CN115259853A - High-entropy fluorite oxide target material and preparation method thereof - Google Patents

High-entropy fluorite oxide target material and preparation method thereof Download PDF

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CN115259853A
CN115259853A CN202210915185.3A CN202210915185A CN115259853A CN 115259853 A CN115259853 A CN 115259853A CN 202210915185 A CN202210915185 A CN 202210915185A CN 115259853 A CN115259853 A CN 115259853A
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entropy
oxide target
target material
fluorite
preparation
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苗洋
成楚飞
侯佳栋
程富豪
王晓敏
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Taiyuan University of Technology
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Abstract

The invention discloses a high-entropy fluorite oxide target material and a preparation method thereof, S1, zrO is weighed 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Placing the powder in a crucible respectively, and calcining in a muffle furnace to remove moisture and impurities; s2, calcining ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Mixing the powder and placing the mixture in a planetary ball mill, after the ball milling is finished, placing the slurry in a drying oven and drying to obtain high-entropy ceramic powder with uniform components; s3, granulating the high-entropy ceramic powder, and sequentially putting the granulated high-entropy ceramic powder into a hydraulic press and a cold isostatic press to be pressed to obtain a ceramic green body; s4, placing the ceramic green body in an atmosphere sintering furnace to obtain the ceramic green body(ZrHfCeYLaPr)O 2‑δ High entropy ceramic block followed by (ZrHfCeYLaPr) O 2‑δ And (3) cleaning and drying the high-entropy ceramic block after machining to obtain the high-entropy oxide target with the fluorite structure. According to the high-entropy fluorite oxide target material and the preparation method thereof, which adopt the structure, six-component high-entropy oxide target materials with higher purity and density are prepared by using oxide powder with equal molar ratio.

Description

High-entropy fluorite oxide target material and preparation method thereof
Technical Field
The invention relates to the technical field of high-entropy fluorite oxide target materials, in particular to a high-entropy fluorite oxide target material and a preparation method thereof.
Background
In recent years, high-entropy materials, particularly high-entropy alloys and high-entropy ceramics, have attracted great interest. In highly disordered, multi-component systems, high entropy materials possess excellent properties. High entropy oxide ceramics are solid solutions of inorganic compounds having one or more Wyckoff sites, with equal or nearly equal atomic ratios of the multiple principal elements. Compared with other ceramic materials, the high-entropy oxide ceramic has better stability, mechanical property, amorphous thermal conductivity, ultra-large dielectric constant and ultra-ionic conductivity. The high-entropy oxide ceramic has wide application prospect in the structural and functional fields of ultra-high temperature thermal protection and heat insulation of supersonic aircrafts, high-speed dry cutting of lithium ion batteries, thermoelectric materials, catalysts, electromagnetic wave absorption, electromagnetic interference shielding and the like. The fluorite structure is a single-phase structure with face-centered cubic lattice, and Djenadic et al prepared the single-phase fluorite high-entropy oxide for the first time in 2017.
The coating target is a sputtering source which forms various functional films on a substrate by sputtering through magnetron sputtering, multi-arc ion plating or other types of coating systems under proper process conditions. The purity, strength and compactness of the ceramic target are main influence indexes of the performance of the sputtered film. The high-entropy oxide target materials with different structures and properties can be prepared by changing the composition and the proportion of specific elements through the performance tailorability of the high-entropy material.
Disclosure of Invention
The invention aims to provide a high-entropy fluorite oxide target material and a preparation method thereof, and the six-component high-entropy oxide target material with higher purity and density is prepared by using oxide powder with equal molar ratio.
In order to achieve the purpose, the invention provides a high-entropy fluorite oxide target material and a preparation method thereof, wherein the preparation method of the high-entropy fluorite oxide target material comprises the following steps:
s1, weighing ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Placing the powder in a crucible respectively, and calcining in a muffle furnace to remove moisture and impurities;
s2, calcining ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Mixing the powder and placing the mixture in a planetary ball mill, after the ball milling is finished, placing the slurry in a drying oven and drying to obtain high-entropy ceramic powder with uniform components;
s3, granulating the high-entropy ceramic powder, and sequentially putting the granulated high-entropy ceramic powder into a hydraulic press and a cold isostatic press to be pressed to obtain a ceramic green body;
s4, placing the ceramic green body in an atmosphere sintering furnace to obtain (ZrHfCeYLaPr) O 2-δ High entropy ceramic block followed by (ZrHfCeYLaPr) O 2-δ And (3) cleaning and drying the high-entropy ceramic block after machining to obtain the high-entropy oxide target with the fluorite structure.
Preferably, the high-entropy ceramic powder of S2 is ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The molar ratio of (A) to (B) is 1: 1.
Preferably, zrO in the high-entropy ceramic powder in S2 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The purity of (2) was 99.99%.
Preferably, the calcining temperature in a muffle furnace in S1 is 850 ℃, and the calcining time is 2h.
Preferably, in S2, the planetary ball mill performs ball milling by using agate balls as a grinding medium and ethanol as a dispersant, and the ball-to-material ratio in the planetary ball mill is 6:1, the rotating speed is 250-300 r/min, the effective ball milling time is 6-8 h, and the planetary ball mill has a rest for 10min every 30min during grinding.
Preferably, the drying temperature of the slurry in S2 is 60 ℃, and the drying time is 12h.
Preferably, the adhesive used for granulation in S3 is a 5wt% PVA aqueous solution, and the amount of the adhesive used is 8% of the volume of the high-entropy ceramic powder.
Preferably, in S3, the pressure of the hydraulic press is 200-250 MPa, the pressure maintaining time is 3-5 min, the pressure of the cold isostatic press is 250-300 MPa, and the pressure maintaining time is 15-20 min.
Preferably, the heat treatment temperature in S4 is 1200-1600 ℃, and the heat treatment time is more than or equal to 2h.
Therefore, the high-entropy fluorite oxide target material with the structure and the preparation method thereof are adopted, and the high-entropy oxide target material with higher purity and density is prepared by using oxide powder with equal molar ratio.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 1 of a high-entropy fluorite oxide target and a method for preparing the same according to the present invention;
FIG. 2 is an X-ray diffraction pattern of comparative example 1 of a high entropy fluorite oxide target of the present invention and a method for preparing the same.
Detailed Description
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
Unless defined otherwise, technical or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The use of "first," "second," and similar terms in the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships may also be changed accordingly.
FIG. 1 is an X-ray diffraction pattern of an example 1 of a high-entropy fluorite oxide target and a method for preparing the same according to the present invention, FIG. 2 is an X-ray diffraction pattern of a comparative example 1 of a high-entropy fluorite oxide target and a method for preparing the same according to the present invention, as shown in the figure, a high-entropy fluorite oxide target and a method for preparing the same, S1, zrO 1, and 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 the powders are respectively placed in crucibles and calcined in a muffle furnace at 850 ℃ for 2h. And calcining to remove moisture and impurities and reduce the adverse effect of the moisture and the impurities on the high-entropy fluorite oxide.
S2, calcining ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 And mixing the powder, placing the mixture in a planetary ball mill, and carrying out ball milling by using agate balls as a grinding medium and ethanol as a dispersing agent, wherein the ball-material ratio is 6:1. the rotating speed of the planetary ball mill is 250-300 r/min, the planetary ball mill alternately operates in forward and reverse directions at intervals, the effective ball milling time is 6-8 h, and the planetary ball mill has a rest for 10min every 30min during grinding.
And after the ball milling is finished, drying the slurry in a drying oven at 60 ℃ for 12h to obtain the high-entropy ceramic powder with uniform components. ZrO in high-entropy ceramic powder 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 In a molar ratio of 1: 1, zrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The purity of (2) was 99.99%.
And S3, granulating the high-entropy ceramic powder, and then sequentially putting the granulated high-entropy ceramic powder into a hydraulic press and a cold isostatic press to press the granulated high-entropy ceramic powder into a ceramic green body, wherein the adhesive used for granulation is a 5wt% PVA (polyvinyl alcohol) aqueous solution, and the using amount of the adhesive is 8% of the volume of the high-entropy ceramic powder. The pressure of the hydraulic press is 200-250 Mpa, the pressure maintaining time is 3-5 min, the pressure of the cold isostatic press is 250-300 Mpa, and the pressure maintaining time is 15-20 min.
S4, placing the ceramic green body in an atmosphere sintering furnace, wherein the heat treatment temperature is 1200-1600 ℃, and the heat treatment time is more than or equal to 2 hours to obtain (ZrHfCeYLaPr) O 2-δ High entropy ceramic blocks. Followed by the reaction of (ZrHfCeYLaPr) O 2-δ And (3) cleaning and drying the high-entropy ceramic block after machining to obtain the high-entropy oxide target with the fluorite structure.
Example 1
S1, weighing ZrO with equal molar ratio 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The powders were respectively placed in crucibles and calcined in a muffle furnace at 850 ℃ for 2h.
S2, calcined ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 And mixing the powder, placing the mixture in a planetary ball milling tank, and carrying out ball milling by using agate balls as a grinding medium and ethanol as a dispersing agent, wherein the ball-material ratio is 6:1. the rotating speed of the planetary ball mill in forward and reverse alternate operation is 250r/min, the alternate operation time is 20min, and the alternate operation interval shutdown time is 10min.
After the ball milling is finished, separating the slurry from the agate balls, and drying the slurry in a drying oven at 60 ℃ for 12h to obtain the high-entropy ceramic powder with uniform components. And then, placing the high-entropy ceramic powder into an agate mortar for granulation, and dripping 5wt% of PVA (polyvinyl alcohol) aqueous solution while manually grinding, wherein the using amount of the adhesive is 8% of the volume of the high-entropy ceramic powder.
And S3, placing the granulated high-entropy ceramic powder into a mold, applying pressure to 200MPa by using a hydraulic press, and maintaining the pressure for 3min. And then placing the ceramic blank in a cold isostatic press, increasing the pressure to 250MPa at the pressure of 50MPa/min, maintaining the pressure for 15min, and reducing the pressure to 0MPa at the pressure of 50MPa/min to obtain a ceramic green body.
S4, placing the ceramic green body in an atmosphere sintering furnace, slowly discharging glue at the speed of 2 ℃/min, then keeping the temperature at 800 ℃ for 2h, heating to 1200 ℃ at the speed of 5 ℃/min, heating to 1600 ℃ at the speed of 2 ℃/min, and keeping the temperature for 4h. After the heat preservation is finished, the temperature is reduced to 1200 ℃ at the speed of 2 ℃/min, and the temperature is reduced to 500 ℃ at the speed of 5 ℃/min and then cooled along with the furnace. To (a) ZrHfCeYLaPr) O 2-δ After the high-entropy ceramic block is machined, the high-entropy ceramic block is cleaned and dried, and as can be seen from figure 1, the high-entropy oxide target with a single-phase fluorite structure is finally obtained.
Comparative example 1
S1, weighing ZrO with equal molar ratio 2 、HfO 2 、CeO 2 、Y 2 O 3 、Sc 2 O 3 、Pr 6 O 11 The powders were respectively placed in crucibles and calcined in a muffle furnace at 850 ℃ for 2h.
S2, calcined ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、Sc 2 O 3 、Pr 6 O 11 And mixing the powder, placing the mixture in a planetary ball milling tank, and carrying out ball milling by using agate balls as a grinding medium and ethanol as a dispersing agent, wherein the ball-material ratio is 6:1. the rotating speed of the planetary ball mill in forward and reverse alternate operation is 250r/min, the alternate operation time is 20min, and the alternate operation interval shutdown time is 10min.
After the ball milling is finished, separating the slurry from the agate balls, and drying the slurry in a drying oven at 60 ℃ for 12h to obtain the high-entropy ceramic powder with uniform components. And then, putting the high-entropy ceramic powder into an agate mortar for granulation, and dripping 5wt% of PVA aqueous solution while manually grinding, wherein the using amount of the adhesive is 8% of the volume of the high-entropy ceramic powder.
And S3, placing the granulated high-entropy ceramic powder into a mold, applying pressure to 200MPa by using a hydraulic press, and maintaining the pressure for 3min. And then placing the ceramic blank in a cold isostatic press, increasing the pressure to 250MPa at the pressure of 50MPa/min, maintaining the pressure for 15min, and reducing the pressure to 0MPa at the pressure of 50MPa/min to obtain a ceramic green body.
S4, placing the ceramic green body in an atmosphere sintering furnace, slowly discharging glue at the speed of 2 ℃/min, then keeping the temperature at 800 ℃ for 2h, and keeping the temperature at 5 DEG CHeating to 1200 ℃ at a speed of/min, heating to 1600 ℃ at a speed of 2 ℃/min, and keeping the temperature for 4h. After the heat preservation is finished, the temperature is reduced to 1200 ℃ at the speed of 2 ℃/min, and the temperature is reduced to 500 ℃ at the speed of 5 ℃/min and then cooled along with the furnace. Para (ZrHfCeYLaPr) O 2-δ After the high-entropy ceramic block is machined, the high-entropy ceramic block is cleaned and dried, and as can be seen from figure 2, the high-entropy oxide target with a single-phase fluorite structure is finally obtained.
Table 1 shows the performance data of the high-entropy oxide target
Components Whether it is single-phase Compactness degree
Example 1 (ZrHfCeYLaPr)O Is that 97.70％
Comparative example 1 (ZrHfCeYScPr)O Is that 90.80％
As can be seen from table 1, the structure and the density of the high-entropy fluorite oxide target in example 1 are superior to those of the high-entropy fluorite oxide target in comparative example 1.
Therefore, according to the high-entropy fluorite oxide target material with the structure and the preparation method thereof, the high-entropy oxide target material with higher purity and density is prepared by using the oxide powder with equal molar ratio.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the disclosed embodiments without departing from the spirit and scope of the present invention.

Claims (9)

1. A high-entropy fluorite oxide target material and a preparation method thereof are characterized in that: the preparation method of the high-entropy fluorite oxide target material comprises the following steps:
s1, weighing ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Placing the powder in a crucible respectively, and calcining in a muffle furnace to remove moisture and impurities;
s2, calcining ZrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 Mixing the powder and placing the mixture in a planetary ball mill, after the ball milling is finished, placing the slurry in a drying oven and drying to obtain high-entropy ceramic powder with uniform components;
s3, granulating the high-entropy ceramic powder, and sequentially putting the granulated high-entropy ceramic powder into a hydraulic press and a cold isostatic press to be pressed to obtain a ceramic green body;
s4, placing the ceramic green body in an atmosphere sintering furnace to obtain (ZrHfCeYLaPr) O 2-δ High entropy ceramic block followed by (ZrHfCeYLaPr) O 2-δ And (3) carrying out mechanical processing on the high-entropy ceramic block, cleaning and drying to obtain the high-entropy oxide target with a fluorite structure.
2. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: the high-entropy ceramic powder, zrO 2 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The molar ratio of (A) to (B) is 1: 1.
3. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: in the high-entropy ceramic powder in S2, zrO 2 、HfO 2 、CeO 2 、Y 2 O 3 、La 2 O 3 、Pr 6 O 11 The purity of (2) was 99.99%.
4. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: in the S1, the calcining temperature in the muffle furnace is 850 ℃, and the calcining time is 2h.
5. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: and S2, ball milling is carried out on the planetary ball mill by taking agate balls as a grinding medium and ethanol as a dispersing agent, wherein the ball-to-material ratio in the planetary ball mill is 6:1, the rotating speed is 250-300 r/min, the effective ball milling time is 6-8 h, and the planetary ball mill has a rest for 10min every 30min during grinding.
6. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: and in the S2, the drying temperature of the slurry is 60 ℃, and the drying time is 12h.
7. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, the method is characterized in that: the adhesive used for granulation in S3 is 5wt% of PVA aqueous solution, and the usage amount of the adhesive is 8% of the volume of the high-entropy ceramic powder.
8. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, characterized in that: and in the S3, the pressure of the hydraulic machine is 200-250 Mpa, the pressure maintaining time is 3-5 min, the pressure of the cold isostatic press is 250-300 Mpa, and the pressure maintaining time is 15-20 min.
9. The high-entropy fluorite oxide target material and the preparation method thereof according to claim 1, wherein the high-entropy fluorite oxide target material comprises the following components: and S4, the heat treatment temperature is 1200-1600 ℃, and the heat treatment time is more than or equal to 2h.
CN202210915185.3A 2022-08-01 2022-08-01 High-entropy fluorite oxide target material and preparation method thereof Pending CN115259853A (en)

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