CN114262229B - Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic - Google Patents
Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic Download PDFInfo
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Abstract
A preparation method and application of high-toughness diboride-carbide complex phase high-entropy ceramic belong to the technical field of ceramic materials, and particularly relate to a preparation method and application of high-toughness diboride-carbide complex phase high-entropy ceramic material. The invention aims to solve the problems that the existing single-phase high-entropy ceramic material is difficult to sinter, low in density and poor in fracture toughness, and the application of the ceramic material is limited. The method comprises the following steps: preparing mixed powder of diboride powder and titanium carbide; secondly, hot-pressing and sintering. A high-toughness diboride-carbide complex phase high-entropy ceramic is applied to nuclear reactors and ultrahigh-temperature fields. The density of the prepared complex phase ceramic is more than 97%, the strength and toughness are remarkably improved, the hardness of the ceramic at room temperature is 35-40 GPa, the three-point bending strength is 800-1100 MPa, and the fracture toughness is 6-8 MPa.m 1/2 . The invention can obtain high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a preparation method and application of a high-toughness diboride-carbide complex phase high-entropy ceramic material.
Background
In recent years, the development of the fields of aerospace, machinery, metallurgy, nuclear energy, chemical industry, military industry and the like is rapid, the requirement on the service performance of materials is more and more rigorous, and the traditional single material cannot meet the use requirement easily. The high-entropy ceramic is a novel material which appears recently, and refers to ceramic with five or more than five components, and the solid solution coupling effect existing among the multiple components enables the material to have a higher entropy value, so that the phase stability of the ceramic can be effectively improved; meanwhile, the ceramic material has high hardness (>25GPa) due to the obvious solid-solution strengthening effect. The appearance of the high-entropy ceramic can widen the design space of the material, coordinate the comprehensive performance of the material and meet the performance requirement under the service of an extreme environment.
In the current reports, the high-entropy ceramics mainly focus on single-phase high-entropy ceramic systems such as carbide, boride, nitride, oxide and the like, and complex-phase high-entropy ceramic materials are rarely reported. In addition, the high melting point and the low self-diffusion coefficient of the high-entropy ceramic material make the single-phase high-entropy ceramic material difficult to sinter, and the low density is a ubiquitous problem; meanwhile, the single-phase high-entropy ceramic lacks a toughening mechanism, and the fracture toughness of the material is generally 3-5 MPa.m 1/2 And the application thereof is limited. Therefore, it is necessary to provide a preparation method of a high-strength and high-toughness complex-phase high-entropy ceramic material.
Disclosure of Invention
The invention aims to solve the problems that the existing single-phase high-entropy ceramic material is difficult to sinter, low in density and poor in fracture toughness, and the application of the single-phase high-entropy ceramic material is limited, and provides a preparation method and application of high-toughness diboride-carbide complex-phase high-entropy ceramic.
A preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
and secondly, placing the mixed powder in a die for sintering to obtain the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
A high-toughness diboride-carbide complex phase high-entropy ceramic is applied to nuclear reactors and ultrahigh-temperature fields.
The invention has the following beneficial effects:
the method comprises the steps of firstly, selecting various diboride powder and titanium carbide which can generate solid phase reaction, preparing mixed powder by adopting a high-energy ball milling process, and carrying out reaction hot-pressing sintering under the protection of inert atmosphere to prepare high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic; the density of the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic prepared by the invention is more than 97%, and the sintering temperature is reduced by more than 200 ℃ compared with that of a single-phase high-entropy ceramic material;
secondly, the complex-phase high-entropy ceramic material has a more complex interface relationship, and two-phase growth is more difficult than that in a single-phase system due to the difference of interface energy and different migration capacities of heterogeneous atoms in different interfaces; therefore, the grain size of the complex phase high-entropy ceramic material is finer, the strength and toughness of the prepared high-toughness diboride-carbide complex phase high-entropy ceramic are obviously improved, the hardness of the ceramic at room temperature is 35-40 GPa, the three-point bending strength is 800-1100 MPa, and the fracture toughness is 6-8 MPa.m 1/2 . Can be applied to nuclear reactors and ultrahigh temperature fields.
The invention can obtain high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
Drawings
FIG. 1 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 XRD pattern of high toughness complex phase high entropy ceramics of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 2 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 SEM microstructure photograph of high-strength and high-toughness complex-phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 3 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 A Ti element surface distribution electron probe diagram of the high-strength and toughness complex phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 4 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 A Zr element surface distribution electron probe diagram of the high-strength and toughness complex phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 5 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 An Hf element surface distribution electron probe diagram of high-strength and toughness complex-phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 6 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 An Nb element surface distribution electron probe diagram of the high-strength and toughness complex-phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 7 shows the preparation of example 1The chemical formula is (Ti, Zr, Hf, Nb, Ta) B 2 A Ta element surface distribution electron probe diagram of the high-strength and toughness complex-phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 8 is a graph of the chemical formula (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 B element surface distribution electron probe diagram of high-toughness complex phase high-entropy ceramic of- (Ti, Zr, Hf, Nb, Ta) C;
FIG. 9 shows the chemical formula of (Ti, Zr, Hf, Nb, Ta) B prepared in example 1 2 A C element surface distribution electron probe diagram of high-toughness complex phase high-entropy ceramics of- (Ti, Zr, Hf, Nb, Ta) C.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the molar ratio of zirconium diboride, hafnium diboride, niobium diboride and tantalum diboride in the step one is 1:1:1: 1;
and secondly, placing the mixed powder in a die for sintering to obtain the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the mole fraction of the titanium carbide powder in the mixed powder in the step one is 30-70%. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is: the mole fraction of the titanium carbide powder in the mixed powder in the first step is 50%. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is (10-100): 1, the ball milling time is 10-40 h, and the rotating speed of the ball mill is 200-600 r/min; the ball milling tank and the milling balls are made of hard alloy. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and the sintering in the second step is hot-pressing sintering. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the hot-pressing sintering process in the second step comprises the following steps: the temperature is increased from the room temperature to 1500-1700 ℃, the temperature is kept at 1500-1700 ℃ for 0.5-1 h, the inert gas is introduced into the furnace body after the temperature is kept, the temperature is increased to 1900-2000 ℃ under the atmosphere of the inert gas, the temperature is kept for 0.5-2 h under the conditions of 1900-2000 ℃ and the sintering pressure of 30-50 MPa, and the temperature rising and falling speed is 10-40 ℃/min. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the inert gas is argon, helium or krypton; the heating rate is 10-40 ℃/min. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the relative density of the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic in the step two>97 percent of room temperature hardness of 35 GPa-40 GPa, three-point bending strength of 800 MPa-1100 MPa and fracture toughness of 6 MPa.m 1/2 ～8MPa·m 1/2 . The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is applied to the fields of nuclear reactors and ultrahigh temperatures.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1: a preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the mole fraction of the titanium carbide powder in the mixed powder in the step one is 50%;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: heating from room temperature to 1650 ℃, preserving heat for 0.5h at 1650 ℃, introducing argon into the furnace body after finishing the heat preservation, heating to the sintering temperature of 2000 ℃ under the argon atmosphere, preserving heat for 1h under the conditions of 2000 ℃ and the sintering pressure of 30MPa, and increasing and decreasing the temperature at the speed of 20 ℃/min; demoulding to obtain the compound with the chemical formula of (Ti) 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 -(Ti 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) C is high-strength and high-toughness complex-phase high-entropy ceramic.
The chemical formula prepared in example 1 is (Ti) 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 -(Ti 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) XRD test is carried out on the high-toughness complex-phase high-entropy ceramic of C, the test result is shown in figure 1, and the '●' in figure 1 is (Ti 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 Corresponding to the diffraction peak, ". diamond-solid" is (Ti) 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) C corresponds to a diffraction peak; the TiB is generated by the following solid exchange reaction of zirconium diboride, hafnium diboride, niobium diboride and tantalum diboride with titanium carbide respectively 2 And a series of carbides:
ZrB 2 +TiC→TiB 2 +ZrC；
HfB 2 +TiC→TiB 2 +HfC；
NbB 2 +TiC→TiB 2 +NbC；
TaB 2 +TiC→TiB 2 +TaC；
various compounds can also be subjected to mutual solid solution, and two solid solution phases are finally generated; the materials obtained by sintering are all complex phases according to the diffraction peak, and the main phases of the materials can be found to be a carbide phase with a face-centered cubic structure and a boride phase with a close-packed hexagonal structure respectively by calibrating the diffraction peak, so that the technical scheme is proved to be capable of obtaining the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
The chemical formula prepared in example 1 is (Ti) 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 -(Ti 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) SEM test is carried out on the high-strength and toughness complex-phase high-entropy ceramic, and the test result is shown in figure 2; as can be seen from FIG. 2, the complex phase high entropy ceramic is composed of a diboride black phase and a carbide white phase; the material almost does not contain air holes, and the densification is basically realized; the material structure is uniformly distributed, and the grain size is small; because each crystal face of the diboride phase has obvious anisotropy, crystal grains are easy to grow into platy crystal grains in the growth process; the plate-shaped crystals cause the deflection or bridging of cracks during the propagation process, thereby improving the toughness of the material.
Prepared as in example 1Has a chemical formula of (Ti) 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 -(Ti 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) EPMA analysis is carried out on the high-strength and high-toughness complex-phase high-entropy ceramic of C, and the test results are shown in figures 3-9. As can be seen from the figure, all the metal elements are unevenly distributed in the complex-phase high-entropy ceramic; ti and Nb tend to concentrate in the diboride phase, while Zr, Hf and Ta are preferentially solid dissolved in the carbides.
The chemical formula prepared in example 1 is (Ti) 0.64 ,Zr 0.07 ,Hf 0.07 ,Nb 0.15 ,Ta 0.07 )B 2 -(Ti 0.35 ,Zr 0.19 ,Hf 0.18 ,Nb 0.10 ,Ta 0.18 ) The mechanical property test of the high-strength and high-toughness complex-phase high-entropy ceramic of C shows that the relative density of the complex-phase ceramic is 98.1 percent at room temperature, the hardness is 37GPa, the three-point bending strength is 1017MPa, and the fracture toughness is 7.2 MPa.m 1/2 。
Example 2: a preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the mole fraction of the titanium carbide powder in the mixed powder in the step one is 30%;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: firstly, the temperature is raised from room temperature to 1Keeping the temperature at 650 ℃ and 1650 ℃ for 0.5h, introducing argon into the furnace body after the heat preservation is finished, heating to the sintering temperature of 1900 ℃ under the argon atmosphere, keeping the temperature for 1h under the conditions of 1900 ℃ and the sintering pressure of 50MPa, and increasing and decreasing the temperature at the rate of 20 ℃/min; demoulding to obtain the compound with the chemical formula of (Ti) 0.36 ,Zr 0.19 ,Hf 0.09 ,Nb 0.20 ,Ta 0.16 )B 2 -(Ti 0.12 ,Zr 0.20 ,Hf 0.25 ,Nb 0.15 ,Ta 0.28 ) C is high-strength and high-toughness complex-phase high-entropy ceramic.
The chemical formula prepared in example 2 is (Ti) 0.36 ,Zr 0.19 ,Hf 0.09 ,Nb 0.20 ,Ta 0.16 )B 2 -(Ti 0.12 ,Zr 0.20 ,Hf 0.25 ,Nb 0.15 ,Ta 0.28 ) The mechanical property test of the high-strength and high-toughness complex-phase high-entropy ceramic of C shows that the relative density of the complex-phase ceramic at room temperature is 98.3 percent, the hardness is 36GPa, the three-point bending strength is 872MPa, and the fracture toughness is 6.6 MPa.m 1/2 。
Example 3: a preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the mole fraction of the titanium carbide powder in the mixed powder in the step one is 40%;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: firstly raising the temperature from room temperatureKeeping the temperature at 1650 ℃ for 0.5h, introducing argon into the furnace body after the heat preservation is finished, heating to the sintering temperature of 2000 ℃ under the argon atmosphere, keeping the temperature for 1h under the conditions that the temperature is 2000 ℃ and the sintering pressure is 30MPa, and increasing and decreasing the temperature at a speed of 20 ℃/min; demoulding to obtain the compound with the chemical formula of (Ti) 0.52 ,Zr 0.13 ,Hf 0.05 ,Nb 0.18 ,Ta 0.12 )B 2 -(Ti 0.19 ,Zr 0.22 ,Hf 0.23 ,Nb 0.15 ,Ta 0.21 ) C is high-strength and high-toughness complex-phase high-entropy ceramic.
The chemical formula prepared in example 3 is (Ti) 0.52 ,Zr 0.13 ,Hf 0.05 ,Nb 0.18 ,Ta 0.12 )B 2 -(Ti 0.19 ,Zr 0.22 ,Hf 0.23 ,Nb 0.15 ,Ta 0.21 ) The mechanical property test of the high-strength and high-toughness complex-phase high-entropy ceramic of C shows that the relative density of the complex-phase ceramic at room temperature is 98.4 percent, the hardness is 36GPa, the three-point bending strength is 914MPa, and the fracture toughness is 7.0 MPa.m 1/2 。
Example 4: a preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the mole fraction of the titanium carbide powder in the mixed powder in the step one is 60%;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: firstly from room temperatureHeating to 1650 ℃, preserving heat for 0.5h at 1650 ℃, introducing argon into the furnace body after finishing the heat preservation, heating to 1900 ℃ under the argon atmosphere, preserving heat for 2h under the conditions of 1900 ℃ and 50MPa of sintering pressure, and increasing and decreasing the temperature at a speed of 20 ℃/min; demoulding to obtain the compound with the chemical formula of (Ti) 0.78 ,Zr 0.06 ,Hf 0.02 ,Nb 0.09 ,Ta 0.05 )B 2 -(Ti 0.44 ,Zr 0.17 ,Hf 0.08 ,Nb 0.13 ,Ta 0.18 ) C is high-strength and high-toughness complex-phase high-entropy ceramic.
The chemical formula prepared in example 4 is (Ti) 0.78 ,Zr 0.06 ,Hf 0.02 ,Nb 0.09 ,Ta 0.05 )B 2 -(Ti 0.44 ,Zr 0.17 ,Hf 0.08 ,Nb 0.13 ,Ta 0.18 ) The mechanical property test of the high-strength and high-toughness complex-phase high-entropy ceramic of C shows that the relative density of the complex-phase ceramic at room temperature is 99.2 percent, the hardness is 35GPa, the three-point bending strength is 883MPa, and the fracture toughness is 6.8 MPa.m 1/2 。
Example 5: a preparation method of high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the mole fraction of the titanium carbide powder in the mixed powder in the step one is 30%;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: first fromRaising the temperature to 1650 ℃ at room temperature, preserving the heat for 0.5h at 1650 ℃, introducing argon into the furnace body after the heat preservation is finished, raising the temperature to 2000 ℃ under the argon atmosphere, preserving the heat for 1h under the conditions of 2000 ℃ and 30MPa of sintering pressure, and increasing and reducing the temperature at a speed of 20 ℃/min; demoulding to obtain the compound with the chemical formula of (Ti) 0.80 ,Zr 0.06 ,Hf 0.03 ,Nb 0.06 ,Ta 0.05 )B 2 -(Ti 0.60 ,Zr 0.11 ,Hf 0.06 ,Nb 0.10 ,Ta 0.13 ) C is high-strength and high-toughness complex-phase high-entropy ceramic.
The chemical formula prepared in example 5 is (Ti) 0.80 ,Zr 0.06 ,Hf 0.03 ,Nb 0.06 ,Ta 0.05 )B 2 -(Ti 0.60 ,Zr 0.11 ,Hf 0.06 ,Nb 0.10 ,Ta 0.13 ) The mechanical property test of the high-strength and high-toughness complex-phase high-entropy ceramic of C shows that the relative density of the complex-phase ceramic at room temperature is 98.1 percent, the hardness is 37GPa, the three-point bending strength is 925MPa, and the fracture toughness is 6.4 MPa.m 1/2 。
Comparative example 1: the preparation method of the single-phase diboride high-entropy ceramic is completed according to the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride and tantalum diboride as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the purity of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
the technological parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is 10:1, the ball milling time is 30h, the rotating speed of the main disc is 250rpm, and the rotating speed of the planetary disc is 500 rpm;
secondly, placing the mixed powder in a mould for hot-pressing sintering, wherein the hot-pressing sintering process comprises the following steps: heating from room temperature to 1650 ℃, preserving heat for 0.5h at 1650 ℃, introducing argon into the furnace body after finishing the heat preservation, heating to 1900 ℃ under the atmosphere of argon, preserving heat for 2h under the conditions of 1900 ℃ and 50MPa of sintering pressure, and increasing and decreasing the temperature at a speed of 20 ℃/min; demoulding to obtain the single-phase diboride high-entropy ceramic.
The mechanical property test of the single-phase diboride high-entropy ceramic prepared by the comparative example 1 shows that the relative density of the high-entropy ceramic at room temperature is 92.3 percent, the hardness is 21GPa, the three-point bending strength is 438MPa, and the fracture toughness is 4.2 MPa.m 1/2 . The comparison example can find that the technical scheme of the invention has obvious advantages in improving the toughening of the ceramic material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of high-toughness diboride-carbide complex phase high-entropy ceramic is characterized in that the relative density of the high-toughness diboride-carbide complex phase high-entropy ceramic>97 percent, the room temperature hardness is 35 GPa-40 GPa, the three-point bending strength is 800 MPa-1100 MPa, and the fracture toughness is 6 MPa.m 1/2 ~8MPa·m 1/2 The preparation method comprises the following steps:
firstly, mixing powder by using zirconium diboride, hafnium diboride, niobium diboride, tantalum diboride and titanium carbide powder as raw materials and adopting a high-energy ball milling method to obtain mixed powder;
the mole fraction of the titanium carbide powder in the mixed powder in the first step is 30-70%;
the molar ratio of the zirconium diboride, the hafnium diboride, the niobium diboride and the tantalum diboride in the step one is 1:1:1: 1;
and secondly, placing the mixed powder in a die for sintering to obtain the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic.
2. The method for preparing high-toughness diboride-carbide complex phase high-entropy ceramic according to claim 1, wherein the molar fraction of the titanium carbide powder in the mixed powder in the step one is 50%.
3. The method for preparing the high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic as claimed in claim 1, wherein in the step one, the purity of the zirconium diboride, the hafnium diboride, the niobium diboride, the tantalum diboride and the titanium carbide powder is more than 99.0wt.%, and the particle size D50 of the powder is 0.1-10 μm.
4. The preparation method of the high-strength and high-toughness diboride-carbide complex phase high-entropy ceramic as claimed in claim 1, wherein the process parameters of the high-energy ball milling method in the step one are as follows: the ball-material ratio is (10-100): 1, the ball milling time is 10-40 h, and the rotating speed of the ball mill is 200-600 r/min; the ball milling tank and the milling balls are made of hard alloy.
5. The method for preparing the high-toughness diboride-carbide complex phase high-entropy ceramic according to claim 1, wherein the sintering in the second step is hot-pressing sintering.
6. The preparation method of the high-toughness diboride-carbide complex phase high-entropy ceramic according to claim 5, wherein the hot-pressing sintering process in the second step is as follows: the temperature is increased from room temperature to 1500-1700 ℃, the temperature is maintained at 1500-1700 ℃ for 0.5-1 h, inert gas is introduced into the furnace body after the temperature is maintained, the temperature is increased to 1900-2000 ℃ under the atmosphere of the inert gas, the temperature is maintained for 0.5-2 h under the conditions of 1900-2000 ℃ and the sintering pressure of 30-50 MPa, and the temperature increase and decrease rate is 10-40 ℃/min.
7. The method for preparing the high-toughness diboride-carbide complex phase high-entropy ceramic as claimed in claim 6, wherein the inert gas is argon, helium or krypton; the heating rate is 10-40 ℃/min.
8. The application of the high-toughness diboride-carbide complex-phase high-entropy ceramic prepared by the preparation method according to any one of claims 1 to 7 is characterized in that the high-toughness diboride-carbide complex-phase high-entropy ceramic is applied to the fields of nuclear reactors and ultrahigh temperature.
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