CN114804864B - Biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering and preparation method thereof - Google Patents
Biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering and a preparation method thereof. The invention relates to a biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering, which is prepared from RETaO of t phase 4 Ceramic and t-phase zirconia ceramic; wherein RE is Sc, Y and lanthanide rare earth elements, and the preparation method of the biphase high-entropy ceramic, RETaO which can exist stably in t phase at room temperature is obtained 4 The ceramic can generate extremely high fracture toughness at room temperature, and simultaneously stably coexist with the t-phase high-entropy zirconia ceramic, so that the final material has the performance advantages of low heat conductivity, high thermal expansion coefficient, high hardness and the like, and the working temperature and the application range of the material are further improved.
Description
Technical Field
The invention belongs to the technical field of high-temperature structural ceramics, and particularly relates to a biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering and a preparation method thereof.
Background
Rare earth tantalate RETaO 4 The ceramic as a novel superhigh temperature heat insulation wear-resistant protective ceramic material has been studied in a great deal at present, and the application range of the ceramic comprises various aspects such as a thermal barrier coating, an environment barrier coating, an acid-base resistant coating, an impact-resistant ablative coating and the like. The rare earth tantalate has the advantages of low heat conductivity, thermal expansion coefficient matching with the matrix, excellent mechanical property, high-temperature steam corrosion resistance and the like when being used as a thermal barrier coating, but the rare earth element contained in the rare earth tantalate can react with oxides of calcium, magnesium, aluminum, silicon and the like in the air at high temperature to be corroded. Rare earth tantalate RETaO 4 An important reason that ceramics have been studied as high temperature structural materials is that their presence of t-m phase transition without phase transition gives them extremely high fracture toughness at a high Wen Shanxie phase (t), and have therefore been considered as novel ultra-high temperature ceramics capable of replacing Yttria Stabilized Zirconia (YSZ). However, the t phase is RETaO 4 Can be stably present only at a temperature of 1400 ℃ or higher, at which RETaO is present 4 Is poor in fracture toughness; at the same time RETaO 4 The problems of low hardness, high thermal conductivity and low Young's modulus exist at low temperature, and the application of the composite material is limited; the t-phase YSZ material has the characteristic of high fracture toughness, but has the problems of high thermal conductivity, low use temperature (less than 1200 ℃) and insufficient thermal expansion coefficient.
Therefore, in order to solve the above-mentioned technical problems, there is an urgent need to design and develop a dual-phase high-entropy ceramic prepared by combining high-temperature high-pressure sintering and a preparation method thereof.
Disclosure of Invention
The first object of the present invention is to provide a dual-phase high-entropy ceramic prepared by combining high-temperature high-pressure sintering, and another object of the present invention is to provide a preparation method of the dual-phase high-entropy ceramic prepared by combining high-temperature high-pressure sintering.
The first object of the invention is achieved in that the biphase high entropy ceramic consists of t-phase RETaO 4 Ceramic and t-phase zirconia ceramic; wherein RE is Sc, Y and lanthanide rare earth elements.
The other object of the invention is realized in that the method is prepared by mixing powder, drying, presintering, re-weighing, re-mixing powder and final sintering in sequence;
the method specifically comprises the following steps: according to RETaO respectively 4 Chemical formula (RE) of the final product 1/x ) x (Ta 1-y Nb y )O 4 And zirconia ceramic final product of formula Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Respectively weighing the required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder, uniformly mixing the two powders through ball milling and mixing, and using alcohol as a ball milling medium in the ball milling process;
drying the slurry after uniform mixing, sintering at high temperature, and cooling to obtain (RE) 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a- b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Is a powder of the above composition;
grinding and sieving the cooled powder, according to (RE 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a-b RE 1 a/2 RE 2 a/2 Ta b/ 2 Nb b/2 O 2 The mass ratio of the two is measured, and the two phases of powder which are uniformly mixed are obtained through ball milling again;
weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process is 100-200MPa, the sintering temperature is 1500-1700 ℃, and the sintering time is 5-10 min.
The invention relates to a biphase high-entropy ceramic prepared by combining high-temperature high-pressure sintering, which is prepared from RETaO of t phase 4 Ceramic and t-phase zirconia ceramic; wherein RE is Sc, Y and lanthanide rare earth elements, and the preparation method of the biphase high-entropy ceramic, RETaO which can exist stably in t phase at room temperature is obtained 4 The ceramic can generate extremely high fracture toughness at room temperature, and simultaneously stably coexist with the t-phase high-entropy zirconia ceramic, so that the final material has the performance advantages of low heat conductivity, high thermal expansion coefficient, high hardness and the like, and the working temperature and the application range of the material are further improved.
Drawings
FIG. 1 is an XRD diffraction pattern of the ceramic materials prepared in examples 1 to 3 and comparative example 1 according to the present invention;
FIG. 2 is a graph showing the comparison of the thermal conductivity of the ceramic materials prepared in examples 1-2 of the present invention with that of comparative example 1;
FIG. 3 is a graph showing the comparison of the thermal expansion coefficients of the ceramic materials prepared in examples 1-2 according to the present invention with those of comparative example 1;
FIG. 4 is a graph showing the comparison of fracture toughness of examples 1-3 of the present invention and comparative examples 1-3.
Detailed Description
The invention is further illustrated, but is not limited in any way, by the following examples, and any alterations or substitutions based on the teachings of the invention are within the scope of the invention.
As shown in fig. 1 to 4, the present invention provides a dual-phase high-entropy ceramic prepared by combining high-temperature high-pressure sintering, which consists of a t-phase RETaO4 ceramic and a t-phase zirconia ceramic;
wherein RE is Sc, Y and lanthanide rare earth elements.
The RETaO 4 The chemical formula of the final product of (E) is (RE) 1/x ) x (Ta 1-y Nb y )O 4 The mass fraction is 10-45%, 1<x<8 and is an integer, and the value of x also represents the amount of added rare earth oxide species, 0.1<y<0.9; the chemical formula of the final product of the zirconia ceramic is Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 55-90% by mass of 0.2<a+b<0.4, a=b+.0, RE1 and RE2 represent two different rare earth elements.
The raw material adopted by the biphase high-entropy ceramic is RE 2 O 3 、Ta 2 O 5 、Nb 2 O 5 And ZrO(s) 2 The two compounds formed consist of.
The RE 2 O 3 、Ta 2 O 5 、Nb 2 O 5 And ZrO(s) 2 The two compounds formed are in particular RETaO of the t phase 4 Ceramics and RE 2 O 3 +Ta 2 O 5 +Nb 2 O 5 Co-stable t-phase zirconia ceramics.
The biphase high-entropy ceramic is specifically a double-t-phase high-entropy ceramic with low thermal conductivity, high thermal expansion, high fracture toughness and high hardness.
The invention also provides a preparation method for preparing the biphase high-entropy ceramic by combining high-temperature high-pressure sintering, which is prepared by mixing powder, drying, pre-sintering, re-weighing, re-mixing powder and final sintering in sequence;
the method specifically comprises the following steps:
according to respectivelyRETaO 4 Chemical formula (RE) of the final product 1/x ) x (Ta 1-y Nb y )O 4 And zirconia ceramic final product of formula Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Respectively weighing the required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder, uniformly mixing the two powders through ball milling and mixing, and using alcohol as a ball milling medium in the ball milling process;
drying the slurry after uniform mixing, sintering at high temperature, and cooling to obtain (RE) 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a- b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Is a powder of the above composition;
grinding and sieving the cooled powder, according to (RE 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a-b RE 1 a/2 RE 2 a/2 Ta b/ 2 Nb b/2 O 2 The mass ratio of the two is measured, and the two phases of powder which are uniformly mixed are obtained through ball milling again;
weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process is 100-200MPa, the sintering temperature is 1500-1700 ℃, and the sintering time is 5-10 min.
The purity of the rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder is more than 99%; in the ball milling mixing process, the rotating speed of the ball mill is 200-500 revolutions per minute, and the ball milling time is 24-48 hours; in the ball milling process, alcohol is used as a ball milling medium, and the mass ratio of the powder to the alcohol is 1:10-1:30.
In the step of drying the evenly mixed slurry, the drying temperature is 90-100 ℃ and the drying time is 10-20 hours; the high-temperature sintering temperature is 1500-1600 ℃ and the sintering time is 5-10h.
And in the two-phase powder which is uniformly mixed by ball milling, the rotating speed of the ball mill is 200-500 revolutions per minute, and the ball milling time is 24-48 hours.
That is, in the scheme of the invention, a high-temperature high-pressure sintering is adopted to prepare the biphase high-entropy ceramic, and the prepared biphase ceramic is prepared from t-phase high-entropy RETaO 4 And zirconia ceramics, wherein RE is Sc, Y, and lanthanide rare earth elements;
the raw material is RE 2 O 3 、Ta 2 O 5 、Nb 2 O 5 And ZrO(s) 2 The final compounds formed are two, RETaO in t phase respectively 4 Ceramics and RE 2 O 3 +Ta 2 O 5 +Nb 2 O 5 Co-stable t-phase zirconia ceramics;
high entropy RETaO 4 The chemical formula of the final product of (E) is (RE) 1/x ) x (Ta 1-y Nb y )O 4 Wherein 1 is<x<8 and is an integer, and the value of x also indicates the amount of the added rare earth oxide species, and 0.1<y<0.9；
The chemical formula of the final product of the high-entropy zirconia ceramic is Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Wherein 0.2<a+b<0.4，a=b≠0，RE 1 And RE (RE) 2 Representing two different rare earth elements;
in the final two-phase high entropy ceramic product (RE 1/x ) x (Ta 1-y Nb y )O 4 Is 10-45% by mass and Zr 1-a- b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The mass fraction of (2) is 55-90%;
the preparation process comprises weighing (RE 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a-b RE 1 a/ 2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The double-t-phase high-entropy ceramic with low thermal conductivity, high thermal expansion, high fracture toughness and high hardness is prepared by mixing powder, drying, pre-sintering, re-weighing, re-mixing powder and final sinteringPorcelain.
In other words, it is an object of the present invention to provide a dual t-phase high entropy RETaO with low thermal conductivity, high coefficient of thermal expansion, high hardness and high fracture toughness 4 +ZrO 2 Ceramic and a preparation method thereof. For the first time realize RETaO of rare earth tantalate 4 The ceramic can exist in stable tetragonal phase at room temperature, has no phase change in the temperature range of room temperature to 1600 ℃, and simultaneously performs synergistic optimization on various mechanical and thermal properties of the material.
The invention also aims to provide the RE as the raw material 2 O 3 、Ta 2 O 5 、Nb 2 O 5 And ZrO(s) 2 The final compounds formed are two, RETaO in t phase respectively 4 Ceramics and RE 2 O 3 +Ta 2 O 5 +Nb 2 O 5 Co-stable t-phase zirconia ceramics in which RETaO 4 The chemical formula of the final product of (E) is (RE) 1/x ) x (Ta 1-y Nb y )O 4 The mass fraction of the composition is 10-45%; the chemical formula of the final product of the zirconia ceramic is Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The mass fraction is 55-90%
Specifically, high entropy RETaO of double t phase 4 +ZrO 2 The ceramic can effectively enhance phonon scattering by utilizing the high entropy effect of the material, reduce the thermal conductivity of the material, and improve the thermal expansion coefficient of the material by improving the non-simple harmonic vibration of crystal lattices, meanwhile, the zirconia-based ceramic has the characteristics of high hardness and high Young modulus, and the mass fraction of the zirconia-based ceramic in the biphase ceramic is larger, so that the problem of insufficient hardness and Young modulus of the rare earth tantalate ceramic material is solved.
Typically single phase high entropy RETaO 4 The ceramic exists in the form of monoclinic phase (m) at room temperature and cannot generate the characteristic of high fracture toughness, while RETaO in the cooling process is inhibited by introducing a second phase, namely a high-entropy zirconia ceramic of t phase, and by final high-temperature sintering (temperature exceeding 1500 ℃) 4 The ceramic t-m phase transition occurs such that RETaO 4 Can be in the form of t phaseExist stably at room temperature, so that the finally obtained material is double t phase RETaO with high entropy 4 +ZrO 2 Ceramics, thereby producing extremely high fracture toughness.
While the common YSZ material changes phase at 1200 ℃, in the technical proposal of the invention, we use different rare earth elements, tantalum and niobium to perform high-entropy stabilization on zirconia simultaneously and pass through a second-phase high-entropy RETaO simultaneously 4 The addition of the ceramic powder ensures that the mutual inhibition of the grains of two phases in the final material not only plays a role in improving the mechanical property of the material by grain refinement, but also effectively inhibits the phase change of the two-phase ceramic.
RETaO which can exist stably in t phase at room temperature is obtained by the scheme of the invention 4 The ceramic has extremely high fracture toughness, and the high-entropy zirconia ceramic combined with t phase finally obtains the material with no phase change, low heat conductivity, high thermal expansion coefficient, high hardness and high Young modulus in the temperature range from room temperature to 1600 ℃, which cooperatively solves RETaO 4 The problems of high thermal conductivity, poor mechanical property and low working temperature of the zirconia-based ceramic cannot exist in a stable t phase at room temperature.
Further, the preparation method of the biphase high-entropy ceramic by high-temperature high-pressure sintering comprises the following steps:
step (1): according to RETaO respectively 4 Chemical formula (RE) of the final product 1/x ) x (Ta 1-y Nb y )O 4 And zirconia ceramic final product of formula Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder (the purity of the used raw materials is more than 99%) are respectively weighed, the two powders are uniformly mixed through ball milling and mixing (the rotating speed of the ball mill is 200-500 revolutions per minute, the ball milling time is 24-48 hours), and alcohol is used as a ball milling medium in the ball milling process (the mass ratio of the powder to the alcohol is 1:10-1:30).
Step (2): drying the uniformly mixed slurry (drying temperature 90-100deg.C, drying time 10-20 h), sintering at high temperature, and cooling to obtain (RE) 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The sintering temperature is 1500-1600 ℃ and the sintering time is 5-10h.
Step (3): grinding and sieving the cooled powder (300 mesh), according to (RE) 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a- b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The mass ratio of the two materials is weighed, and the two-phase powder which is uniformly mixed is obtained through ball milling again (the rotating speed of the ball mill is 200-500 revolutions per minute, and the ball milling time is 24-48 hours).
Step (4): weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process is 100-200MPa, the sintering temperature is 1500-1700 ℃, and the sintering time is 5-10 min.
The beneficial effects are that: the materials prepared by adopting the steps (1) - (4) are prepared from t-phase RETaO 4 And zirconia ceramics, a RETaO which can exist stably in t phase at room temperature is obtained for the first time 4 Ceramics, which utilize mutual inhibition between two phases to obtain RETaO without phase change in the temperature range of room temperature to 1600 DEG C 4 And zirconia ceramics (typically RETaO 4 The t-m phase transition temperature of (1) is 1300-1450 ℃, the YSZ is 1200 ℃), and the finally obtained ceramic material has fine crystal grains and low thermal conductivity (1.2-1. W.m) -1 ·K -1 ) High thermal expansion coefficient (10-13X 10) -6 K -1 ) High fracture toughness (3-5 MPa.m) 1/2 ) High Young's modulus (180-240 GPa) and excellent high-temperature phase stability.
Example 1
According to RETaO respectively 4 The chemical formula (Sm) of the final product 1/3 Y 1/3 Yb 1/3 )(Ta 0.5 Nb 0.5 )O 4 And Zr (Zr) 0.7 Y 0.075 Yb 0.075 Ta 0.075 Nb 0.075 O 2 Respectively are provided withWeighing required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder (the purity of the used raw materials is more than 99%), uniformly mixing the two powders through ball milling and mixing (the rotating speed of the ball milling machine is 200 revolutions per minute, the ball milling time is 48 hours), and using alcohol as a ball milling medium in the ball milling process (the mass ratio of the powder to the alcohol is 1:10); drying the uniformly mixed slurry (drying temperature 90 ℃ C., drying time 20 h), sintering at high temperature and cooling to obtain (Sm) 1/3 Y 1/3 Yb 1/3 )(Ta 0.5 Nb 0.5 )O 4 And Zr (Zr) 0.7 Y 0.075 Yb 0.075 Ta 0.075 Nb 0.075 O 2 The initial powder (sintering temperature 1500 ℃ C., sintering time 10 h) of (C.) and grinding and sieving the cooled powder (300 mesh), according to (RE) 1/x ) x (Ta 1-y Nb y )O 4 (10 wt%) and Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The mass ratio of (90 wt%) is used for weighing the two masses, and the uniformly mixed two-phase powder is obtained through ball milling again (the rotation speed of the ball mill is 500 revolutions per minute, and the ball milling time is 24 hours); weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process of the ceramic is 100MPa, the sintering temperature is 1500 ℃, and the sintering time is 10 min.
Example 2
According to RETaO respectively 4 The chemical formula (Y) of the final product 1/2 Lu 1/2 )(Ta 0.7 Nb 0.3 )O 4 And Zr (Zr) 0.76 Lu 0.06 Yb 0.06 Ta 0.06 Nb 0.06 O 2 Respectively weighing the required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder (the purity of the used raw materials is more than 99%), uniformly mixing the two powders through ball milling and mixing (the rotating speed of the ball milling machine is 500 revolutions per minute, the ball milling time is 24 hours), and using alcohol as a ball milling medium in the ball milling process (the mass ratio of the powder to the alcohol is 1:30); drying the uniformly mixed slurry (drying temperature 100 ℃ C., drying time 10 h), sintering at high temperature and cooling to obtain (Y) 1/2 Lu 1/2 )(Ta 0.7 Nb 0.3 )O 4 And Zr (Zr) 0.76 Lu 0.0 6 Yb 0.06 Ta 0.06 Nb 0.06 O 2 The initial powder (sintering temperature 1600 ℃ C., sintering time 5 h) of (C.) and grinding and sieving the cooled powder (300 mesh), according to (RE) 1/x ) x (Ta 1-y Nb y )O 4 (45 wt%) and Zr 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 The mass ratio of (55 wt%) is used for weighing the mass of the two materials, and the two-phase powder which is uniformly mixed is obtained through ball milling again (the rotating speed of the ball mill is 200 revolutions per minute, and the ball milling time is 48 hours); weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process of the ceramic is 200MPa, the sintering temperature is 1600 ℃, and the sintering time is 5 min.
Example 3
According to RETaO respectively 4 The chemical formula (Sm) of the final product 1/4 Eu 1/4 Y 1/4 Lu 1/4 )(Ta 0.4 Nb 0.6 )O 4 And Zr (Zr) 0.64 Sm 0.09 Dy 0.09 Ta 0.09 Nb 0.09 O 2 Respectively weighing the required rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powder (the purity of the used raw materials is more than 99%), uniformly mixing the two powders through ball milling and mixing (the rotating speed of the ball milling machine is 350 revolutions per minute, the ball milling time is 30 and h), and using alcohol as a ball milling medium in the ball milling process (the mass ratio of the powder to the alcohol is 1:24); drying the uniformly mixed slurry (drying temperature 95 ℃ C., drying time 8 h), sintering at high temperature and cooling to obtain (Sm) 1/4 Eu 1/4 Y 1/4 Lu 1/4 )(Ta 0.4 Nb 0.6 )O 4 And Zr (Zr) 0.64 Sm 0.09 Dy 0.09 Ta 0.09 Nb 0.09 O 2 The initial powder of (sintering temperature 1570 ℃ C., sintering time 7 h), grinding the cooled powder, sieving (300 mesh), and the powder was prepared according to (RE) 1/x ) x (Ta 1-y Nb y )O 4 (30 wt%) and Zr 1-a-b RE 1 a/2 RE 2 a/ 2 Ta b/2 Nb b/2 O 2 The mass ratio of (70 wt%) is used for weighing the mass of the two materials, and the two-phase powder which is uniformly mixed is obtained through ball milling again (the rotation speed of the ball mill is 410 revolutions per minute, and the ball milling time is 36 hours); weighing about 2.0g of mixed powder, and preparing the compact double-t-phase high-entropy RETaO by high-temperature high-pressure sintering 4 +ZrO 2 The pressure in the sintering process of the ceramic is 160MPa, the sintering temperature is 1520 ℃, and the sintering time is 6 min.
Comparative example 1, which differs from example 1 in that the final sintering temperature is 1300 ℃, since the final sintering temperature is lower than RETaO 4 The t-m phase transition temperature of (2) is such that m ceramic is present in the final sample.
Comparative example 2, which is different from example 1 in that the high entropy zirconia ceramic was mixed with Zr 0.4 Y 0.15 Yb 0.15 Ta 0.15 Nb 0.15 O 2 The proportion exceeds the stabilizer atoms which can be contained in the zirconia crystal lattice, so that the final product cannot exist stably in the t-phase ceramic.
Comparative example 3, which differs from example 1 in that the first sintering temperature was 1400℃and that the initial two-phase powder was obtained as a complete reaction, RETaO was not obtained as a single phase 4 And zirconia-based ceramics such that the final product contains a plurality of precipitated phases.
Preferably, FIG. 1 shows XRD diffraction patterns of the ceramic materials prepared in examples 1-3 and comparative example 1 of the present invention, and it can be seen that the materials prepared in examples 1-3 are all double t-phase high entropy RETaO 4 +ZrO 2 Ceramic, whereas in comparative example 1, monoclinic phase zirconia of the third phase is present;
FIG. 2 is a comparison of the thermal conductivity of the ceramic materials prepared in inventive examples 1-2 with that of comparative example 1, and can be seen as a double t-phase high entropy RETaO 4 +ZrO 2 The thermal conductivity of the ceramic is obviously lower than that of comparative example 1, which shows that the material prepared by the scheme of the invention has lower thermal conductivity;
FIG. 3 shows the results of comparison of the thermal expansion coefficients of the ceramic materials prepared in examples 1-2 according to the present invention with those of comparative example 1, and can be seen to see the high entropy RETaO of the double t phase 4 +ZrO 2 Ceramic materialHas a high coefficient of thermal expansion (10-13X 10) at 1200 DEG C -6 K -1 ) And no phase change occurs, whereas in comparative example 1, the phase change occurs due to the presence of the third phase, resulting in an unstable thermal expansion coefficient thereof with an increase in temperature;
FIG. 4 is a graph comparing fracture toughness of examples 1-3 of the present invention with that of comparative examples 1-3, and it can be seen that the dual t-phase high entropy RETaO prepared in examples 1-3 of the present invention 4 +ZrO 2 The fracture toughness of the ceramic is 3-5 MPa m 1/2 1-3 MPa.m significantly higher than comparative examples 1-3 1/2 。
Claims (5)
1. Double-t-phase high-entropy RETaO prepared by combining high-temperature high-pressure sintering 4 +ZrO 2 Ceramic, characterized by the fact that it is composed of RETaO in t phase 4 The ceramic and t-phase zirconia ceramic, wherein RE is Sc, Y and lanthanide rare earth elements; RETaO 4 The final product of the ceramic has the chemical formula (RE 1/x ) x (Ta 1-y Nb y )O 4 The mass fraction is 10-45%, 1<x<8 and is an integer, and the value of x represents the number of the added rare earth oxide species, 0.1<y<0.9; the chemical formula of the final product of the zirconia ceramic is Zr 1-a-b RE 1 a/ 2 RE 2 a/2 Ta b/2 Nb b/2 O 2 55-90% by mass of 0.2<a+b<0.4，a=b≠0，RE 1 And RE (RE) 2 Representing two different rare earth elements; the preparation method comprises the following steps:
(1) According to RETaO 4 The chemical formulas of the final products of the ceramics and the zirconia ceramics respectively weigh the required rare earth oxide, tantalum oxide, niobium oxide and zirconia powder, the two powders are uniformly mixed through ball milling and mixing, and alcohol is used as a ball milling medium in the ball milling process; drying the uniformly mixed slurry, presintering at 1500-1600 ℃ for 5-10h, cooling to obtain (RE) 1/x ) x (Ta 1-y Nb y )O 4 And Zr (Zr) 1-a-b RE 1 a/2 RE 2 a/2 Ta b/2 Nb b/2 O 2 Is ground and sieved after cooling；
(2) According to RETaO 4 Weighing two initial powders according to the mass ratio of the ceramic to the zirconia ceramic, and obtaining uniformly mixed two-phase powder through ball milling;
(3) Weighing 2.0g of two-phase powder, and finally sintering at high temperature and high pressure of 100-200Mpa and 1500-1700 ℃ for 5-10min to obtain compact double-t-phase high-entropy RETaO 4 +ZrO 2 And (3) ceramics.
2. The dual t-phase high entropy ceramic of claim 1, wherein the rare earth oxide, tantalum oxide, niobium oxide and zirconium oxide powders have a purity of greater than 99%.
3. The dual t-phase high entropy ceramic according to claim 1, wherein the ball mill in step (1) has a rotational speed of 200-500 revolutions per minute, a ball milling time of 24-48 hours, and a mass ratio of powder to alcohol of 1:10-1:30.
4. The dual t-phase high entropy ceramic according to claim 1, wherein the slurry in step (1) is dried at a temperature of 90-100 ℃ for a drying time of 10-20 hours.
5. The dual t-phase high entropy ceramic according to claim 1, wherein the rotation speed of the ball mill in the step (2) is 200-500 revolutions per minute, and the ball milling time is 24-48 hours.
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