The preparation method of the/TiC ceramic material is characterized in that in the step (1) or (2), the dispersion medium comprises but is not limited to absolute ethyl alcohol or absolute methyl alcohol;
or, in the step (2), the dispersing agent includes but is not limited to polyethylene glycol, specifically, polyethylene glycol 6000;
or, in the step (3), ball milling is carried out for 40-50 h in a protective atmosphere by adding ball milling balls according to the ball material weight ratio of 10: 0.5-1.5; specifically, the protective atmosphere is nitrogen;
or, in the step (3), the ball grinding balls are cemented carbide pellets YG6 or YG 8;
or, in the step (3), the drying manner of the ball milling liquid includes but is not limited to one of atmospheric drying, vacuum drying, spray drying or freeze drying; specifically, the drying adopts vacuum drying, and the drying is carried out for 12 to 24 hours at a temperature of between 80 and 120 ℃;
or, in the step (3), the ball milling liquid is dried and sieved by a sieve with 100-120 meshes to obtain mixed powder;
or, in the step (4), the discharge plasma sintering parameters are as follows: the heating rate is as follows: before 1300 ℃, 90-110 ℃/min, higher than 1300 ℃, 30-50 ℃/min; the sintering temperature is 1650-1750 ℃; the heat preservation time is 20-35min, and the heat preservation time is 10-17min after the temperature is 1600 ℃ and the sintering temperature is reached respectively; the axial pressure is 25-35 MPa.
8. Si based on spark plasma sintering according to claim 73N4The preparation method of the/TiC ceramic material is characterized by comprising the following steps of:
(1) weighing alpha-Si in proportion3N4Adding a proper amount of absolute ethyl alcohol into the TiC powder respectively to serve as a dispersion medium, performing ultrasonic dispersion and mechanically stirring for 10-20min to obtain alpha-Si3N4Suspension liquid and TiC suspension liquid, and mixing the two suspension liquids to obtain complex phase suspension liquid;
(2) weighing alpha-Si3N4Dissolving 1-5 wt% of polyethylene glycol 6000 in anhydrous ethanol, adding into the multiphase suspension, and adding Al in proportion2O3And Y2O3Ultrasonically dispersing the powder and mechanically stirring for 30-50 min;
(3) pouring the final suspension obtained in the step (2) into a ball milling tank, adding ball milling balls according to the ball material weight ratio of 10:1, carrying out ball milling for 48 hours under a protective atmosphere, drying the ball milling liquid in a vacuum drying oven at 80-120 ℃ for 12-24 hours, sieving the ball milling liquid through a 100-sand-screening 120-mesh sieve to obtain mixed powder, and sealing and storing for later use;
(4) and (4) filling the mixed powder obtained in the step (3) into a graphite die, and putting the graphite die into a discharge plasma sintering furnace for sintering after cold press molding.
9. Si based on spark plasma sintering according to any of claims 1 to 83N4Si prepared by preparation method of TiC ceramic material3N4A TiC ceramic material.
10. Si according to claim 93N4The TiC ceramic material is applied to the fields of producing cutting tools, wear-resistant parts, inserts, products for the aviation industry and the like.
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