CN116217230B - Preparation method of low-thermal-conductivity wide-mid-infrared band-pass high-entropy nano composite ceramic - Google Patents
Preparation method of low-thermal-conductivity wide-mid-infrared band-pass high-entropy nano composite ceramic Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000003825 pressing Methods 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001513 hot isostatic pressing Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000002490 spark plasma sintering Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract 2
- 229910003015 Lu(NO3)3 Inorganic materials 0.000 abstract 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 abstract 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(III) nitrate Inorganic materials [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 abstract 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 abstract 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 abstract 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 238000005498 polishing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- 229910003443 lutetium oxide Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method of high-entropy nano composite ceramic with low thermal conductivity and wide middle infrared band transmission, which is prepared by combining a wet chemical method with a sintering process, wherein the chemical formula is (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO. The invention takes Y(NO3)3、Gd(NO3)3、Yb(NO3)3、Lu(NO3)3、Mg(NO3)2 as a raw material, the solution is mixed according to the volume ratio of a final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO of 1:1), then powder is obtained by heating, stirring, calcining, ball milling, drying and sieving, and the powder is formed by dry pressing, and finally the high-entropy ceramic is obtained by sintering.
Description
Technical Field
The invention belongs to the technical field of infrared windows, and particularly relates to a preparation method of a low-thermal-conductivity wide-mid-infrared band-transparent high-entropy nano composite ceramic.
Background
The infrared transparent ceramic is one of important components for integrating the functional structure of the unmanned aerial vehicle, the ground-to-air high Mach missile as one of candidates for infrared window materials. As the flying and attacking rates of unmanned aerial vehicles and missiles are continuously accelerated in the future, the service environment of the infrared window material is worse, the front end of the infrared window material can be rubbed with the atmosphere during high-speed flying, and in this case, more stringent requirements are put forward on the optical and mechanical properties of the infrared window material.
The traditional infrared window materials suitable for high-speed aircrafts are single-phase transparent ceramics such as sapphire, alON, mgAl 2O4、MgF2, Y 2O3 and the like, and although the infrared window materials have excellent optical and mechanical properties, the optical and mechanical properties of the infrared window materials are obviously reduced under certain severe conditions, so that the infrared window materials are not suitable for the requirements of future wars. The nano composite ceramic represented by Y 2O3 -MgO solves the defect of single-phase infrared transparent ceramic, and has good application prospect in the field of infrared window materials required by future war. However, there are two disadvantages, firstly, there is a strong absorption peak at 7 μm in the infrared band, resulting in a smaller infrared transmission band; secondly, the thermal conductivity of the system material is too high (the thermal conductivity of the room temperature is more than 15W/m.K), and the infrared transmittance is obviously reduced at high temperature, so that the service performance of the system material is affected. Therefore, development of a nanocomposite infrared transparent ceramic with low thermal conductivity and no absorption at the infrared band of 7 μm is a problem to be solved by those skilled in the art to meet the requirements of future war on infrared window materials.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of nano composite ceramic with low thermal conductivity, wide middle infrared band and high entropy.
In order to simultaneously meet the low thermal conductivity, wide mid-infrared band transmission and economic benefit, the invention synthesizes nano composite powder by a nitrate thermal decomposition method without participation of carbon fuel, and eliminates the absorption of the mid-wave infrared 7 mu m; through the thermodynamic high entropy effect of the high entropy material and the structural lattice distortion, phonon scattering of the material is enhanced, and the thermal conductivity of a material system is reduced. Based on the above, the rare earth high-entropy nano composite ceramic system ((Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO) developed by the invention has the following component design criteria:
(1) The difference in ionic radius between rare earth elements is as small as possible in order to more easily form a single solid solution;
(2) Each single rare earth element has the same sesquioxide structure;
(3) Each rare earth element is not absorbed in the mid-infrared band;
(4) At service temperatures, no phase transition occurs. Although Gd 2O3 has phase change behavior under high temperature or pressure environment, as the intervention of Y, lu and Yb ions, the ionic radius of the Gd 2O3 is smaller than that of Gd ions, the Gd 2O3 crystal form can be stabilized, and the phase change of the Gd 2O3 crystal form can be inhibited.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The composite ceramic is prepared from (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 and MgO nano composite powder serving as raw materials, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO) in the nano composite powder is 1:1.
According to the invention, the preparation method of the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder comprises the following specific steps:
S1: preparing a metal ion nitric acid solution containing Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO 1:1;
s2: heating and stirring the mixture prepared in the step S1 to form colorless transparent viscous solution;
S3: drying the colorless transparent viscous solution obtained in the step S2 to obtain precursor powder, and finally calcining the precursor powder to obtain (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder;
in the step S3, the precursor powder is calcined under the oxygen atmosphere at the temperature of 500 ℃ at the heating rate of 1 ℃/min for 1h, and then the precursor powder is calcined under the air atmosphere at the temperature of 600 ℃ at the heating rate of 5 ℃/min for 2h.
According to the invention, the preparation method of the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder comprises the following specific steps:
Mixing Y 2O3、Gd2O3、Yb2O3、Lu2O3 and MgO as raw materials according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO 1:1 to obtain a mixture;
According to the invention, Y 2O3、Gd2O3、Yb2O3、Lu2O3 and MgO are nano-scale powder, and the purity is more than 99.99%.
According to the invention, the preparation method of the nano composite ceramic with low thermal conductivity, wide middle infrared band and high entropy transmission comprises the following specific steps:
SS1: ball milling is carried out on the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder for 60h, the ball milled slurry is put into a baking oven for drying, and the high-entropy nano composite powder is obtained after sieving treatment;
SS2: dry-pressing the mixed powder prepared in the step SS1 in an axial unidirectional pressurizing mode under the condition of 50-100 MPa for 1-2 min to obtain a molded blank;
SS3: and (3) drying the molded green body obtained in the step (SS 2), heating and sintering, and then annealing to obtain the low-heat-conductivity wide middle-infrared band transparent high-entropy nano composite ceramic.
According to the present invention, in step SS3, hot press sintering, vacuum hot press sintering, spark plasma sintering, and hot isostatic pressing sintering are performed.
According to the hot press sintering process, the applied pressure is 50MPa, the sintering temperature is 1400 ℃, and the heat preservation time is 1h.
In the vacuum hot-pressing sintering process, the applied pressure is 70MPa, the sintering temperature is 1350 ℃, the heat preservation time is 0.5h, and the vacuum degree is 10 -3 Pa.
In the spark plasma sintering process, the applied pressure is 75MPa, the sintering temperature is 1300 ℃, and the heat preservation time is 5min.
In the hot isostatic pressing sintering process, the applied pressure is 200MPa, the sintering temperature is 1250 ℃, and the heat preservation time is 1h.
According to the invention, in step SS3, the annealing atmosphere is one of air or oxygen atmosphere, the temperature is 1000-1250 ℃, and the heat preservation time is 12-36h.
The invention has the beneficial effects that
The average grain size of the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder is smaller than 150nm, the nano composite ceramic has high mid-infrared transmittance and Vickers hardness, and meanwhile, the powder synthesis method without participation of carbon fuel is adopted, so that the absorption at the position of 7 mu m is eliminated, and in addition, phonon scattering of the material is enhanced and the thermal conductivity of a material system is reduced through the thermodynamic high-entropy effect of the high-entropy material and the lattice distortion of the structure.
Drawings
FIG. 1 is an XRD pattern of the high-entropy nanocomposite ceramic obtained in example 1 of the present invention;
FIG. 2 is a BSE image of the high entropy nanocomposite ceramic obtained in example 1 of the present invention;
FIG. 3 is an infrared transmittance spectrum of the high-entropy nanocomposite ceramic obtained in example 1 of the present invention;
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
The invention provides a preparation method of a nano composite ceramic with low thermal conductivity, wide middle infrared band and high entropy, which takes (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high entropy nano composite powder as raw material, and then the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high entropy nano composite ceramic is obtained through sintering and annealing treatment.
The following features and effects of the present invention are described in conjunction with specific embodiments:
Example 1
(1) Preparing a metal ion nitric acid solution with the concentration of 1mol/L Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO of 1:1 to obtain a mixed solution;
(2) Placing the mixed solution in a water bath kettle at 80 ℃, and heating and stirring to obtain colorless transparent viscous solution;
(3) Placing the colorless transparent viscous solution into a baking oven at 120 ℃ for 24 hours, and then placing the dried mixture into a muffle furnace for calcining at 600 ℃ for 4 hours to obtain (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO) is 1:1;
(4) Ball milling is carried out on the high-entropy nano composite powder for 60 hours, the slurry after ball milling is put into an oven at 120 ℃ for 3 hours, and 200-mesh sieving is carried out to obtain the high-entropy nano composite powder;
(5) Dry-pressing the high-entropy nano composite powder in an axial unidirectional pressurizing mode under the condition of 100MPa for 2min to obtain a molded blank;
(6) And (3) placing the formed blank body into a hot pressing furnace, preserving heat for 1h at the temperature of 1400 ℃ at the heating rate of 18 ℃/min, applying pressure of 50MPa during sintering, placing a sample into a muffle furnace for annealing at 1100 ℃ for 12h after sintering, and performing grinding and polishing treatment to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
FIG. 1 is an XRD pattern of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO) high-entropy nanocomposite ceramic prepared in example 1, and as can be seen from FIG. 1, the high-entropy nanocomposite ceramic phase consists of cubic phases Y 2O3 and MgO, and no other impurity phases appear, indicating (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 forms a uniform solid solution).
FIG. 2 is a BSE image of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nanocomposite ceramic) prepared in example 1, and as can be seen from FIG. 2, the high-entropy nanocomposite ceramic has a uniform phase domain distribution and a fine grain size of about 150nm.
FIG. 3 is an infrared transmittance spectrum of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nanocomposite ceramic) prepared in this example 1, and as can be seen from FIG. 3, the high-entropy nanocomposite ceramic has a high transmittance in the range of 3 to 8. Mu.m, up to 84.3% at 5. Mu.m, and no absorption at 7. Mu.m.
Table 1 shows the Vickers hardness, flexural strength and thermal conductivity of the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nanocomposite ceramic) prepared in this example 1, and it can be seen from Table 1 that the thermal conductivity of the high-entropy nanocomposite ceramic is 7.2W/mK, which is much lower than that of Y 2O3 -MgO (> 15W/mK).
TABLE 1 Vickers hardness, flexural Strength and thermal conductivity of the high entropy nanocomposite ceramics prepared in this example 1
| Vickers hardness/GPa | Flexural Strength/MPa | Thermal conductivity/W/mK |
| 13.8±0.2 | 201.6±12.3 | 7.2 |
Example 2
(1) Preparing a metal ion nitric acid solution with the concentration of 1mol/L Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO of 1:1 to obtain a mixed solution;
(2) Placing the mixed solution in a water bath kettle at 90 ℃, and heating and stirring to obtain a colorless transparent viscous solution;
(3) Placing the colorless transparent viscous solution into a 100 ℃ oven for 60h drying treatment, and then placing the dried mixture into a muffle furnace for calcining at 550 ℃ for 6h to obtain (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO) is 1:1;
(4) Ball milling is carried out on the high-entropy nano composite powder for 60 hours, the slurry after ball milling is put into an oven at 120 ℃ for 3 hours, and 200-mesh sieving is carried out to obtain the high-entropy nano composite powder;
(5) Dry-pressing the high-entropy nano composite powder in an axial unidirectional pressurizing mode under the condition of 100MPa for 2min to obtain a molded blank;
(6) And (3) placing the formed blank body into a vacuum hot pressing furnace, preserving heat for 1h at 1350 ℃ at a heating rate of 30 ℃/min, applying pressure of 70MPa during sintering, placing a sample into a muffle furnace for annealing at 1000 ℃ for 24h after sintering, and performing grinding and polishing treatment to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
Example 3
(1) Preparing a metal ion nitric acid solution with the concentration of 2mol/L Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO of 1:1 to obtain a mixed solution;
(2) Placing the mixed solution in a water bath kettle at 95 ℃, and heating and stirring to obtain colorless transparent viscous solution;
(3) Placing the colorless transparent viscous solution into a 110 ℃ oven for 24 hours of drying treatment, and then placing the dried mixture into a muffle furnace for calcining at 600 ℃ for 4 hours to obtain (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO) is 1:1;
(4) Ball milling is carried out on the high-entropy nano composite powder for 60 hours, the slurry after ball milling is put into an oven at 120 ℃ for 3 hours, and 200-mesh sieving is carried out to obtain the high-entropy nano composite powder;
(5) Dry-pressing the high-entropy nano composite powder in an axial unidirectional pressurizing mode under the condition of 100MPa for 1min to obtain a molded blank;
(6) And (3) performing spark plasma sintering on the formed blank, preserving heat for 5min at the temperature of 1300 ℃ at the heating rate of 50 ℃/min, applying the pressure of 75MPa during sintering, and after sintering, placing a sample into a muffle furnace for annealing at the temperature of 1000 ℃ for 12h, and performing grinding and polishing treatment to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
Example 4
(1) Preparing a metal ion nitric acid solution with the concentration of 2mol/L Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO of 1:1 to obtain a mixed solution;
(2) Placing the mixed solution in a water bath kettle at 90 ℃, and heating and stirring to obtain a colorless transparent viscous solution;
(3) Placing the colorless transparent viscous solution into a baking oven at 150 ℃ for 10 hours, and then placing the dried mixture into a muffle furnace for calcining at 600 ℃ for 3 hours to obtain (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO) is 1:1;
(4) Ball milling is carried out on the high-entropy nano composite powder for 60 hours, the slurry after ball milling is put into an oven at 80 ℃ for drying for 10 hours, and 200-mesh sieving is carried out to obtain the high-entropy nano composite powder;
(5) Dry-pressing the high-entropy nano composite powder in an axial unidirectional pressurizing mode under the condition of 100MPa for 1min to obtain a molded blank;
(6) And (3) carrying out hot isostatic pressing sintering on the formed blank, adopting a heating rate of 30 ℃/min, preserving heat for 1h at 1250 ℃, applying pressure of 200MPa during sintering, and carrying out grinding and polishing treatment on the sample after the sintering is finished to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
Example 5
(1) Mixing high-purity Y 2O3、Gd2O3、Yb2O3、Lu2O3 and MgO nano powder serving as raw materials according to a final product (the volume ratio of Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO is 1:1 to obtain mixed powder;
(2) Ball milling is carried out on the mixed powder for 60 hours, the ball milled slurry is put into an oven at 80 ℃ to be dried for 24 hours, and then 200-mesh sieving treatment is carried out, so as to obtain the processed mixed powder;
(3) Dry-pressing the mixed powder under 100MPa in an axial unidirectional pressurizing mode for molding, and maintaining the pressure for 1min to obtain a molded blank;
(4) And (3) carrying out hot isostatic pressing sintering on the formed blank, adopting a heating rate of 30 ℃/min, preserving heat for 1h at 1250 ℃, applying pressure of 200MPa during sintering, and carrying out grinding and polishing treatment on the sample after the sintering is finished to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
Example 6
(1) Mixing high-purity Y 2O3、Gd2O3、Yb2O3、Lu2O3 and MgO nano powder serving as raw materials according to a final product (the volume ratio of Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO is 1:1 to obtain mixed powder;
(2) Ball milling is carried out on the mixed powder for 60 hours, the ball milled slurry is put into an oven at 80 ℃ to be dried for 24 hours, and then 200-mesh sieving treatment is carried out, so as to obtain the processed mixed powder;
(3) Dry-pressing the mixed powder under 100MPa in an axial unidirectional pressurizing mode for molding, and maintaining the pressure for 1min to obtain a molded blank;
(4) And (3) performing spark plasma sintering on the formed blank, preserving heat for 5min at 1300 ℃ by adopting a heating rate of 100 ℃/min, applying pressure of 75MPa during sintering, and performing polishing treatment on the sample after sintering to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite ceramic.
It should be understood that the above description of the specific embodiments of the present invention is only for illustrating the technical route and features of the present invention, and it is intended that those skilled in the art will be able to understand the present invention and implement it accordingly, but the present invention is not limited to the above-described specific embodiments. All changes or modifications that come within the scope of the appended claims are intended to be embraced therein.
Claims (3)
1. A preparation method of low-thermal conductivity wide mid-infrared band transparent high-entropy nano composite ceramic is characterized by comprising the following steps: the composite ceramic is prepared by taking (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 and MgO nano composite powder as raw materials, wherein the volume ratio of (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO in the nano composite powder is 1:1;
the preparation method of the composite ceramic comprises the following steps:
SS1: ball milling is carried out on the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder for 60h, the ball milled slurry is put into a baking oven for drying, and the mixed powder is obtained after sieving treatment;
SS2: dry-pressing the high-entropy nano composite powder synthesized in the step SS1 in an axial unidirectional pressurizing mode under the condition of 50-100 MPa for 1-2 min to obtain a molded blank;
SS3: drying the formed blank obtained in the step SS2, heating to sinter, and then annealing in air or oxygen atmosphere at 1000-1250 ℃ for 12-36h to obtain the low-thermal conductivity wide middle-infrared band transparent high-entropy nano composite ceramic;
The preparation method of the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder comprises the following specific steps:
S1: preparing a metal ion nitric acid solution containing Y 3+、Gd3+、Yb3+、Lu3+、Mg2+, and mixing the five according to the volume ratio of the final product (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 to MgO 1:1;
S2: heating and stirring the mixed solution prepared in the step S1 to form a colorless transparent viscous solution;
S3: and (3) drying the colorless transparent viscous solution obtained in the step (S2) to obtain precursor powder, and finally calcining the precursor powder to obtain the (Y 0.25Gd0.25Yb0.25Lu0.25)2O3 -MgO high-entropy nano composite powder.
2. The method for preparing the nano composite ceramic with low thermal conductivity, wide middle infrared band and high entropy, according to claim 1, is characterized in that:
In the step SS3, the sintering includes hot press sintering, vacuum hot press sintering, spark plasma sintering or hot isostatic pressing sintering.
3. The method for preparing the nano composite ceramic with low thermal conductivity, wide middle infrared band and high entropy transmission according to claim 2, which is characterized in that:
In the hot-pressing sintering process, the applied pressure is 50MPa, the sintering temperature is 1400 ℃, and the heat preservation time is 1h;
in the vacuum hot-pressing sintering process, the applied pressure is 70MPa, the sintering temperature is 1350 ℃, the heat preservation time is 0.5h, and the vacuum degree is 10 -3 Pa;
In the spark plasma sintering process, the applied pressure is 75MPa, the sintering temperature is 1300 ℃, and the heat preservation time is 5min;
in the hot isostatic pressing sintering process, the applied pressure is 200MPa, the sintering temperature is 1250 ℃, and the heat preservation time is 1h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650890A (en) * | 2019-02-28 | 2019-04-19 | 东北大学 | A kind of gadolinium oxide-bitter earth nano composite ceramics and preparation method thereof |
| CN110342907A (en) * | 2019-07-22 | 2019-10-18 | 中国科学院上海光学精密机械研究所 | A kind of Y2O3The preparation method of-MgO Nanocomposite infra-red china |
| EP3670481A1 (en) * | 2018-12-21 | 2020-06-24 | Rolls-Royce Corporation | Thermal and/or environmental barrier coating system |
| CA3106049A1 (en) * | 2018-10-09 | 2020-07-09 | Oerlikon Metco (Us) Inc. | High-entropy oxides for thermal barrier coating (tbc) top coats |
| CN113754422A (en) * | 2020-06-01 | 2021-12-07 | 厦门稀土材料研究所 | Porous high-entropy rare earth ferrite ceramic material and preparation method and application thereof |
| CN114436656A (en) * | 2022-01-29 | 2022-05-06 | 北京工业大学 | High-entropy silicate ceramic with low thermal conductivity and high thermal stability and preparation method and application thereof |
| CN114956820A (en) * | 2022-05-31 | 2022-08-30 | 西北工业大学 | Rare earth composite oxide porous high-entropy ceramic and preparation method and application thereof |
| CN115745607A (en) * | 2021-12-20 | 2023-03-07 | 中国科学院上海光学精密机械研究所 | Infrared transparent ceramic material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220411901A1 (en) * | 2021-06-29 | 2022-12-29 | General Electric Company | Oxide dispersion strengthened refractory based alloy |
-
2023
- 2023-03-15 CN CN202310246625.5A patent/CN116217230B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3106049A1 (en) * | 2018-10-09 | 2020-07-09 | Oerlikon Metco (Us) Inc. | High-entropy oxides for thermal barrier coating (tbc) top coats |
| EP3670481A1 (en) * | 2018-12-21 | 2020-06-24 | Rolls-Royce Corporation | Thermal and/or environmental barrier coating system |
| CN109650890A (en) * | 2019-02-28 | 2019-04-19 | 东北大学 | A kind of gadolinium oxide-bitter earth nano composite ceramics and preparation method thereof |
| CN110342907A (en) * | 2019-07-22 | 2019-10-18 | 中国科学院上海光学精密机械研究所 | A kind of Y2O3The preparation method of-MgO Nanocomposite infra-red china |
| CN113754422A (en) * | 2020-06-01 | 2021-12-07 | 厦门稀土材料研究所 | Porous high-entropy rare earth ferrite ceramic material and preparation method and application thereof |
| CN115745607A (en) * | 2021-12-20 | 2023-03-07 | 中国科学院上海光学精密机械研究所 | Infrared transparent ceramic material and preparation method thereof |
| CN114436656A (en) * | 2022-01-29 | 2022-05-06 | 北京工业大学 | High-entropy silicate ceramic with low thermal conductivity and high thermal stability and preparation method and application thereof |
| CN114956820A (en) * | 2022-05-31 | 2022-08-30 | 西北工业大学 | Rare earth composite oxide porous high-entropy ceramic and preparation method and application thereof |
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