CN117902890B - Spinel-corundum dual-phase high-entropy ceramic powder material and preparation method thereof - Google Patents
Spinel-corundum dual-phase high-entropy ceramic powder material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 239000000843 powder Substances 0.000 title claims abstract description 98
- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 33
- 239000010431 corundum Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 16
- 239000011029 spinel Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 45
- 238000001354 calcination Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000002051 biphasic effect Effects 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 abstract description 6
- 239000011358 absorbing material Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 38
- 238000001228 spectrum Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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Abstract
The invention relates to a spinel-corundum dual-phase high-entropy ceramic powder material, which has a chemical formula of AFe xOy, wherein A is 4-5 transition metal elements in Cu, ni, co, zn, mg, mn and Cr, and the molar ratio of each element is equal to 1< x <2,3< y <4; the ceramic is a biphase intergrowth structure ceramic, and has a cubic spinel phase and a trigonal corundum phase crystal structure. Meanwhile, the invention also discloses a preparation method of the biphase high-entropy ceramic powder material. The biphase high-entropy ceramic powder material has the characteristics of coexistence of two phases, high purity and uniform element distribution, has excellent solar absorptivity (> 0.87), infrared emissivity (> 0.90) and high-temperature thermal stability (1700 ℃), and can be widely used as an infrared radiation material and a solar energy absorbing material in the fields of aerospace, power station boilers, photo-thermal power generation, interface evaporation, photo-thermal deicing and the like.
Description
Technical Field
The invention relates to the field of infrared radiation heating/radiating materials and solar energy absorbing materials, in particular to a spinel-corundum dual-phase high-entropy ceramic powder material and a preparation method thereof.
Background
Ceramic materials with high solar absorptivity and high infrared emissivity are widely used in civil, industrial, aerospace, and even military fields. However, as the modernization degree of industry is continuously improved, the environment facing the material is more and more complex, the requirements of various fields on ceramic materials are also increased, and new ceramic materials with more excellent performances are more required to be researched. The high-entropy ceramic is a novel material derived from the design concept of high-entropy alloy, and has become a research hot spot in the field of inorganic nonmetallic materials in recent years due to the unique structure, high-entropy effect, lattice distortion effect, delayed diffusion effect and cocktail effect, and has been applied to the high-end technological key fields of high-temperature wave absorption, energy storage, catalysis, thermoelectricity and the like.
Since A, B of spinel structure (AB 2O4) of cubic crystal system can easily fill gaps, replace or displace transition metal oxide ions, alkali metals and rare elements, doping elements with the effect of improving solar absorptivity and infrared emissivity can effectively improve infrared radiation performance. Meanwhile, spinel has excellent physical and chemical stability, and the crystal structure is not easy to change after long-time use. The corundum phase of the trigonal system is in an octahedral structure, has the temperature resistance reaching 1800 ℃, and has excellent wear resistance and fire resistance.
At present, many researches on ceramic materials are changed from a binary system to a high-entropy system, and gradually expanded to a high-entropy alloy ceramic dual-phase, and good results are obtained. Feng Jing, et al, chinese patent application publication No. CN 114773059A, a symbiotic biphase high-entropy ceramic, and a preparation method and application thereof, and a biphase high-entropy ceramic material is prepared by combining a ball milling method and a spark plasma sintering process. In 2022, G Dai and the like prepared a dual-phase high-entropy oxide material (Fe 0.2x,Co0.2,Ni0.2,Cr0.2,Mn0.2)3O4 (x=1 to 5)) by using a conventional high-temperature solid-phase synthesis method, and the spinel-phase and alloy-phase dual-phase intergrowth （G. Dai, R. Deng, T. Zhang, et al. Quantitative evaluation of loss capability for in situ conductive phase enhanced microwaveabsorption of high-entropy transition metal oxides[J]. Adv. Funct. Mater. 2022,32, 2205325). high-entropy dual-phase material has excellent properties due to strong lattice distortion, a large number of crystal interfaces and abundant oxygen vacancies, but the combination of a ceramic phase and an alloy phase has poor high-temperature thermal stability.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the spinel-corundum dual-phase high-entropy ceramic powder material with good performance.
The invention aims to provide a preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material.
In order to solve the problems, the spinel-corundum dual-phase high-entropy ceramic powder material is characterized by comprising the following components in percentage by weight: the chemical formula of the biphase high-entropy ceramic powder material is AFe xOy, wherein A is 4-5 transition metal elements in Cu, ni, co, zn, mg, mn and Cr, and the molar ratio of the elements is 1< x <2,3< y <4; the ceramic is a biphase intergrowth structure ceramic, and has a cubic spinel phase and a trigonal corundum phase crystal structure.
The solar energy absorptivity of the biphasic high-entropy ceramic powder material is more than 0.87 within the range of 0.3-2.5 mu m, and the infrared emissivity is more than 0.90 within the range of 2-22 mu m.
The average grain size of the biphase high-entropy ceramic powder material is in the range of 200-500 nm.
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps of:
Step 1: the molar ratio of metal elements is 1: 6-10 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is four of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; or the molar ratio of metal elements is 1: 8-12 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is five of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; the raw materials are subjected to ball milling, mixing, drying and grinding to obtain precursor powder;
Step 2: the precursor powder is calcined in sections in air atmosphere, cooled and ground to obtain the high-entropy ceramic powder material with spinel and corundum dual-phase coexistence structure.
The ball milling condition in the step 1 is that a planetary ball mill is adopted for ball milling, the ball milling solvent is ultrapure water, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-10 hours, and the mass ratio of ball material water is 2-5: 1:3.
The drying condition in the step 1 means that the temperature is 80-100 ℃ and the drying time is 12-24 hours.
The condition of the sectional calcination in the step 2 is that the temperature is raised to 500 ℃ at 5 ℃/min, then the temperature is raised at 2-5 ℃/min, the calcination temperature is 500-1400 ℃ and the calcination time is 1-10 hours.
And the cooling mode in the step 2 is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.
Compared with the prior art, the invention has the following advantages:
1. The biphasic high-entropy ceramic powder material has two crystal structures of a cubic spinel phase and a trigonal corundum phase, wherein the spinel phase is Fd-3m space group, A ions and 4 oxygen ions form a coordination structure and are positioned in tetrahedral gaps, B ions and 6 oxygen atoms form a coordination structure and are positioned in octahedral gaps; the corundum phase is an R-3c space group, and is in a coordination structure formed by ions and 6 oxygen atoms, and is positioned in an octahedral gap. The two phases coexist in a symbiotic way, so that the grain growth can be restrained, the ceramic particles have smaller size (200-500 nm), and the ceramic particles have the characteristics of high purity, stable phase structure, uniform element distribution and the like.
2. The biphase high-entropy ceramic powder material provided by the invention has an emissivity of more than 0.90 within a range of 2-22 mu m after a thermal stability test at 1700 ℃ due to the combination of a unique biphase symbiotic structure and a high-entropy effect, which shows that the material has good high-temperature thermal stability.
3. The biphasic high-entropy ceramic powder material has higher infrared emissivity and solar absorptivity in air, wherein the emissivity reaches more than 0.9 in a wave band of 2-22 mu m, and the solar absorptivity reaches more than 0.87 in a wave band of 0.3-2.5 mu m. Compared with single-phase spinel high-entropy ceramic, the reasons for the high-entropy ceramic powder material with high sunlight absorptivity and infrared emissivity mainly include the following points:
(1) The method comprises the steps of reacting and calcining in a high-temperature environment to cause a large amount of oxygen atoms to overflow to form oxygen vacancies, and generating a corundum phase structure by partial valence change of Fe ions in order to keep ionization balance, so that a unique biphasic symbiotic characteristic is formed, serious lattice distortion is caused, asymmetric lattice vibration is increased, vibration absorption is enhanced, and the solar light absorptivity and infrared emissivity of a mid-infrared band (2.5-25 mu m) are improved;
(2) The change of valence of the polyvalent element can generate small polarons to promote electron transition, impurity energy levels are formed locally by doping ions with different valence states and valence bond structures, and the concentration of free carriers (electrons and holes) in a valence band and the transition between band gaps are enhanced, so that the solar absorptivity and infrared emissivity of a near infrared band (0.75-2.5 mu m) are improved;
(3) The biphase high-entropy ceramic powder material belongs to a nanoscale material, the grain boundary number is increased when the size is small (200-500 nm), the defect structure is increased, the heat radiation selectivity is reduced, and the solar energy absorptivity and infrared emissivity of the material can be obviously improved.
4. The high-entropy ceramic powder material prepared by the invention adopts mechanical wet grinding and solid phase synthesis method calcination, can ensure that metal elements are fully and uniformly mixed, has the advantages of simple operation, short production period, realization of industrial production and the like, and can be widely used as an infrared radiation material and a solar energy absorbing material in the fields of aerospace, power station boilers, photo-thermal power generation, interface evaporation, photo-thermal deicing and the like.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows XRD patterns of Fe xOy of example 1 (Cu, ni, zn, co) of the present invention.
FIG. 2 is an XRD pattern of Fe xOy of example 2 (Cu, zn, mg, co) of the present invention.
FIG. 3 shows XRD patterns of Fe xOy of example 3 (Cu, ni, co, cr) of the present invention.
FIG. 4 shows the EDS results of Fe xOy of example 3 (Cu, ni, co, cr) of the present invention.
FIG. 5 shows SEM results of Fe xOy of example 3 (Cu, ni, co, cr) of the present invention.
FIG. 6 is a graph showing the solar light absorptivity of Fe xOy of example 3 (Cu, ni, co, cr) of the present invention in the 0.3-2.5 μm band.
FIG. 7 is an XRD pattern after thermal stability testing of Fe xOy of example 3 (Cu, ni, co, cr) of the present invention.
FIG. 8 shows XRD results for Fe xOy of example 4 (Cu, ni, co, mn, cr) of the present invention.
Detailed Description
The chemical formula of the spinel-corundum dual-phase high-entropy ceramic powder material is AFe xOy, wherein the A site is 4-5 transition metal elements in Cu, ni, co, zn, mg, mn and Cr, and the elements are in equimolar ratio of 1< x <2,3< y <4; the ceramic is a biphase intergrowth structure ceramic, and has a cubic spinel phase and a trigonal corundum phase crystal structure.
The solar energy absorptivity of the biphasic high-entropy ceramic powder material is more than 0.87 within the range of 0.3-2.5 mu m, and the infrared emissivity is more than 0.90 within the range of 2-22 mu m. The average grain size is 200-500 nm.
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps:
Step 1: the molar ratio of metal elements is 1: 6-10 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is four of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; or the molar ratio of metal elements is 1: 8-12 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is five of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; ball milling is carried out on all the raw materials by adopting a planetary ball mill, the ball milling solvent is ultrapure water, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-10 hours, and the mass ratio (g/g) of ball material water is 2-5: 1:3. and then drying at 80-100 ℃ for 12-24 hours, and grinding to obtain precursor powder.
Step 2: the precursor powder is calcined in sections in an air atmosphere, the temperature is firstly increased to 500 ℃ at 5 ℃/min, then the temperature is continuously increased at 2-5 ℃/min, the calcining temperature ranges from 500 ℃ to 1400 ℃, and the calcining time is 1-10 hours. And cooling by adopting one of furnace-following cooling, air quenching cooling and liquid nitrogen quenching cooling after the calcination is finished, and grinding to obtain the high-entropy ceramic powder material with the spinel and corundum dual-phase coexistence structure.
Example 1
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps:
Step 1: the mole ratio of metal atoms is 1:1:1:1:6, respectively weighing CuO (0.7955 g), niO (0.4030 g), znO (0.8139 g), coO (0.7493 g) and Fe 3O4 (4.6318 g) powder, ball milling by adopting a planetary ball mill, wherein the ball milling solvent is ultrapure water, and the mass ratio (g/g) of ball material water is 2:1:3, ball milling is carried out for 1 hour at the rotating speed of 400 r/min, then 10min is stopped, the ball milling period is taken as one ball milling period, and ball milling is carried out for 1 hour after 10min, the rotating speed is 400 r/min, and total ball milling is carried out for 5 hours. And then drying at 80-100 ℃ for 12-24 hours, and grinding to obtain precursor powder.
Step 2: the precursor powder is calcined in stages in an air atmosphere, and the temperature is raised to 500 ℃ at 5 ℃/min, and the calcination time is 1 hour. And (3) cooling along with the furnace after the calcination is finished, and grinding to obtain the biphase (Cu, ni, zn, co) Fe xOy high-entropy ceramic powder material, wherein x is 1< 2, y is 3< 4.
The X-ray diffraction test is carried out on the obtained (Cu, ni, zn, co) Fe xOy high-entropy ceramic powder material, and the result is shown in figure 1, and the spectrum line is very consistent with the CuFe 2O4 spectrum line (PDF#25-0283) with a spinel structure and the Fe 2O3 spectrum line (PDF#33-0664) with a corundum structure in an ICDD database, which shows that the high-entropy ceramic powder material prepared by the embodiment has a biphase coexistence structure.
The solar energy absorption of this material was evaluated by using a Lambda 950 type ultraviolet/visible/near infrared spectrophotometer (equipped with a 150mm integrating sphere) manufactured by PerkinElmer corporation of usa, the absorption in the 0.3 to 2.5 μm band was measured, and then the solar energy absorption was calculated according to the calculation formula in international standard ISO 9845-1 (1992). The infrared emissivity of the material was evaluated by using a TSS-5X-2 infrared emissivity detector manufactured by the company Senor of Japan, and the normal infrared emissivity in the 2-22 μm band was measured. The biphase high-entropy ceramic powder material is placed in the air atmosphere of a box-type furnace, and a thermal stability experiment of 200 h is carried out at 1700 ℃.
Taking 0.2 g (Cu, ni, zn, co) Fe xOy high-entropy ceramic powder material, and measuring that the normal infrared emissivity of the material is 0.87 in a wave band of 2-22 mu m and the solar absorptivity of the material is 0.870 in a wave band of 0.3-2.5 mu m; after a thermal stability experiment, the material is measured to have the normal infrared emissivity of 0.90 in a wave band of 2-22 mu m and the solar absorptivity of 0.871 in a wave band of 0.3-2.5 mu m.
Example 2
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps:
Step 1: the mole ratio of metal atoms is 1:1:1:1:10, respectively weighing CuO (0.7955 g), znO (0.8139 g), coO (0.7493 g) and MgO 2（0.4030 g）、Fe3O4 (7.7180 g) powder, ball milling by adopting a planetary ball mill, wherein the ball milling solvent is ultrapure water, and the mass ratio (g/g) of ball material water is 2:1:3, ball milling is carried out for 1 hour at the rotating speed of 300 r/min, then 10 min is paused, the ball milling period is taken as one ball milling period, after 10 min, ball milling is carried out for 1 hour at the rotating speed of 300 r/min, and ball milling is carried out for 5 hours. And then drying at 80-100 ℃ for 12-24 hours, and grinding to obtain precursor powder.
Step 2: the precursor powder is calcined in sections in air atmosphere, the temperature is firstly raised to 500 ℃ for calcination, the temperature raising rate is 5 ℃/min, then the temperature is raised to 800 ℃ at the temperature raising rate of 2 ℃/min, and the calcination time is 3 hours. And (3) cooling along with the furnace after the calcination is finished, and grinding to obtain the biphase (Cu, zn, mg, co) Fe xOy high-entropy ceramic powder material, wherein x is 1< 2, y is 3< 4.
X-ray diffraction test is carried out on the obtained (Cu, zn, mg, co) Fe xOy high-entropy ceramic powder material, and the result is shown in figure 2, and the spectrum line is shown as a dual-phase coexistence structure of the high-entropy ceramic material prepared by the embodiment, namely, the CuFe 2O4 spectrum line (PDF#25-0283) with a spinel structure and the Fe 2O3 spectrum line (PDF#33-0664) with a corundum structure in an ICDD database.
An absorption rate of 0.3-2.5 μm band, a normal infrared emissivity of 2-22 μm band, and a thermal stability test were the same as in example 1.
Taking 0.2 g (Cu, zn, mg, co) Fe xOy high-entropy ceramic powder material, and measuring that the normal infrared emissivity of the material is 0.91 in a wave band of 2-22 mu m and the solar absorptivity of the material is 0.880 in a wave band of 0.3-2.5 mu m; after a thermal stability experiment, the material has the normal infrared emissivity of 0.90 in a wave band of 2-22 mu m and the solar absorptivity of 0.895 in a wave band of 0.3-2.5 mu m.
Example 3
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps:
Step 1: the mole ratio of metal atoms is 1:1:1:1:8, respectively weighing CuO（0.7955 g）、NiO（0.7469 g）、CoO（0.7493 g）、Cr2O3（0.7599 g）、Fe3O4（6.1744 g） powder, ball milling by adopting a planetary ball mill, wherein a ball milling solvent is ultrapure water, and the mass ratio (g/g) of ball material water is 2:1:3, ball milling is carried out for 1 hour at the rotating speed of 300 r/min, then 10min is paused, the ball milling period is taken as one ball milling period, after 10min, ball milling is carried out for 1 hour at the rotating speed of 300 r/min, and the total ball milling time is 8 hours. And then drying at 80-100 ℃ for 12-24 hours, and grinding to obtain precursor powder.
Step 2: the precursor powder is calcined in sections in air atmosphere, the temperature is firstly increased to 500 ℃ for calcination, the temperature increasing rate is 5 ℃/min, then the temperature is increased to 1000 ℃ at the temperature increasing rate of 4 ℃/min, and the calcination time is 5 hours. Cooling with a furnace after the calcination is finished, and grinding to obtain the biphase (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material, wherein x is 1< 2, y is 3< 4.
X-ray diffraction test is carried out on the obtained (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material, and the result is shown in figure 3, and the spectrum line is shown as a dual-phase coexistence structure of the high-entropy ceramic powder material prepared by the embodiment, namely, the CuFe 2O4 spectrum line (PDF#25-0283) with a spinel structure and the Fe 2O3 spectrum line (PDF#33-0664) with a corundum structure in an ICDD database.
FIG. 4 is an SEM image of (Cu, ni, co, cr) Fe xOy high entropy ceramic powder material, and the powder particle size is 200-500: 500 nm.
Fig. 5 shows EDS results of (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material, showing that the molar ratio of each metal element in the material conforms to the original composition design, and is a typical high-entropy compound state.
An absorption rate of 0.3-2.5 μm band, a normal infrared emissivity of 2-22 μm band, and a thermal stability test were the same as in example 1.
Taking 0.2 g (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material, and measuring that the normal infrared emissivity of the material is 0.91 in a wave band of 2-22 mu m and the solar absorptivity of the material is 0.883 in a wave band of 0.3-2.5 mu m; after a thermal stability experiment, the material is measured to have the normal infrared emissivity of 0.90 in a wave band of 2-22 mu m and the solar absorptivity of 0.910 in a wave band of 0.3-2.5 mu m.
FIG. 6 is a graph of solar energy absorption spectrum of (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material in a wave band of 0.3-2.5 μm, showing that the material has higher solar energy absorption rate in the wave band.
FIG. 7 shows XRD patterns of (Cu, ni, co, cr) Fe xOy high-entropy ceramic powder material before and after thermal stability test at 1700 ℃. The result shows that the biphase high-entropy material does not generate phase change after the thermal stability test at 1700 ℃, and the biphase high-entropy material has good thermal stability, which benefits from the larger configuration entropy in the high-entropy effect, so that the material forms a stable solid solution structure.
Example 4
The preparation method of the spinel-corundum dual-phase high-entropy ceramic powder material comprises the following steps:
Step 1: the mole ratio of metal atoms is 1:1:1:1:1:10, respectively weighing CuO（0.7955 g）、NiO（0.7469 g）、MnO2（0.8694 g）、CoO（0.7493 g）、Cr2O3（0.7599 g）、Fe3O4（11.5770 g） powder, ball milling by adopting a planetary ball mill, wherein a ball milling solvent is ultrapure water, and the mass ratio (g/g) of ball material water is 2:1:3, ball milling is carried out for 1 hour at the rotating speed of 500 r/min, then 10min is stopped, the ball milling period is taken as one ball milling period, after 10min, ball milling is carried out for 1 hour, and the rotating speed is 500 r/min, and the total ball milling is carried out for 10 hours. And then drying at 80-100 ℃ for 12-24 hours, and grinding to obtain precursor powder.
Step 2: the precursor powder is calcined in stages in an air atmosphere, the temperature is raised to 500 ℃ at 5 ℃/min, and then the temperature is raised at 5 ℃/min, the calcining temperature is 1400 ℃, and the calcining time is 10 hours. Cooling with a furnace after the calcination is finished, and grinding to obtain the biphase (Cu, ni, co, mn, cr) Fe xOy high-entropy ceramic powder material, wherein x is 1< 2, y is 3< 4.
The X-ray diffraction test is carried out on the obtained (Cu, ni, co, mn, cr) Fe xOy high-entropy ceramic powder material, and the result is shown in figure 8, and the spectrum line is shown as a dual-phase coexistence structure of the high-entropy ceramic powder material prepared by the embodiment and a CuFe 2O4 spectrum line (PDF#25-0283) with a spinel structure and a Fe 2O3 spectrum line (PDF#33-0664) with a corundum structure in an ICDD database.
An absorption rate of 0.3-2.5 μm band, a normal infrared emissivity of 2-22 μm band, and a thermal stability test were the same as in example 1.
Taking 0.2 g (Cu, ni, co, mn, cr) Fe xOy high-entropy ceramic powder material, and measuring that the normal infrared emissivity of the material is 0.92 in a wave band of 2-22 mu m and the solar absorptivity of the material is 0.885 in a wave band of 0.3-2.5 mu m; after a thermal stability experiment, the material is measured to have the normal infrared emissivity of 0.91 in a wave band of 2-22 mu m and the solar absorptivity of 0.893 in a wave band of 0.3-2.5 mu m.
In summary, the infrared emissivity of the materials obtained in examples 1 to 4 in the wavelength range of 2 to 22 μm is 0.90 to 0.92, and the solar absorptivity in the wavelength range of 0.3 to 2.5 μm is 0.87 to 0.91. A long-time thermal stability experiment shows that the crystal structure of the material is stable, and the fluctuation of the solar energy absorptivity and the infrared emissivity is only 0.01-0.02. The data show that the high-entropy ceramic powder material prepared by the invention has higher solar absorptivity and infrared emissivity and good thermal stability in air, so that the photo-thermal conversion efficiency of the solar energy absorbing material and the heating/heat dissipation efficiency of the infrared radiation material can be ensured.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (8)
1. A spinel-corundum dual-phase high-entropy ceramic powder material is characterized in that: the chemical formula of the biphase high-entropy ceramic powder material is AFe xOy, wherein A is 4-5 transition metal elements in Cu, ni, co, zn, mg, mn and Cr, and the molar ratio of the elements is 1< x <2,3< y <4; the ceramic is a biphase intergrowth structure ceramic, and has a cubic spinel phase and a trigonal corundum phase crystal structure.
2. The spinel-corundum dual-phase high-entropy ceramic powder material as claimed in claim 1, wherein: the solar energy absorptivity of the biphasic high-entropy ceramic powder material is more than 0.87 within the range of 0.3-2.5 mu m, and the infrared emissivity is more than 0.90 within the range of 2-22 mu m.
3. The spinel-corundum dual-phase high-entropy ceramic powder material as claimed in claim 1, wherein: the average grain size of the biphase high-entropy ceramic powder material is in the range of 200-500 nm.
4. The method for preparing the spinel-corundum dual-phase high-entropy ceramic powder material according to claim 1, which comprises the following steps:
Step 1: the molar ratio of metal elements is 1: 6-10 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is four of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; or the molar ratio of metal elements is 1: 8-12 of AOx powder and Fe 3O4 powder which are used as raw materials, wherein the AOx is five of CuO, niO, coO, znO, mgO, mnO 2、Cr3O4 powder, and the elements are in equimolar ratio; the raw materials are subjected to ball milling, mixing, drying and grinding to obtain precursor powder;
Step 2: the precursor powder is calcined in sections in air atmosphere, cooled and ground to obtain the high-entropy ceramic powder material with spinel and corundum dual-phase coexistence structure.
5. The method for preparing the spinel-perovskite dual-phase high-entropy ceramic powder material according to claim 4, which is characterized by comprising the following steps: the ball milling condition in the step 1 is that a planetary ball mill is adopted for ball milling, the ball milling solvent is ultrapure water, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-10 hours, and the mass ratio of ball material water is 2-5: 1:3.
6. The method for preparing the spinel-perovskite dual-phase high-entropy ceramic powder material according to claim 4, which is characterized by comprising the following steps: the drying condition in the step 1 means that the temperature is 80-100 ℃ and the drying time is 12-24 hours.
7. The method for preparing the spinel-perovskite dual-phase high-entropy ceramic powder material according to claim 4, which is characterized by comprising the following steps: the condition of the sectional calcination in the step 2 is that the temperature is raised to 500 ℃ at 5 ℃/min, then the temperature is raised at 2-5 ℃/min, the calcination temperature is 500-1400 ℃ and the calcination time is 1-10 hours.
8. The method for preparing the spinel-perovskite dual-phase high-entropy ceramic powder material according to claim 4, which is characterized by comprising the following steps: and the cooling mode in the step 2 is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.
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