CN110655404A - Titanium silicon carbide based composite ceramic material and preparation process thereof - Google Patents

Titanium silicon carbide based composite ceramic material and preparation process thereof Download PDF

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CN110655404A
CN110655404A CN201911044709.0A CN201911044709A CN110655404A CN 110655404 A CN110655404 A CN 110655404A CN 201911044709 A CN201911044709 A CN 201911044709A CN 110655404 A CN110655404 A CN 110655404A
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ceramic material
composite ceramic
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钟志宏
李振
袁邦国
陈畅
吴玉程
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Hefei University of Technology
Hefei Polytechnic University
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Abstract

The invention discloses a titanium silicon carbide based composite ceramic material and a preparation process thereof, which is prepared from Ti3SiC2、B4C and Si as raw materials, and is prepared by spark plasma sintering technology, in which Ti is added3SiC2TiB with fine and uniformly distributed grains is generated in situ reaction in the substrate2SiC and TiC hard reinforcing phase, in refining Ti3SiC2While organizing, effectively improves the hardness, the strength and the fracture toughness of the composite ceramic. Ti obtained by the invention3SiC2The base composite ceramic material has the characteristics of high density, high hardness, high bending strength, high fracture toughness and the like, and has higher practical value.

Description

Titanium silicon carbide based composite ceramic material and preparation process thereof
Technical Field
The invention relates to a titanium silicon carbide (Ti)3SiC2) A base composite ceramic material and a preparation process thereof belong to the field of reaction sintering preparation of ceramic matrix composite materials.
Background
Ti3SiC2The material is a ternary layered MAX phase ceramic which combines a plurality of excellent properties of metal and ceramic. It is combined withThe metal is the same as the metal, has good heat-conducting property and electric conductivity at normal temperature, relatively low Vickers hardness and high elastic modulus, and has ductility at normal temperature. Meanwhile, the ceramic material has the properties of a ceramic material, has high yield strength, high melting point, high thermal stability and good oxidation resistance, and can maintain high strength at high temperature. More importantly, the material is different from the traditional carbide ceramic, can be processed in a traditional processing mode like metal, and has lower friction coefficient and excellent self-lubricating property compared with molybdenum disulfide and graphite. Thus, Ti3SiC2The ceramic is considered to have wide application prospect in the fields of high-temperature structural materials, self-lubricating materials, electrode materials and the like. However, due to Ti3SiC2The hardness is low, the creep resistance is poor, and the potential application of the high-temperature structural material is limited. To make up for Ti3SiC2The disadvantage of the material is that Ti is required3SiC2Introduction of reinforcing phase into material to develop Ti3SiC2A base composite ceramic or composite material. Ti3SiC2The wide application prospect of the composite material promotes the development of the ceramic sintering technology, and the development of the ceramic material sintering preparation technology can also widen Ti3SiC2The field of application of (1). Therefore, Ti was investigated3SiC2And the sintering preparation process of the composite material thereof has important significance.
Studies have shown that in Ti3SiC2Proper amount of titanium carbide (TiC) is introduced to improve the mechanical property of the alloy. Similarly, in Ti3SiC2Adding a certain amount of silicon carbide (SiC) and titanium diboride (TiB)2) Or aluminum oxide (Al)2O3) The Ti can be improved by using the materials as the reinforcing phase3SiC2Mechanical properties of the block material. If, however, directly at Ti3SiC2Adding SiC and TiB2When the ceramic reinforcing phase is adopted, higher compactness can be obtained under higher sintering temperature. In addition, if the sintering temperature is too high, Ti may be caused3SiC2To form TiCx(>1500 ℃ C.). In addition, mixing with common powderBy contrast, in situ reaction at Ti3SiC2Formation of SiC and TiB in the matrix2The equal reinforcing phase can not only reduce the sintering temperature of the reaction, but also obtain the reinforcing phase with fine grains and uniform distribution, thereby obtaining the composite ceramic material with more excellent performance under the action of various strengthening mechanisms such as dispersion strengthening and the like. Therefore, the method for preparing Ti with high density and excellent performance by sintering at lower temperature is explored3SiC2The composite ceramic material has important practical significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a titanium silicon carbide-based composite ceramic material with good comprehensive mechanical properties and a preparation process thereof.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention firstly discloses a titanium silicon carbide based composite ceramic material which is characterized in that: the Ti3SiC2The base composite ceramic material is Ti3SiC2、B4C and Si are used as raw materials and are prepared by a spark plasma sintering technology.
The Ti3SiC2The base composite ceramic material comprises the following raw materials in percentage by mass: ti3SiC277.5-92.5 wt.% powder, 2.5-7.5 wt.% Si powder, B4C powder 5-15 wt.%.
Further, the Ti3SiC2The purity of the powder is more than or equal to 98 percent, the particle size is less than or equal to 50 mu m, and B4The purity of the C powder is more than or equal to 97 percent, the particle size is less than or equal to 5 mu m, the purity of the Si powder is more than or equal to 99 percent, and the particle size is less than or equal to 10 mu m.
The preparation process of the silicon titanium carbide-based composite ceramic material comprises the following steps:
step 1, preparation of reaction sintering mixed powder
Weighing Ti according to the proportion3SiC2Powder, B4Pouring the C powder and the Si powder into a ball milling tank, taking ethanol as a ball milling medium, uniformly mixing in a ball mill of a planet, and drying the mixed powder in a vacuum drying oven at 50 ℃ for 12 hours to obtain the reverseThe mixed powder should be sintered;
step 2, in-situ reaction discharge plasma sintering
Assembling the reaction sintering mixed powder into a graphite mold, and then placing the graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the furnace chamber to below 20Pa at room temperature, heating to sintering temperature, keeping the temperature for 10min, loading the pressure to 50MPa, and cooling and depressurizing the furnace after the heat preservation stage is finished to obtain Ti3SiC2A base composite ceramic material.
Further, in the step 1, the rotation speed of the planetary ball mill is 150-.
Further, in step 2, the sintering temperature is 1330-1380 ℃.
Further, in the step 2, the temperature rise rate in the discharge plasma sintering process is 50-100 ℃/min.
Further, in step 2, the pressure is reduced to 0MPa at a pressure reduction rate of 30 MPa/min.
The invention utilizes the spark plasma sintering technology to prepare Ti through in-situ reaction under the technological parameters of the sintering temperature of 1330-1380 ℃, the heat preservation time of 10min and the pressure of 50MPa3SiC2A base composite ceramic material. Wherein 10 wt.% B is added4C and wt.% Si, and when the sintering temperature is 1350 ℃, Ti with better comprehensive mechanical property is obtained3SiC2The Vickers hardness, bending strength, fracture toughness and relative density of the base composite ceramic material are respectively 13.5GPa, 539.8MPa and 7.2 MPa.m1 /299.3 percent and has higher practical value.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention explores Ti3SiC2、B4The ratio of the C powder to the Si powder and the discharge plasma sintering process parameters are adopted to obtain Ti through the in-situ reaction sintering of the mixed powder at relatively low sintering temperature and relatively high heating speed3SiC2A base composite ceramic material. Obtained by the inventionThe composite ceramic material has the characteristics of high density, high hardness, excellent bending strength and fracture toughness, and the like, and has higher practical value.
2. The composite ceramic material obtained by the invention mainly comprises Ti3SiC2、SiC、TiB2And TiC. Compared with using Ti3SiC2、SiC、TiB2The invention can reduce sintering temperature and obtain composite ceramic with finer crystal grains.
3. The invention utilizes Ti3SiC2、B4The in-situ reaction of C and Si obtains Ti3SiC2-TiB2-SiC-TiC multiphase composite ceramic. High-strength ceramic reinforcing phase TiB with fine grains is generated by reaction2The components of (25-35 GPa), SiC (20-27 GPa) and TiC (22-28 GPa) are uniformly distributed in Ti with relatively low hardness3SiC2In the matrix, under the action of a dispersion strengthening mechanism, the hardness and the strength of the composite ceramic are effectively improved. Meanwhile, in the process of material fracture, the cracks deflect at the interfaces of different ceramic phases, so that the fracture path is increased, and the fracture toughness is improved.
4. The invention utilizes Ti3SiC2、B4In-situ reaction of C and Si to generate TiB2(～8.1×10-6K-1)、SiC(～4.1×10-6K-1)、TiC(～7.4×10-6K-1) Ceramic phase and Ti3SiC2(～9.1×10-6K-1) The matrix phase has certain thermal expansion coefficient difference, and the residual stress at the interface of different phases can improve the strength of the composite ceramic, and simultaneously, the purpose of improving the fracture toughness is achieved under the toughening mechanisms of crack deflection, crack bridging, crack branching and the like.
Drawings
FIG. 1 is Ti3SiC2Ceramic material and addition of B in different mass fractions4Ti made of C and Si3SiC2A microstructure photograph of a base composite ceramic material, wherein: (a) ti prepared corresponding to comparative example 13SiC2A ceramic material; (b) corresponding embodiment1 prepared Ti3SiC2Base composite ceramic material (Ti)3SiC2+5wt.％B4C +2.5 wt.% Si); (c) ti prepared in accordance with example 23SiC2Base composite ceramic material (Ti)3SiC2+10wt.％B4C +5 wt.% Si); (d) ti prepared in accordance with example 33SiC2Base composite ceramic material (Ti)3SiC2+15wt.％B4C+7.5wt.％Si)。
FIG. 2 is Ti3SiC2Ceramic material and addition of B in different mass fractions4Ti made of C and Si3SiC2An XRD pattern of the base composite ceramic, wherein: curve (a) corresponds to the Ti as prepared in comparative example 13SiC2A ceramic material; curve (b) corresponds to the Ti prepared in example 13SiC2Base composite ceramic material (Ti)3SiC2+5wt.％B4C +2.5 wt.% Si); curve (c) corresponds to the Ti prepared in example 23SiC2Base composite ceramic material (Ti)3SiC2+10wt.％B4C +5 wt.% Si); curve (d) corresponds to the Ti prepared in example 33SiC2Base composite ceramic material (Ti)3SiC2+15wt.％B4C+7.5wt.％Si)。
FIG. 3 shows the addition of different mass fractions B4Ti made of C and Si3SiC2Mechanical properties of the base composite ceramic material, wherein: graph (a) shows vickers hardness and flexural strength of the composite ceramic material; the graph (b) shows the fracture toughness and the relative density of the composite ceramic.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the examples described below, the Ti3SiC2The purity of the powder is more than or equal to 98 percent, the particle size is less than or equal to 50 mu m, and B4The purity of the C powder is more than or equal to 97 percent, the particle size is less than or equal to 5 mu m, the purity of the Si powder is more than or equal to 99 percent, and the particle size is less than or equal to 10 mu m.
Comparative example 1
This example prepares Ti by spark plasma sintering3SiC2Ceramic materialThe sintering process of the material is as follows:
mixing Ti3SiC2Assembling the powder into a graphite mold with the inner diameter of 40mm, and then putting the graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the sintering furnace to below 20Pa at room temperature, loading the sintering furnace under the pressure of 50MPa, heating to the sintering temperature of 1350 ℃ and preserving the temperature for 10min, and cooling and reducing the pressure (reducing the pressure to 0MPa at the pressure reduction rate of 30 MPa/min) along with the furnace after the heat preservation stage is finished to obtain Ti3SiC2A ceramic material.
By testing, Ti obtained in this example3SiC2The Vickers hardness, bending strength, fracture toughness and relative density of the ceramic material are respectively 4.7GPa, 413.8MPa and 5.3 MPa.m1/2、98.5％。
Example 1
This example prepares Ti by in situ reaction using spark plasma sintering preparation technique3SiC2The sintering preparation process of the base composite ceramic material comprises the following steps:
step 1, preparation of reaction sintering mixed powder
According to 92.5% Ti3SiC2+5％B4Weighing Ti according to the mass ratio of C + 2.5% Si3SiC2、B4Pouring C and Si into a nylon ball milling tank, ball milling for 8 hours in a planetary ball mill by using agate milling balls and ethanol as a ball milling medium, and drying the mixed powder in a vacuum drying oven at 50 ℃ for 12 hours to obtain reaction sintering mixed powder;
step 2, in-situ reaction discharge plasma sintering
Assembling the reaction sintering mixed powder into a graphite mold with the inner diameter of 40mm, and then placing the assembled graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the sintering furnace to below 20Pa at room temperature, loading the sintering furnace under the pressure of 50MPa, heating to the sintering temperature of 1350 ℃ and preserving the temperature for 10min, and cooling and reducing the pressure (reducing the pressure to 0MPa at the pressure reduction rate of 30 MPa/min) along with the furnace after the heat preservation stage is finished to obtain Ti3SiC2Base composite ceramic material (Ti)3SiC2+5wt.％B4C+2.5wt.％Si)。
After testing, the results obtained in this exampleTi of (A)3SiC2The Vickers hardness, bending strength, fracture toughness and relative density of the base composite ceramic material are respectively 7.3GPa, 497.3MPa and 6.7 MPa.m1/2、99.1％。
Example 2
This example prepares Ti by in situ reaction using spark plasma sintering preparation technique3SiC2The sintering preparation process of the base composite ceramic material comprises the following steps:
step 1, preparation of reaction sintering mixed powder
According to 85% Ti3SiC2+10％B4Weighing Ti according to the mass ratio of C + 5% Si3SiC2、B4Pouring C and Si into a nylon ball milling tank, ball milling for 8 hours in a planetary ball mill by using agate milling balls and ethanol as a ball milling medium, and drying the mixed powder in a vacuum drying oven at 50 ℃ for 12 hours to obtain reaction sintering mixed powder;
step 2, in-situ reaction discharge plasma sintering
Assembling the reaction sintering mixed powder into a graphite mold with the inner diameter of 40mm, and then placing the assembled graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the sintering furnace to below 20Pa at room temperature, loading the sintering furnace under the pressure of 50MPa, heating to the sintering temperature of 1350 ℃ and preserving the temperature for 10min, and cooling and reducing the pressure (reducing the pressure to 0MPa at the pressure reduction rate of 30 MPa/min) along with the furnace after the heat preservation stage is finished to obtain Ti3SiC2Base composite ceramic material (Ti)3SiC2+10wt.％B4C+5wt.％Si)。
By testing, Ti obtained in this example3SiC2The Vickers hardness, bending strength, fracture toughness and relative density of the base composite ceramic material are respectively 13.5GPa, 539.8MPa and 7.2 MPa.m1/2、99.3％。
Example 3
This example prepares Ti by in situ reaction using spark plasma sintering technique3SiC2The sintering process of the base composite ceramic material comprises the following steps:
step 1, preparation of reaction sintering mixed powder
According to 77.5% Ti3SiC2+15％B4Weighing Ti according to the mass ratio of C + 7.5% Si3SiC2、B4Pouring C and Si into a nylon ball milling tank, ball milling for 8 hours in a planetary ball mill by using agate milling balls and ethanol as a ball milling medium, and drying the mixed powder in a vacuum drying oven at 50 ℃ for 12 hours to obtain reaction sintering mixed powder;
step 2, in-situ reaction discharge plasma sintering
Assembling the reaction sintering mixed powder into a graphite mold with the inner diameter of 40mm, and then placing the assembled graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the sintering furnace to below 20Pa at room temperature, loading the sintering furnace under the pressure of 50MPa, heating to the sintering temperature of 1350 ℃ and preserving the temperature for 10min, and cooling and reducing the pressure (reducing the pressure to 0MPa at the pressure reduction rate of 30 MPa/min) along with the furnace after the heat preservation stage is finished to obtain Ti3SiC2Base composite ceramic material (Ti)3SiC2+15wt.％B4C+7.5wt.％Si)。
By testing, Ti obtained in this example3SiC2The Vickers hardness, bending strength, fracture toughness and relative density of the base composite ceramic material are respectively 24.7GPa, 590.2MPa and 6.1 MPa.m1/2、98.9％。
FIG. 1 is Ti3SiC2Ceramic material and addition of B in different mass fractions4Ti made of C and Si3SiC2A microstructure photograph of a base composite ceramic material, wherein: (a) ti prepared corresponding to comparative example 13SiC2A ceramic material; (b) ti prepared in accordance with example 13SiC2Base composite ceramic material (Ti)3SiC2+5wt.％B4C +2.5 wt.% Si); (c) ti prepared for example 23SiC2Base composite ceramic material (Ti)3SiC2+10wt.％B4C +5 wt.% Si); (d) ti prepared for example 33SiC2Base composite ceramic material (Ti)3SiC2+15wt.％B4C +7.5 wt.% Si). As can be seen from FIG. 1, high-density Ti can be obtained at 1350 deg.C3SiC2And Ti3SiC2A base composite ceramic. Addition of B4C and Si, refining the microstructure, and in-situ reacting to generate SiC and TiB with fine grains2And TiC is uniformly distributed in Ti3SiC2In the matrix.
FIG. 2 is Ti3SiC2Ceramic material and addition of B in different mass fractions4Ti made of C and Si3SiC2An XRD pattern of the base composite ceramic, wherein: curve (a) corresponds to the Ti as prepared in comparative example 13SiC2A ceramic material; curve (b) corresponds to the Ti prepared in example 13SiC2Base composite ceramic material (Ti)3SiC2+5wt.％B4C +2.5 wt.% Si); curve (c) corresponds to the Ti prepared in example 23SiC2Base composite ceramic material (Ti)3SiC2+10wt.％B4C +5 wt.% Si); curve (d) corresponds to the Ti prepared in example 33SiC2Base composite ceramic material (Ti)3SiC2+15wt.％B4C +7.5 wt.% Si). From the XRD result, Ti was confirmed3SiC2The composition of the phase in the base composite ceramic.
FIG. 3 shows the addition of different mass fractions B4Ti made of C and Si3SiC2Mechanical properties of the base composite ceramic material, wherein: graph (a) shows vickers hardness and flexural strength of the composite ceramic material; the graph (b) shows the fracture toughness and the relative density of the composite ceramic. From FIG. 3, it can be seen that Vickers hardness and bending strength vary with B4The mass fractions of C and Si are increased, and the fracture toughness and the compactness are improved along with the B4The increase in the mass fractions of C and Si increases first and then decreases.
As can be seen from the above examples, the present invention is achieved by adjusting Ti3SiC2Si and B4The proportion of the C powder is that Ti with high density, high hardness, excellent bending strength and excellent fracture toughness is obtained by the in-situ reaction of the mixed powder at relatively low temperature and high heating speed3SiC2A base composite ceramic material. High-strength ceramic reinforcing phase TiB with fine grains is generated by reaction2SiC and TiC are uniformly distributed in Ti with relatively low hardness3SiC2In the matrix, effectively improveHardness and strength of the composite ceramic. Meanwhile, in the process of material fracture, the cracks deflect at the interfaces of different ceramic phases, so that the fracture path is increased, and the fracture toughness is improved. The invention can prepare Ti with excellent comprehensive mechanical property3SiC2Based on composite ceramic material, solves the problem of Ti3SiC2A technical problem for preparing and applying the base composite ceramic.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A titanium silicon carbide based composite ceramic material is characterized in that: the Ti3SiC2The base composite ceramic material is Ti3SiC2、B4C and Si are used as raw materials and are prepared by a spark plasma sintering technology.
2. The silicon titanocarbide-based composite ceramic material according to claim 1, wherein: the Ti3SiC2The base composite ceramic material comprises the following raw materials in percentage by mass: ti3SiC277.5-92.5 wt.% powder, 2.5-7.5 wt.% Si powder, B4C powder 5-15 wt.%.
3. The silicon titanocarbide-based composite ceramic material according to claim 1, wherein: the Ti3SiC2The purity of the powder is more than or equal to 98 percent, and the particle size is less than or equal to 50 mu m; b is4The purity of the C powder is more than or equal to 97 percent, and the particle size is less than or equal to 5 mu m; the purity of the Si powder is more than or equal to 99 percent, and the grain diameter is less than or equal to 10 mu m.
4. A preparation process of the silicon titanium carbide-based composite ceramic material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
step 1, preparation of reaction sintering mixed powder
Weighing Ti according to the proportion3SiC2Powder, B4Pouring the powder C and the powder Si into a ball milling tank, taking ethanol as a ball milling medium, carrying out ball milling and uniformly mixing in a planetary ball mill, and then placing the mixed powder in a vacuum drying oven for drying at 50 ℃ for 12 hours to obtain reaction sintering mixed powder;
step 2, in-situ reaction discharge plasma sintering
Assembling the reaction sintering mixed powder into a graphite mold, and then placing the graphite mold into a furnace chamber of a discharge plasma sintering furnace; vacuumizing the sintering furnace to below 20Pa at room temperature, heating to the sintering temperature, keeping the temperature for 10min, loading the pressure to 50MPa, and cooling and depressurizing the furnace after the heat preservation stage is finished to obtain Ti3SiC2A base composite ceramic material.
5. The process according to claim 4, characterized in that: in the step 1, the rotating speed of the planetary ball mill is 150-250rpm, and the ball milling time is 8-12 h.
6. The process according to claim 4, characterized in that: in step 2, the sintering temperature is 1330-1380 ℃.
7. The process according to claim 4, characterized in that: in step 2, the heating rate is 50-100 ℃/min.
8. The process according to claim 4, characterized in that: in the step 2, the pressure is reduced to 0MPa at a pressure reduction rate of 30 MPa/min.
CN201911044709.0A 2019-10-30 2019-10-30 Titanium silicon carbide based composite ceramic material and preparation process thereof Pending CN110655404A (en)

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