CN116354730A - (Ti, zr, hf) B 2 Intermediate entropy ceramic matrix composite material and preparation method thereof - Google Patents

(Ti, zr, hf) B 2 Intermediate entropy ceramic matrix composite material and preparation method thereof Download PDF

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CN116354730A
CN116354730A CN202310337520.0A CN202310337520A CN116354730A CN 116354730 A CN116354730 A CN 116354730A CN 202310337520 A CN202310337520 A CN 202310337520A CN 116354730 A CN116354730 A CN 116354730A
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medium
ceramic
entropy ceramic
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王新刚
王小飞
高巍
王铭
蒋丹宇
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention provides a (Ti, zr, hf) B 2 Intermediate entropy ceramic matrix composite and method for preparing same, comprising (Ti, zr, hf) B 2 BN and B 4 C, adopting oxide raw material, B 4 The C powder is prepared by ball milling, mixing, pressurizing and sintering by using a silicon nitride ball milling medium. The technical scheme of the invention has simple process, low oxygen content of the synthesized complex phase powder and the prepared ceramic, small crystal grains and uniform grain size distribution, and the prepared intermediate entropy ceramic-based complex phase material has excellent mechanical properties such as strength, toughness and the like at high temperature.

Description

(Ti, zr, hf) B 2 Intermediate entropy ceramic matrix composite material and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of ultrahigh-temperature ceramic materials, in particular to a low-temperature densification high-strength high-toughness (Ti, zr, hf) B 2 A medium entropy ceramic matrix composite and a preparation method thereof.
Background
In 2004, the concept of High-entropy alloys (High-entopy alloys) was almost simultaneously proposed by two subject groups, taiwan university of Qinghai She Junwei and the university of oxford, uk Cantor. They found that (near) equiatomic ratio of various alloying elements were melted at high temperature and that single-phase solid solutions having simple crystal structures such as face-centered cubes, body-centered cubes and hexagonal close-packed stacks where metal atoms were randomly distributed were easily formed. And then, the concept of the high-entropy alloy is expanded to the field of high-entropy ceramics, and non-oxide ultrahigh-temperature ceramic systems such as high-entropy boride, carbide, nitride and the like are also gradually valued by scientific researchers. High entropy materials generally exhibit four major effects, namely, a thermodynamic high entropy effect, a crystallographic lattice distortion effect, a kinetic delayed diffusion effect, and a performance "cocktail" effect. Entropy ceramics tend to exhibit good structural stability and functional characteristics compared to conventional low entropy ceramics. The diboride ceramic of IVB and VB group transition metals (M=Ti, zr and Hf) has excellent comprehensive properties of high melting point, low saturated vapor pressure, no solid phase change and the like, and has important application potential in extreme high-temperature service environments such as hypersonic aircrafts, rocket propulsion systems and the like. However, low-temperature densification and high-temperature mechanical properties of the intermediate-entropy boride ceramic are rarely reported at home and abroad.
Literature (Demirsky D, suzuki TS, yoshimi K, vasylkiv O.Synthesis of medium-entopy (Zr) 1/3 Hf 1/3 Ta 1/3 )B 2 using the spark plasma consolidation of diboride probes journal of the Ceramic Soiety of Japan 2020;128 (11): 977-80.) reported as a monobromide powder (HfB) 2 、TiB 2 And ZrB 2 ) As a raw material, a catalyst (Hf) was prepared at 1927 ℃ 1/3 Ti 1/3 Zr 1/3 )B 2 The grain size of the obtained compact ceramic is 10-20 mu m, the room temperature strength of the material is only 310-318 MPa, and the fracture toughness is 2.9-3.0 MPa.m 1/2 . The above-mentioned intermediate entropy ceramic prepared by using monobasic boride powder as raw material can make the grain size of material in the course of sintering difficult to be effectively controlledAnd a certain amount of impurities can be introduced into the powder in the mixing process, which is not beneficial to controlling the grain size and grain boundary strength of the material and improving the high-temperature mechanical property of the material.
Literature (Zhang W, zhang Y, guo WM, et al powder systems, densitation, microstructure and mechanical properties of Hf-based ternary boride ceramics J Eur ceramic Soc.2021, 41:3922-3928.) reports on HfO 2 、TiO 2 、ZrO 2 、B 4 C and graphite were used as raw materials, and (Hf) was synthesized at 1600 ℃ 1/3 Ti 1/3 Zr 1/3 )B 2 Boride ceramic powder, method for synthesizing (Hf 1/3 Ti 1/3 Zr 1/3 )B 2 The unreacted complete HfO exists in the powder 2 The presence of the impurity phase, oxygen impurity phase, is detrimental to densification of the material, (Hf 1/3 Ti 1/ 3 Zr 1/3 )B 2 The density of the sintered ceramic is 97.2% after the sintering at the temperature of up to 2000 ℃, and the sintered ceramic still contains the HfO of monoclinic phase 2 。HfO 2 The phase change from monoclinic phase to tetragonal phase can occur at high temperature, which is unfavorable for the improvement of the high-temperature mechanical property of the material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a low-temperature densification high-strength high-toughness (Ti, zr, hf) B 2 A medium entropy ceramic matrix composite and a preparation method thereof.
According to an aspect of the present invention, there is provided (Ti, zr, hf) B 2 A medium entropy ceramic-based complex phase material consisting of (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase.
Preferably: the (Ti, zr, hf) B 2 The chemical composition of (A) is (Ti x Zr y Hf z )B 2 Wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z=1.0.
According to another aspect of the present invention, there is provided the above (Ti, zr, hf) B 2 The preparation method of the medium-entropy ceramic-based composite material comprises the following steps:
step 1, preparing ceramic complex phase powder, wherein the ceramic complex phase powder is prepared by adopting a method of preparing a ceramic complex phase powderThe powder is (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase, wherein the mass fraction of BN is (1.6-3.2) wt%, B 4 The mass fraction of C is (2-4) wt%;
step 2, the ceramic complex phase powder is pressed and sintered to obtain (Ti, zr, hf) B 2 A medium entropy ceramic matrix composite.
Preferably: the step 1 comprises the following steps:
step 1.1, oxide raw material TiO 2 Powder, zrO 2 Powder, hfO 2 Powder and B 4 C powder which is TiO according to the mole ratio of raw materials 2 :ZrO 2 :HfO 2 :B 4 C=x, y, z, u; wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z= 1.0,0.89 and less than or equal to u is more than or equal to 0.96;
step 1.2, mixing, drying and sieving the powder after the proportioning by using ethanol or acetone as a dispersing agent and silicon nitride ceramic balls as ball milling media;
and 1.3, heating the mixed powder to 1200-1400 ℃ under vacuum condition, preserving heat for 0.5-4 h, and then heating to 1500-1650 ℃ and preserving heat for 0.5-4 h to obtain the ceramic composite powder.
Preferably: the mass loss of the silicon nitride grinding balls in the step 1.2 accounts for 1.8 to 3.5 weight percent of the mixed powder.
Preferably: in the step 1.2, a planetary ball mill or a roll shaft type tank mill is adopted for mixing, and the rotation rate is 50-600 r/min.
Preferably: in the step 2, heating to 1650 ℃ under the protection of vacuum or high-purity argon, preserving heat for 0.5h, applying 30-120MPa axial pressure, heating to 1700-1900 ℃ and sintering for 0.1-4 h to obtain (Ti, zr, hf) B 2 A medium entropy ceramic matrix composite.
Preferably: the (Ti, zr, hf) B prepared in the step 2 2 The oxygen content of the medium-entropy ceramic-based composite material is not more than 0.7wt%.
Preferably: the (Ti, zr, hf) B prepared in the step 2 2 The relative density of the medium-entropy ceramic-based composite material is not lower than 97.5%.
Preferably: the (Ti, zr, hf) B prepared in the step 2 2 Mid entropyThe bending strength and fracture toughness of the ceramic matrix composite at 1600 ℃ are 450-850 MPa and 4.0-7.0 MPa.m respectively 1/2 。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The technical proposal has simple process, low oxidation amount of synthesized complex phase powder and prepared ceramic, small crystal grains and uniform grain size distribution;
(2) According to the technical scheme, through a primary mixing mode, on one hand, the in-situ reaction is utilized to effectively remove impurity phases of ball milling media introduced in the ball milling mixing process, and on the other hand, the second phase is introduced, and meanwhile, the secondary mixing is avoided from introducing ball milling impurities and oxygen impurities.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the following drawings.
FIG. 1 shows the synthesis of (Ti, zr, hf) B in example 1 2 XRD patterns of the base powder are shown with the ordinate representing the Intensity and the abscissa representing 2 Theta.
FIG. 2 is a diagram of (Ti, zr, hf) B in example 1 2 And (3) a fracture SEM morphology graph and an energy spectrum point scanning result graph of the medium-entropy ceramic-based composite material.
FIG. 3 is a diagram of (Ti, zr, hf) B in example 1 2 And (5) an energy spectrum point scanning result diagram of the BN phase of the intermediate-entropy ceramic-based complex phase material.
FIG. 4 is a diagram of (Ti, zr, hf) B in example 1 2 And (3) an energy spectrum point scanning result diagram of the B4C phase of the medium-entropy ceramic-based complex phase material.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the example embodiments may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus a repetitive description thereof will be omitted.
Due to B 4 C has high hardness and high wear resistance, and is formed by (Ti, zr, hf) B 2 In the process of preparing ceramics, B is adopted 4 In the mixed material taking the C powder as the raw material, the impurities which are inevitably introduced into the ball milling medium are mixed. Ball milling medium quilt B 4 The grinding abrasion of the C powder is introduced into the ceramic, and the purity and the high-temperature mechanical property of the material are adversely affected.
The embodiment of the invention uses oxide powder (TiO 2 Powder, zrO 2 Powder, hfO 2 Powder) and B 4 C powder is used as raw material, silicon nitride ceramic balls are adopted for ball milling and uniform mixing, and (Ti, zr, hf) B with small particle size and low oxygen content is prepared through reduction reaction under the conditions of vacuum and lower temperature 2 And (3) powder. At the same time, by introducing an excessive amount of B 4 C, utilize a portion B 4 C and silicon nitride introduced by ball milling are subjected to in-situ reaction, so that silicon nitride impurities can be removed, a BN second phase with fine crystal grains and uniform dispersion can be generated by the reaction, and the other part B 4 C exists in the form of residual second phase, BN generated by in-situ reaction and residual B 4 The phase C is favorable for inhibiting the densification of the growth promoting material in the material sintering process, and meanwhile, the phase B 4 C is favorable for improving the high-temperature interface strength of the material, BN is favorable for improving the fracture toughness of the material, B 4 The introduction of the C and BN second phases can be beneficial to improving the comprehensive mechanical properties such as strength, toughness and the like of the material at high temperature.
In an embodiment of the present invention, there is provided (Ti, zr, hf) B 2 Intermediate entropy ceramic base complex phase material, complex phase material is (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase. Not only utilizes silicon nitride impurities, but also is beneficial to densification and comprehensive mechanical properties.
Preferably (Ti, zr, hf) B 2 The chemical composition of (A) is (Ti x Zr y Hf z )B 2 Wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z=1.0.
And preferably the content of BN in the complex phase material is from 1.6 to 3.2 wt%, B 4 The content of C is (2-4) wt% and the balance is main phase. The oxygen content is not more than 0.7wt%.
Further preferably (Ti, zr, hf) B 2 The relative density of the entropy ceramic material in the matrix is not lower than 97.5%, and the open porosity is not higher than 1.0%.
Major phase (Ti, zr, hf) B 2 The average grain size is 0.5 to 8.0. Mu.m, more preferably 0.5 to 5.0. Mu.m. The secondary phase BN is in a flaky shape and distributed in (Ti, zr, hf) B 2 The average grain size is 0.1-1.5 μm at the grain boundary and the three-fork grain boundary; b (B) 4 C is spherical, and the average grain size is 0.3-3 mu m.
And preferably the ceramic matrix composite has a flexural strength at 1600 ℃ and a fracture toughness of 450-850 MPa and 4.0-7.0 MPa-m, respectively 1/2 。
Meanwhile, in the embodiment of the present invention, a kind of (Ti, zr, hf) B 2 Preparation method of intermediate entropy ceramic matrix composite material comprises mixing oxide raw material (TiO 2 Powder, zrO 2 Powder, hfO 2 Powder) and B 4 The powder C is ball milled and evenly mixed by adopting silicon nitride ceramic ball medium, and is heated to 1200-1650 ℃ in two steps under vacuum condition, and the synthesized powder is complex phase powder. The powder is (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase. Then (Ti, zr, hf) B 2 The base entropy ceramic complex phase powder is pressed and sintered to obtain (Ti, zr, hf) B with high strength and high toughness 2 Entropy ceramic material in matrix phase.
Preferably, the method comprises the following steps in sequence:
step 1, oxide raw material TiO 2 Powder (purity is more than or equal to 99.5%, 0.01-0.5 μm), zrO 2 Powder (purity is more than or equal to 99.5%, 0.05-0.5 μm), hfO 2 Powder (purity not less than 99.5%, 0.05-0.5 μm) and B 4 C powder (purity is more than or equal to 99.5 percent, 0.1-2.0 mu m) according to the mole ratio of the raw materials of TiO 2 :ZrO 2 :HfO 2 :B 4 C=x, y, z, u; wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z= 1.0,0.89 and u is more than or equal to 0.96;
step 2, mixing, drying and sieving the powder prepared in the step 1 by using ethanol or acetone as a dispersing agent and silicon nitride ceramic balls as ball milling media; wherein the mass ratio of the ball materials is preferably 2:1-4:1.
Preferably, a planetary ball mill or a roll shaft type tank mill is adopted for mixing, the rotation rate is 50-600 r/min, and the mass loss of the silicon nitride grinding balls in the ball milling mixing process is 1.8-3.5 wt% of the mixed powder; further preferably, a roller type tank mill is adopted for mixing, and the rotation rate is 50-300 r/min.
Step 3, heating the mixed powder in the step 2 to 1200-1400 ℃ under vacuum condition, preserving heat for 0.5-4 h, and then heating to 1500-1650 ℃ and preserving heat for 0.5-4 h;
preferably, the oxygen content of the prepared ceramic powder is not more than 0.7wt%, the mass fraction of BN is (1.6-3.2) wt%, and B is contained in the powder 4 The mass fraction of C is (2-4) wt% and the balance is main phase.
Step 4, the (Ti, zr, hf) B prepared in step 3 2 Grinding and sieving the base entropy ceramic complex phase powder, heating to 1650 ℃ under the protection of vacuum or high purity argon, preserving heat for 0.5h, applying axial pressure, heating to 1700-1900 ℃ and sintering for 0.1-4 h to obtain the high-strength and high-toughness (Ti, zr, hf) B 2 And (5) a medium entropy ceramic.
Preferably, the axial pressure is 30-120MPa, and the pressurizing rate is 3-12 MPa/min.
The invention is described below in the following by way of specific examples:
example 1
TiO of oxide raw material 2 Powder (purity is more than or equal to 99.5%, 0.01-0.5 μm), zrO 2 Powder (purity is more than or equal to 99.5%, 0.05-0.5 μm), hfO 2 Powder (purity not less than 99.5%, 0.05-0.5 μm) and B 4 C powder (purity is more than or equal to 99.5 percent, 0.1-2.0 mu m) according to the mole ratio of the raw materials of TiO 2 :ZrO 2 :HfO 2 :B 4 C=x, y, z, u; where x=0.333, y=0.333, z=0.334, u=0.89.
Ethanol is adopted as a solvent, silicon nitride ceramic balls are adopted as grinding media, the ball-to-material mass ratio is 2:1, and mixing is carried out on a mixer at the speed of 150 r/min. The ball milling time was set according to the abrasion of the silicon nitride balls so that the silicon nitride content was introduced at about 1.8wt%. The ethanol solvent in the slurry was removed by evaporation at 55 ℃ using a rotary evaporator, then dried at 70 ℃ in a forced air drying oven, and then sieved.
Mixing the raw materials to obtain powderThe reaction is carried out for 2.5h by heating to 1300 ℃ at a speed of 10 ℃/min under vacuum condition, then heating to 1650 ℃ at a speed of 10 ℃/min, and preserving heat for 0.5h, the XRD spectrum of the synthesized powder is shown in figure 1, and the powder is (Ti, zr, hf) B 2 The powder had an oxygen content of 0.49wt% as the main phase, and no oxide impurity phase was found by XRD.
To be synthesized (Ti, zr, hf) B 2 Grinding and sieving the base ceramic composite powder in a mortar, loading the ground and sieved base ceramic composite powder into a graphite mold, heating to 1650 ℃ at a speed of 10 ℃/min under vacuum condition, preserving heat for 0.5h, then introducing flowing argon, starting pressure to 30MPa at a speed of 3MPa/min, heating to 1800 ℃ at a speed of 10 ℃/min, preserving heat and sintering for 1h, cooling to 1700 ℃ at a speed of 15 ℃/min, unloading the pressure, and cooling along with a furnace.
Prepared (Ti, zr, hf) B 2 The fracture of the medium entropy ceramic matrix composite material is shown in figure 2, wherein the fracture contains a flaky phase which is BN, the energy spectrum result is shown in figure 3, and the fracture also contains B 4 Phase C, the energy spectrum results are shown in FIG. 4.
The material composition was about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C. Due to BN and B 4 The C content is relatively small, so that the XRD pattern does not detect both phases. The density is 98.5%, the open porosity is 0.3%, and the oxygen content is 0.55% by weight.
The SEM morphology of the fracture surface of the ceramic is shown in fig. 3, and the average grain size is 2.5 μm. Through high temperature mechanical property test, (Ti, zr, hf) B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 651MPa and 6.5MPa m respectively 1/2 。
Example 2
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: the powder is sintered for 1h under 60MPa.
Prepared (Ti, zr, hf) B 2 The density of the medium-entropy ceramic matrix composite material reaches 98.9%, the open porosity is 0.2%, and the average grain size is 2.0 μm.
Through high temperature mechanical property test, (Ti, zr, hf) B 2 Flexural strength of medium entropy ceramic matrix composite at 1600 DEG CAnd fracture toughness of 733MPa and 6.8 MPa.m respectively 1/2 。
Example 3
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: sintering the powder for 0.5h under 120 MPa.
Prepared (Ti, zr, hf) B 2 The density of the medium-entropy ceramic matrix composite is 98.9%, the open porosity is 0.2%, and the average grain size is 1.0 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 763MPa and 7.0 MPa-m respectively 1/2 。
Example 4
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: the powder was sintered at 1900℃for 1h.
Prepared (Ti, zr, hf) B 2 The density of the medium-entropy ceramic matrix composite is 98.9%, the open porosity is 0.2%, and the average grain size is 3.5 μm.
(Ti,Zr,Hf)B 2 The bending strength and fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 680MPa and 4.8 MPa-m respectively 1/2 。
Example 5
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: the pressure applied by the powder is 60MPa, and the powder is sintered for 1h at 1900 ℃.
Prepared (Ti, zr, hf) B 2 The density of the medium-entropy ceramic matrix composite is 99.2%, the open porosity is 0.1%, and the average grain size is 2.5 μm.
(Ti,Zr,Hf)B 2 The bending strength and fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 697MPa and 5.8 MPa-m respectively 1/2 。
Example 6
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: the pressure applied by the powder is 120MPa, and the powder is sintered for 0.1h at 1900 ℃.
The resulting (Ti, zr,Hf)B 2 the density of the medium-entropy ceramic matrix composite is 99.5%, the open porosity is 0.1%, and the average grain size is 0.9 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 779MPa and 4.0 MPa.m respectively 1/2 。
Example 7
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1: the pressure applied by the powder is 120MPa, and sintering is carried out for 1.0h at 1700 ℃.
Prepared (Ti, zr, hf) B 2 The density of the medium-entropy ceramic matrix composite is 97.9%, the open porosity is 0.2%, and the average grain size is 0.5 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 700MPa and 7.0 MPa-m respectively 1/2 。
Example 8
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.2, y=0.4, z=0.4, u=0.89. Prepared (Ti, zr, hf) B 2 The intermediate entropy ceramic composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 97.5%, the open porosity is 0.4%, and the average grain size is 3.0 μm.
(Ti,Zr,Hf)B 2 The bending strength and fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 450MPa and 5.2 MPa-m respectively 1/2 。
Example 9
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.2, y=0.4, z=0.4, u=0.89, the powder was applied at a pressure of 60MPa.
Prepared (Ti, zr, hf) B 2 The intermediate entropy ceramic composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 98.5%, the open porosity is 0.3%, and the average grain size is 2.8 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 489MPa and 6.0 MPa.m respectively 1/2 。
Example 10
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.2, y=0.4, z=0.4, u=0.89, the pressure applied by the powder was 120MPa, and the sintering time was 0.5h.
Prepared (Ti, zr, hf) B 2 The intermediate entropy ceramic composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 99.2%, the open porosity is 0.1%, and the average grain size is 1.3 μm.
(Ti,Zr,Hf)B 2 The four-point bending strength and the fracture toughness of the base entropy ceramic at 1600 ℃ are 583MPa and 6.2 MPa-m respectively 1/2 。
Example 11
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.4, y=0.4, z=0.2, u=0.89, the powder was applied at a pressure of 60MPa and the sintering temperature was 1700 ℃.
Prepared (Ti, zr, hf) B 2 The composition of the base entropy ceramic complex phase material is 96.1wt% (Ti, zr, hf) B 2 -1.9wt％BN-2wt％B 4 C。
The density of the material is 98.0%, the open porosity is 0.3%, and the average grain size is 0.7 μm.
(Ti,Zr,Hf)B 2 The four-point bending strength and the fracture toughness of the base entropy ceramic at 1600 ℃ are 634MPa and 6.8 MPa-m respectively 1/2 。
Example 12
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.4, y=0.4, z=0.2, u=0.89, the powder was applied at a pressure of 60MPa and the sintering temperature was 1800 ℃.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.1wt% (Ti, zr, hf) B 2 -1.9wt％BN-2wt％B 4 C。
The density of the material is 98.5%, the open porosity is 0.2%, and the average grain size is 0.9 μm.
The four-point bending strength and fracture toughness of the entropy ceramic matrix composite phase in (Ti, zr, hf) B2 at 1600 ℃ are 674MPa and 6.5 MPa.m respectively 1/2 。
Example 13
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.4, y=0.4, z=0.2, u=0.89, the powder was applied at a pressure of 120MPa and the sintering temperature was 1900 ℃ for 0.1h.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.1wt% (Ti, zr, hf) B 2 -1.9wt％BN-2wt％B 4 C。
The density of the material is 97.9%, the open porosity is 0.3%, and the average grain size is 0.7 μm.
(Ti,Zr,Hf)B 2 The four-point bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 739MPa and 4.8 MPa.m respectively 1/2 。
Example 14
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.4, y=0.4, z=0.2, u=0.96, the content of silicon nitride introduced by ball milling was 3.5wt%, and the pressure applied by the powder was 60MPa.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 92.8wt% (Ti, zr, hf) B 2 -3.2wt％BN-4wt％B 4 C。
The density of the material is 99.5%, the open porosity is 0.1%, and the average grain size is 1.5 μm.
(Ti,Zr,Hf)B 2 The four-point bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 700MPa and 6.0 MPa.m respectively 1/2 。
Example 15
The batch mixing, powder preparation and sintering were performed in the same manner as in example 1, except that in example 1, heating was performed at 1200 c for 0.5h and at 1500 c for 4h in the preparation of the complex phase powder.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 99.1%, the open porosity is 0.1%, and the average grain size is 2.0 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 610MPa and 6.3 MPa-m respectively 1/2 。
Example 16
The batch mixing, powder preparation and sintering were performed in the same manner as in example 1, except that in example 1, heating was performed at 1200℃for 4 hours and at 1650℃for 0.5 hours in the preparation of the complex phase powder.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 98.7%, the open porosity is 0.2%, and the average grain size is 1.5 μm.
(Ti,Zr,Hf)B 2 The bending strength and fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 695MPa and 5.8 MPa-m respectively 1/2 。
Example 17
The batch mixing, powder preparation and sintering were performed in the same manner as in example 1, except that in example 1, heating was performed at 1400℃for 2 hours and at 1500℃for 2 hours in the preparation of the complex phase powder.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 99.2%, the open porosity is 0.1%, and the average grain size is 0.8 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 756MPa and 6.0 MPa-m respectively 1/2 。
Comparative example 1
The batch mixing, powder preparation and sintering were performed as in example 1, except that in example 1, two-step solid phase heating was not employed in preparing the complex phase powder, but sintering was directly performed at 1650 ℃ for 3 hours.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2 -1.6wt％BN-2wt％B 4 C。
The density of the material is 97.0%, the open porosity is 1.2%, and the average grain size is 10.0 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are 400MPa and 2.5 MPa-m respectively 1/2 。
Comparative example 2
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, instead of silicon nitride, zrO was used 2 The ball is mixed.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 97wt% (Ti, zr, hf) B 2 -3wt％B 4 C。
The density of the material is 96.5%, the open porosity is 2.8%, and the average grain size is 12 μm.
(Ti,Zr,Hf)B 2 The bending strength and the fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are respectively 350MPa and 2.5 MPa-m 1/2 。
Comparative example 3
The batch mixing, powder preparation and sintering were carried out as in example 1, except that in example 1, x=0.1, y=0.45, z=0.45, u=0.89.
Prepared (Ti, zr, hf) B 2 The medium entropy ceramic matrix composite material has a composition of about 96.4wt% (Ti, zr, hf) B 2- 1.6wt％BN-2wt％B 4 C。
The density of the material is 95.5%, the open porosity is 3.2%, and the average grain size is 9 μm.
(Ti,Zr,Hf)B 2 Intermediate entropy ceramic matrix composite materialThe bending strength and fracture toughness of the material at 1600 ℃ are 300MPa and 3.0 MPa.m respectively 1/2 。
According to the embodiment, after the preparation method, the silicon nitride spheres and the proportion of the technical scheme are not adopted, the prepared intermediate-entropy ceramic-based composite phase material has the advantages of lower density, higher porosity, larger grain size and poorer comprehensive mechanical property. The technical scheme of the invention has simple process, low oxidation amount of the synthesized complex phase powder and the prepared ceramic, small crystal grains and uniform grain size distribution, and the prepared intermediate entropy ceramic-based complex phase material has excellent mechanical properties such as strength, toughness and the like at high temperature.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (10)

1. (Ti, zr, hf) B 2 The medium entropy ceramic-based composite material is characterized in that the composite material is prepared from (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase.
2. (Ti, zr, hf) B according to claim 1 2 The medium entropy ceramic matrix composite material is characterized in that: the (Ti, zr, hf) B 2 The chemical composition of (A) is (Ti x Zr y Hf z )B 2 Wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z=1.0.
3. (Ti, zr, hf) B according to claim 1 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the method comprises the following steps:
step 1, preparing ceramic complex phase powder, wherein the ceramic complex phase powder is prepared by using (Ti, zr, hf) B 2 As main phase, with BN and B 4 C is the minor phase, wherein the mass fraction of BN is (1.6-3.2) wt%, B 4 The mass fraction of C is%2～4)wt％；
Step 2, the ceramic complex phase powder is pressed and sintered to obtain (Ti, zr, hf) B 2 A medium entropy ceramic matrix composite.
4. The (Ti, zr, hf) B of claim 3 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the step 1 comprises the following steps:
step 1.1, oxide raw material TiO 2 Powder, zrO 2 Powder, hfO 2 Powder and B 4 C powder which is TiO according to the mole ratio of raw materials 2 :ZrO 2 :HfO 2 :B 4 C=x, y, z, u; wherein x is more than or equal to 0.2 and less than or equal to 0.40,0.2, y is more than or equal to 0.40, and x+y+z= 1.0,0.89 and less than or equal to u is more than or equal to 0.96;
step 1.2, mixing, drying and sieving the powder after the proportioning by using ethanol or acetone as a dispersing agent and silicon nitride ceramic balls as ball milling media;
and 1.3, heating the mixed powder to 1200-1400 ℃ under vacuum condition, preserving heat for 0.5-4 h, and then heating to 1500-1650 ℃ and preserving heat for 0.5-4 h to obtain the ceramic composite powder.
5. (Ti, zr, hf) B according to claim 4 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the mass loss of the silicon nitride grinding balls in the step 1.2 accounts for 1.8 to 3.5 weight percent of the mixed powder.
6. (Ti, zr, hf) B according to claim 4 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: in the step 1.2, a planetary ball mill or a roll shaft type tank mill is adopted for mixing, and the rotation rate is 50-600 r/min.
7. The (Ti, zr, hf) B of claim 3 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: in the step 2, heating to 1650 ℃ under the protection of vacuum or high-purity argon, preserving heat for 0.5h, applying 30-120MPa axial pressure, heating to 1700-1900 ℃ and sintering for 0.1-4 h to obtain (Ti, Z)r,Hf)B 2 A medium entropy ceramic matrix composite.
8. (Ti, zr, hf) B according to claim 7 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the (Ti, zr, hf) B prepared in the step 2 2 The oxygen content of the medium-entropy ceramic-based composite material is not more than 0.7wt%.
9. (Ti, zr, hf) B according to claim 7 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the (Ti, zr, hf) B prepared in the step 2 2 The relative density of the medium-entropy ceramic-based composite material is not lower than 97.5%.
10. (Ti, zr, hf) B according to claim 7 2 The preparation method of the medium-entropy ceramic-based complex phase material is characterized by comprising the following steps of: the (Ti, zr, hf) B prepared in the step 2 2 The bending strength and fracture toughness of the medium-entropy ceramic-based complex phase material at 1600 ℃ are respectively 450-850 MPa and 4.0-7.0 MPa.m 1/2 。
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