CN113387684A - Preparation method of high-entropy oxide with good infrared radiation performance - Google Patents
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Abstract
The invention discloses a preparation method of high-entropy oxide with good infrared radiation performance, which uses CuO and MnO2、Fe2O3、Cr2O3、Co3O4、TiO2And any four of ZnO and MgO powder are taken as raw materials, ball-milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in the air atmosphere, and the product is cooled and ground to obtain the high-entropy oxide with the spinel structure. The invention adopts the method of combining the mechanical wet milling method and the solid phase synthesis method to prepare the high entropy oxide, can ensure that the metal elements are fully mixed, has the advantages of simple preparation technology, strong repeatability, high production efficiency, suitability for industrial production and the like, andthe prepared high-entropy oxide has the advantages of single phase, high purity, small particle size, uniform element distribution, high infrared emissivity and good thermal stability, and can be used as an infrared radiation material in the fields of infrared radiation heating and heat dissipation materials.
Description
Technical Field
The invention relates to a high-entropy oxide, in particular to a high-entropy oxide with good infrared radiation performance and a preparation method thereof, belonging to the field of infrared radiation materials.
Background
With the development of industrial technology, the contradiction between supply and demand of energy is increasingly deepened. Due to the specific properties of infrared ceramics, their applications in various areas of national economy are increasing and developing. The infrared radiation material is used as a novel energy-saving material, and is coated on the surface of the base material, so that the energy-saving effect is good, the base material is well protected, the service life of the base material is prolonged, and the production cost is reduced. Therefore, the infrared radiation ceramic material has wide application prospect.
The high-emissivity coating is mostly used at medium and high temperature, and the infrared emissivity of the coating is reduced in practical use because the crystal structure of the filler is unstable. From the relationship between symmetry and group theory, researchers think according to irreducible representation theory of groups that: among high-emissivity filler materials, particularly ceramic materials, ceramic materials having a spinel crystal structure have a relatively high infrared emissivity compared to other crystal structure types of ceramic materials. Therefore, the ceramic material with spinel crystal structure is the first choice for the research and application of high-radiation ceramic materials at home and abroad at present. The countries such as Europe, America and Russia have developed a nickel-chromium spinel type high-temperature high-radiation ceramic coating material used at a high temperature of 450-750 ℃, and the ceramic coating material has stable infrared radiation performance and slow infrared radiation rate attenuation under high vacuum and high temperature. The infrared emissivity of spinel-type ceramic materials is affected by a number of factors, of which the filling state of tetrahedral and octahedral gaps in the spinel structure by transition metal cations is an important factor, and it is empirically known that the infrared emissivity of spinels of partially inverted and mixed type structures is higher.
The high-entropy oxide material has higher entropy value, lower Gibbs free energy and larger lattice distortion, thereby showing excellent performances in the aspects of electricity, optics, magnetism, catalysis and the like, and being one of the important discoveries in the field of high-entropy materials in recent years. The preparation methods of the spinel type high-entropy oxide reported at present mainly comprise a solid-phase reaction method and a wet chemical method. In 2017, Dabrowa J and the like firstly adopt a traditional high-temperature solid-phase synthesis method to prepare high-entropy oxide materials (Ni, Mn, Fe, Co and Cr) with a spinel structure3O4. CN108933248A discloses a preparation method of a spinel-type spherical high-entropy oxide material as a negative electrode material of a lithium ion battery, and the high-entropy oxide material is prepared by combining a sol-gel self-propagating combustion method and low-temperature heat treatment. CN 111620681A discloses that a hydrothermal method and a plasma technology are combined to prepare the high-entropy oxide material. The solid-phase reaction method in the above documents has the disadvantages of long heat preservation time (20 hours), complicated process and long period, and needs to be placed on an aluminum plate for air quenching; the spinel type high-entropy oxide prepared by a wet chemical method has the defects of high raw material cost, multiple preparation steps, complex and uncontrollable process and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a high-entropy oxide with good infrared radiation performance.
Preparation of mono-and high-entropy oxides
With CuO, MnO2、Fe2O3、Cr2O3、Co3O4、TiO2And any four of ZnO and MgO powder are taken as raw materials, ball-milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in the air atmosphere, and the product is cooled and ground to obtain the high-entropy oxide with the spinel structure.
The raw materials are proportioned according to the equimolar ratio of metal atoms.
The ball milling is carried out by adopting a planetary ball mill, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-12 hours, and the ball material-water ratio is (2-5): 1: 3. The ball milling process comprises the following steps: ball milling is carried out for 1 hour, then ball milling is suspended for 10 minutes, ball milling is carried out for 1 hour, ball milling is suspended for 10 minutes, and the ball milling is cycled and cycled according to the period.
The calcination temperature is 500-1200 ℃, the heating rate is 10-15 ℃/min, and the calcination time is 1-10 hours.
The cooling mode is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.
EDS (electronic discharge machining) characterization results show that the molar ratio of each metal element in the high-entropy oxide prepared by the method is equal, meets the original component design and is in a typical high-entropy compound state.
The high-entropy oxide prepared by the invention has a spinel crystal structure as shown by the characteristics of an SEM image, a TEM image and an XRD (X-ray diffraction) through the combination of a mechanical wet grinding method and a solid phase synthesis method. Compared with binary ternary spinel, the disordered arrangement of multiple elements of the high-entropy ceramic causes serious lattice distortion and changes the lattice vibration period, so that the lattice vibration is increased, and the infrared radiation performance of the material is improved. The high-entropy ceramic has a unique multi-spinel structure, metal elements are distributed in oxygen octahedral gaps and oxygen tetrahedral gaps, and the metal elements and oxygen form stronger chemical bonds, so that the crystal structure is stable, and the high-entropy ceramic has good thermal stability.
Performance of di, high entropy oxides
1. Infrared radiation property
The infrared emissivity of the high-entropy oxide is evaluated by adopting a TSS-5X-2 infrared emissivity detector manufactured by Senor corporation of Japan, and the normal infrared emissivity of the high-entropy oxide in a 2-22 mu m wave band is measured. Through testing, the prepared high-entropy oxide has the infrared emissivity of 0.89-0.92.
2. Thermal stability
The high-entropy oxide was placed in a box furnace air atmosphere and subjected to a thermal stability test at 1500 ℃ for 100 hours. A long-time thermal stability experiment shows that the prepared high-entropy oxide has a stable crystal structure, and the fluctuation of the infrared emissivity is only 0.01-0.03.
The data show that the high-entropy oxide prepared by adopting the method combining the mechanical wet grinding method and the solid-phase synthesis method can ensure that the metal elements are fully and uniformly mixed, has the advantages of simple preparation technology, strong repeatability, high production efficiency, suitability for industrial production and the like, has single phase, high purity, smaller particle size, uniform element distribution, higher infrared emissivity and good thermal stability, and can be used as an infrared radiation material in the field of infrared radiation heating and heat dissipation materials.
Drawings
FIG. 1 shows (Cu, Mn, Zn, Fe) in example 1 of the present invention3O4XRD pattern of (a);
FIG. 2 shows (Cu, Mn, Zn, Fe) in example 1 of the present invention3O4SEM picture of (1);
FIG. 3 shows (Cu, Mn, Zn, Fe) in example 1 of the present invention3O4A TEM image of (B);
FIG. 4 shows (Cu, Mn, Zn, Fe) in example 1 of the present invention3O4EDS results of (a);
FIG. 5 shows (Cu, Mn, Zn, Fe) in example 1 of the present invention3O4XRD pattern after thermal stability experiment;
FIG. 6 shows (Cu, Mg, Cr, Ti) in example 2 of the present invention3O4XRD pattern of (a);
FIG. 7 shows (Cu, Cr, Co, Ti) in example 3 of the present invention3O4XRD pattern of (a);
FIG. 8 shows (Cu, Mg, Fe, Ti) in example 4 of the present invention3O4XRD pattern of (a);
FIG. 9 shows (Cu, Zn, Cr, Ti) in example 5 of the present invention3O4XRD pattern of (a).
Detailed Description
Example 1
CuO11.933g (0.15 mol) and MnO were weighed respectively213.041g（0.15mol）、ZnO12.207g（0.15mol）、Fe2O311.977g (0.075 mol) of powder; pouring the ball milling beads, the raw materials and the ultrapure water into a ball milling tank according to the mass ratio of the ball to the materials to the water of 4:1: 3; placing the ball milling tank on a ball milling machine station, performing ball milling for 1 hour at a rotation speed of 450r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10 minutes, and performing ball milling at a rotation speed of 450r/min, ball milling for 7 hours to obtain mixed powder; then drying and grinding the mixed powder obtained after ball milling, placing the powder in a box type resistance furnace, heating to 650 ℃ (the heating rate is 14 ℃/min) in the air atmosphere, calcining for 7 hours, then quenching in air and cooling to room temperature to obtain single-phase (Cu, Mn, Zn, Fe)3O4High entropy oxide powder.
FIG. 1 shows the prepared (Cu, Mn, Zn, Fe)3O4XRD pattern of high entropy oxides, this line being in agreement with Fe in the ICDD database with spinel structure3O4The lines (PDF #74-0748) are very consistent, indicating that the high entropy oxide produced in this example is a single phase solid solution with a face centered cubic crystal structure.
FIGS. 2 and 3 show the results for preparation (Cu, Mn, Zn, Fe)3O4SEM images and TEM images of the high-entropy oxide powder are consistent with XRD results.
FIG. 4 shows (Cu, Mn, Zn, Fe)3O4The EDS result of the high-entropy oxide shows that the molar ratio of each metal element in the high-entropy oxide is equimolar, meets the original component design and is in a typical high-entropy compound state.
FIG. 5 shows the results of preparation (Cu, Mn, Zn, Fe)3O4XRD patterns before and after a high-entropy oxide thermal stability experiment show that the high-entropy oxide does not have phase change after 1500 ℃ thermal stability experiment, and the high-entropy oxide is shown to have good thermal stability.
0.2 g of the prepared (Cu, Mn, Zn, Fe)3O4Measuring the normal infrared emissivity of the high-entropy oxide at a wave band of 2-22 mu m to be 0.92; after a thermal stability experiment, the normal infrared emissivity of the high-entropy oxide in a wave band of 2-22 mu m is measured to be 0.91.
Example 2
CuO11.933g (0.15 mol), MgO6.045g (0.15 mol) and Cr are respectively weighed2O311.399g（0.075mol）、TiO211.985g (0.15 mol) of powder; pouring the ball milling beads, the raw materials and the ultrapure water into a ball milling tank according to the mass ratio of the ball to the materials to the water of 2:1: 3; placing the ball milling tank on a ball milling machine station, firstly performing ball milling for 1 hour at the rotating speed of 300r/min, and then temporarily performing ball millingStopping the ball milling for 10min, taking the ball milling period as one ball milling period, carrying out ball milling for 1 hour after 10min, wherein the rotating speed is 300r/min, and carrying out ball milling for 5 hours in total to obtain mixed powder; then, the mixed powder obtained after ball milling is dried and ground, then the mixed powder is placed in a box type resistance furnace, the temperature is raised to 500 ℃ in the air atmosphere (the temperature raising rate is 10 ℃/min), the mixed powder is calcined for 1 hour, and then the mixed powder is cooled to room temperature along with the furnace to obtain single-phase (Cu, Mg, Cr, Ti)3O4A high entropy oxide.
FIG. 6 shows the results of preparation (Cu, Mg, Cr, Ti)3O4XRD pattern of high entropy oxides, this line being in agreement with Fe in the ICDD database with spinel structure3O4The lines (PDF #74-0748) are very consistent, indicating that the high entropy oxide produced in this example is a face centered cubic crystal structure.
0.2 g of prepared (Cu, Mg, Cr, Ti)3O4Measuring the normal infrared emissivity of the high-entropy oxide at a wave band of 2-22 mu m to be 0.89; after a thermal stability experiment, the normal infrared emissivity of the high-entropy oxide in a wave band of 2-22 mu m is measured to be 0.90.
Example 3
CuO11.933g (0.15 mol) and Cr are respectively weighed2O311.399g（0.075 mol）、Co3O412.040g（0.05 mol）、TiO211.985g (0.15 mol) of powder; pouring ball grinding beads, raw materials and ultrapure water into a ball grinding tank according to the mass ratio of the ball to the materials to the water of 4:1: 3; placing the ball milling tank on a ball milling machine station, performing ball milling for 1 hour at the rotation speed of 400r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10 minutes, and performing ball milling for 9 hours at the rotation speed of 400r/min to obtain mixed powder; then drying and grinding the mixed powder after ball milling, placing the powder in a box type resistance furnace, heating to 970 ℃ (the heating rate is 11 ℃/min) in the air atmosphere, calcining for 2 hours, and then cooling to room temperature along with the furnace to obtain single-phase (Cu, Cr, Co, Ti)3O4A high entropy oxide.
FIG. 7 shows the results (Cu, Cr, Co, Ti)3O4XRD pattern of high entropy oxides, this line being in agreement with Fe in the ICDD database with spinel structure3O4Line (a)PDF #74-0748) are very consistent, indicating that the high entropy oxide prepared in this example is a single phase solid solution with a face centered cubic crystal structure.
0.2 g of the prepared (Cu, Cr, Co, Ti)3O4Measuring the normal infrared emissivity of the high-entropy oxide at a wave band of 2-22 mu m to be 0.89; after a thermal stability experiment, the normal infrared emissivity of the high-entropy oxide in a wave band of 2-22 mu m is measured to be 0.88.
Example 4
CuO11.933g (0.15 mol), MgO6.045g (0.15 mol) and Fe are weighed respectively2O311.977g（0.075 mol）、TiO211.985g (0.15 mol) of powder; pouring the ball milling beads, the raw materials and the ultrapure water into a ball milling tank according to the mass ratio of the ball to the materials to the water of 3:1: 3; placing the ball milling tank on a ball milling machine station, performing ball milling for 1 hour at the rotation speed of 500r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10 minutes, and performing ball milling for 8 hours at the rotation speed of 500r/min to obtain mixed powder; then drying and grinding the mixed powder after ball milling, placing the powder in a box type resistance furnace, heating to 830 ℃ in air atmosphere (the heating rate is 13 ℃/min), calcining for 9 hours, then quenching and cooling to room temperature by liquid nitrogen to obtain single-phase (Cu, Mg, Fe, Ti)3O4A high entropy oxide.
FIG. 8 shows the results of preparation (Cu, Mg, Fe, Ti)3O4XRD pattern of high entropy oxides, this line being in agreement with Fe in the ICDD database with spinel structure3O4The lines (PDF #74-0748) are very consistent, indicating that the high entropy oxide produced in this example is a single phase solid solution with a face centered cubic crystal structure.
Taking 0.2 g (Cu, Mg, Fe, Ti)3O4Measuring the normal infrared emissivity of the high-entropy oxide at a wave band of 2-22 mu m to be 0.91; after a thermal stability experiment, the normal infrared emissivity of the high-entropy oxide in a wave band of 2-22 mu m is measured to be 0.88.
Example 5
Separately weighing MnO213.041g（0.15mol）、ZnO12.207g（0.15mol）、Cr2O311.399g（0.075mol）、TiO211.985g (0.15 mol) of powder; pouring the ball milling beads, the raw materials and the ultrapure water into a ball milling tank according to the mass ratio of the ball to the materials to the water of 5:1: 3; placing the ball milling tank on a ball milling machine station, performing ball milling for 1 hour at the rotation speed of 500r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10 minutes, and performing ball milling at the rotation speed of 500r/min for 12 hours in total to obtain mixed powder; then drying and grinding the mixed powder after ball milling, putting the mixed powder into a box-type resistance furnace, heating the mixed powder to 1200 ℃ in the air atmosphere (the heating rate is 15 ℃/min), calcining the mixed powder for 10 hours, and then cooling the calcined mixed powder to room temperature along with the furnace to obtain single-phase (Cu, Zn, Cr and Ti)3O4A high entropy oxide.
FIG. 9 shows preparation (Cu, Zn, Cr, Ti)3O4XRD pattern of high entropy oxides, this line being in agreement with Fe in the ICDD database with spinel structure3O4The lines (PDF #74-0748) are very consistent, indicating that the high entropy oxide produced in this example is a single phase solid solution with a face centered cubic crystal structure.
0.2 g of (Cu, Zn, Cr, Ti) prepared in this example was taken3O4Measuring the normal infrared emissivity of the high-entropy oxide at a wave band of 2-22 mu m to be 0.90; after a thermal stability experiment, the normal infrared emissivity of the high-entropy oxide in a wave band of 2-22 mu m is measured to be 0.89.
Claims (6)
1. A process for preparing high-entropy oxide with high infrared radiation performance from CuO and MnO2、Fe2O3、Cr2O3、Co3O4、TiO2And any four of ZnO and MgO powder are taken as raw materials, ball-milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in the air atmosphere, and the product is cooled and ground to obtain the high-entropy oxide with the spinel structure.
2. The process for preparing a high-entropy oxide with good infrared radiation properties according to claim 1, wherein: the raw materials are proportioned according to the equimolar ratio of metal atoms.
3. The process for preparing a high-entropy oxide with good infrared radiation properties according to claim 1, wherein: the ball milling is carried out by adopting a planetary ball mill, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-12 hours, and the ball material-water ratio is (2-5): 1: 3.
4. A process for the preparation of a high entropy oxide with good infrared radiation properties according to claim 3, characterized in that: the ball milling process comprises the following steps: ball milling is carried out for 1 hour, then ball milling is suspended for 10 minutes, ball milling is carried out for 1 hour, ball milling is suspended for 10 minutes, and the ball milling is cycled and cycled according to the period.
5. The process for preparing a high-entropy oxide with good infrared radiation properties according to claim 1, wherein: the calcination temperature is 500-1200 ℃, the heating rate is 10-15 ℃/min, and the calcination time is 1-10 hours.
6. The process for preparing a high-entropy oxide with good infrared radiation properties according to claim 1, wherein: the cooling mode is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.
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