CN113912394A - Zirconium dioxide-based ceramic heat insulation material substituted and doped by multi-element rare earth elements and preparation method thereof - Google Patents
Zirconium dioxide-based ceramic heat insulation material substituted and doped by multi-element rare earth elements and preparation method thereof Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000919 ceramic Substances 0.000 title claims abstract description 62
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012774 insulation material Substances 0.000 title claims description 26
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011810 insulating material Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 35
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 34
- 239000000843 powder Substances 0.000 abstract description 30
- 238000010791 quenching Methods 0.000 abstract description 9
- 230000000171 quenching effect Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000011033 desalting Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 11
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000000329 molecular dynamics simulation Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000012720 thermal barrier coating Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical group 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention provides a zirconium dioxide-based ceramic heat-insulating material substituted and doped by multiple rare earth elements and a preparation method thereof, compared with the traditional YSZ, the zirconium dioxide-based ceramic heat-insulating material has better high-temperature service performance and lower heat conductivity. The invention weighs nanometer Gd according to the stoichiometric ratio2O3、Sc2O3、Y2O3、ZrO2Mixing the powder, taking absolute ethyl alcohol as a solvent, carrying out wet ball milling treatment for a certain time to form a suspension of the mixed oxide, spraying the suspension into a container filled with water by using low-temperature plasma equipment, standing, drying and grinding to obtain the required doped zirconia powder. The preparation of the material adopts the technical route of preparing original oxide suspension, namely low-temperature plasma fast burning and collecting in water fast quenching, does not need further desalting treatment, and has the advantages of simple process, controllable operation and little environmental pollution.
Description
Technical Field
The invention relates to the field of thermal protection of turbine blades of aero-engines, in particular to a zirconium dioxide-based ceramic thermal insulation material substituted and doped by multiple rare earth elements and a preparation method thereof.
Background
High-temperature materials, air film cooling and thermal barrier coatings are three key core technologies of an aeroengine. With the development of the aero-engine towards the direction of large thrust-weight ratio and high fuel efficiency, the forward inlet air temperature of the turbine is greatly increased, the improvement potential of high-temperature materials and an air film cooling technology is very limited, and the thermal barrier coating is the internationally accepted measure which is most feasible for increasing the forward inlet temperature of the turbine of the engine at present. The yttria partially stabilized zirconia (YSZ) material is widely applied to engine hot end components due to the advantages of low thermal conductivity, high mechanical strength and the like, but the yttria partially stabilized zirconia (YSZ) material has poor high-temperature phase stability, and can generate the transformation from a tetragonal phase to a monoclinic phase when being in service for a long time at 1200 ℃, so that the spalling failure of the yttria partially stabilized zirconia (YSZ) material is caused by the volume expansion of a coating. In addition, the YSZ material has poor sintering resistance, and the densification of the coating occurs during high-temperature sintering, so that the porosity and the number of microcracks of the coating are reduced, the thermal conductivity is increased, and the thermal insulation performance is reduced, so that the YSZ material cannot meet the requirement of further increasing the turbine inlet temperature. Therefore, the design and development of the novel thermal barrier coating material have great significance for improving the level of national aeroengines.
Disclosure of Invention
The invention aims to provide a zirconium dioxide-based ceramic heat-insulating material substituted and doped by multiple rare earth elements and a preparation method thereof. In addition, the preparation of the material adopts the technical route of preparing the original oxide suspension, namely quickly burning the low-temperature plasma and quickly quenching and collecting in water, does not need further desalting treatment, and has the advantages of simple operation, controllable process and small environmental pollution.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a zirconium dioxide-based ceramic heat-insulating material substituted and doped by multiple rare earth elements is composed of xGd2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3)；3mol％≤x≤4mol％，1mol≤y≤2mol％。
Further, the ceramic heat-insulating material has a composition of 3.0 mol% Gd2O3-1.0mol％Sc2O3-95.0mol％ZrO2-1.0mol％Y2O3。
Further, the ceramic heat-insulating material has a composition of 3.0 mol% Gd2O3-2.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
Further, the ceramic heat-insulating material has a composition of 4.0 mol% Gd2O3-1.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
Furthermore, the granularity of the zirconium dioxide-based ceramic heat-insulating material substituted and doped by the multi-element rare earth elements is 0.2-2 mu m.
A preparation method of a zirconium dioxide-based ceramic heat insulating material substituted and doped by multiple rare earth elements comprises the following steps:
using absolute ethyl alcohol as solvent, according to stoichiometric ratio xGd2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3) (ii) a X is more than or equal to 3 mol% and less than or equal to 4 mol%, y is more than or equal to 1 mol% and less than or equal to 2 mol%, and Gd is added2O3、Sc2O3、Y2O3And ZrO2And performing wet ball milling on the mixture to obtain a suspension, treating the suspension by using low-temperature plasma equipment to atomize, crush, evaporate and sinter the suspension, transferring the suspension into a container filled with deionized water, standing, drying and grinding to obtain the multi-rare earth element substituted and doped zirconium dioxide-based ceramic heat-insulating material.
Further, Gd2O3、Sc2O3、Y2O3And ZrO2The particle diameters of the particles are all 20-40 nm.
Further, the solid content of the suspension is 30-60%.
Furthermore, the ball milling time is 24-48 h.
Further, the voltage of the low-temperature plasma device is 80-100V, and the current is 300-350A.
Compared with the prior art, the invention has the following beneficial effects:
the preparation of the material adopts the technical route of preparing the original oxide suspension, quickly burning the low-temperature plasma and quickly quenching and collecting in water, does not need further desalting, and has simple process and little environmental pollution. The prepared material is a single tetragonal phase structure with uniform components, is different from a cubic phase structure, and the zirconium oxide with the tetragonal phase structure has higher fracture toughness due to a phase change toughening mechanism and an iron elastic domain transition toughening mechanism, so that the thermal cycle performance of the material can be obviously improved. In the preparation of the coating, Gd is present2O3The doping can inhibit the grain growth of the powder in the high-temperature annealing process, is beneficial to improving the anti-sintering performance of the material, and can inhibit the densification of the coating in the preparation process of the coating, so that the coating can keep a microporous structure at high temperature for a long time, thereby enhancing the heat insulation performance of the coating. Based on the open source platform LAMMPS, the multi-element rare earth substituted and doped zirconium dioxide-based ceramic thermal insulation material prepared by the method is predicted by utilizing molecular dynamics simulation, so that the thermal conductivity can be further reduced, a higher thermal expansion coefficient is kept, and the multi-element rare earth substituted and doped zirconium dioxide-based ceramic thermal insulation material has more excellent high-temperature service performance compared with the traditional YSZ material. The multi-element rare earth element (Gd-Sc-Y) replaces the doped ZrO2The preparation method of the base ceramic heat insulation material is simple and easy to operate, low in cost and strong in reliability.
Drawings
FIG. 1 is an XRD pattern of a multi-element rare earth element-substituted doped zirconium dioxide-based ceramic thermal insulation material prepared in example 1 of the present invention and heat-treated at 1500 ℃ for 10 hours.
Fig. 2 is a graph of thermal conductivity of example 1 compared to a conventional YSZ material predicted using molecular dynamics simulations based on the open source platform LAMMPS.
Fig. 3 is a graph of the thermal expansion coefficient of example 1 compared to a conventional YSZ material predicted by molecular dynamics simulation based on the open source platform LAMMPS.
Detailed Description
The present invention will now be described in further detail with reference to specific embodiments and drawings, which are provided for purposes of illustration and not for limitation.
Among the rare earth elements, 6 to 8 wt% (3.5 to 4.5 mol%) of Y2O3Partially stabilized ZrO2(YSZ) is the most mature ceramic material for thermal barrier coatings; sc and Y belong to the same group, have similar chemical properties, do not cause large structural mutation after doping, and are more favorable for stabilizing tetragonal-phase ZrO compared with other stabilizers2(ii) a The thermal conductivity of the material is proportional to the lattice vibration frequency at RE2O3(RE ═ Ce, Gd, Nd, Yb) doped ZrO2In the middle, the Gd-O bond population is the smallest, indicating that Gd2O3Can reduce ZrO more remarkably2Thermal conductivity.
In accordance with one aspect of the present invention, a series of multi-rare earth element substituted doped zirconia-based ceramic thermal insulation materials having a composition of xGd is provided2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3). X is more than or equal to 3 mol% and less than or equal to 4 mol%, and y is more than or equal to 1mol and less than or equal to 2 mol%. Namely, the ceramic heat insulating material is gadolinium, scandium and yttrium co-doped zirconia powder, and the powder comprises Gd2O3、Sc2O3、Y2O3And ZrO2Wherein, Gd2O3The content is as follows: 3.0-4.0 mol.%; sc (Sc)2O3The content is as follows: 1.0-2.0 mol.%; y is2O3The content is as follows: 1.0 mol.% of the balance ZrO2. Since the trivalent oxide is in ZrO2The amount of the ZrO added is strictly controlled because the solid solubility is reduced with the increase of the temperature or the increase of the thermal cycle time, and when the total addition is higher than the range of the invention, the ZrO addition is difficult to control2The crystal phase cannot maintain a single tetragonal phase structure.
Preferably, the multi-rare earth element substituted and doped zirconium dioxide-based ceramic heat insulating material has the composition of 3.0 mol% Gd2O3-1.0mol％Sc2O3-95.0mol％ZrO2-1.0mol％Y2O3. When x and y are not values in the present invention, the crystal phase is not a tetragonal phase.
Preferably, the multi-rare earth element substituted and doped zirconium dioxide-based ceramic heat insulating material has the composition of 3.0 mol% Gd2O3-2.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
Preferably, the multi-rare earth element substituted and doped zirconium dioxide-based ceramic heat insulating material has the composition of 4.0 mol% Gd2O3-1.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
The use of rare earth ions (Gd)3+、Sc3+、Y3+) Para ZrO2Middle part of Zr4+The random substitution is carried out to complete the doping, so that the material has better high-temperature thermophysical properties and tetragonal phase stability compared with the traditional YSZ material.
The ceramic heat-insulating material does not generate monoclinic phase after being subjected to heat treatment at 1500 ℃ for 10 hours, and still keeps a single tetragonal phase structure.
Based on the open source platform LAMMPS, the thermal conductivity of the ceramic thermal insulation material can be predicted to be 15-20% lower than that of the traditional YSZ material by utilizing molecular dynamics simulation.
Based on the open source platform LAMMPS, the thermal expansion coefficient of the ceramic heat-insulating material is predicted to be equivalent to that of the traditional YSZ material by utilizing molecular dynamics simulation, and the ceramic heat-insulating material has good thermal matching property with the bonding layer as a ceramic layer material, so that the service performance and the service life at high temperature are ensured.
The invention also provides a preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements, which adopts a route of preparing original oxide suspension liquid, namely low-temperature plasma fast burning and collecting in water fast quenching, and specifically comprises the following steps:
1) using absolute ethyl alcohol as solvent, according to stoichiometric ratio xGd2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3)；3X is more than or equal to mol% and less than or equal to 4 mol%, y is more than or equal to 1mol and less than or equal to 2 mol%, weighing Gd2O3、Sc2O3、Y2O3And ZrO2Ball-milling the mixed oxide for 24-48h by a wet method to obtain white suspension of the mixed oxide;
2) and conveying the suspension to the flame center of low-temperature plasma jet by using low-temperature plasma equipment, atomizing, crushing, evaporating solvent, quickly sintering, spraying into a container filled with water to finish water quenching, standing, drying and grinding to obtain the zirconium dioxide-based ceramic heat-insulating material substituted and doped by the multi-element rare earth elements. Wherein, the voltage of the low-temperature plasma equipment is 80-100V, and the current is 300-350A.
Example 1
Preparing zirconium dioxide based ceramic heat insulating material substituted and doped by multi-element rare earth element by adopting original oxide suspension liquid, namely low-temperature plasma fast burning and water fast quenching collection, wherein the material composition is 4.0 mol% Gd2O3-1.0mol％Sc2O3-1.0mol％Y2O3-94.0mol％ZrO2Abbreviated as 8Gd2Sc2 YSZ.
The preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements comprises the following steps:
1) calculating the required oxide Gd according to the doping amount2O3、Sc2O3、Y2O3And ZrO2Respectively 0.361088g, 0.067794g, 0.076602g and 3.02915g (Gd)2O3、Sc2O3、Y2O3And ZrO2In a molar ratio of 4:1:1: 94). Weighing Gd2O3、Sc2O3、Y2O3And ZrO2Mixing and placing the mixture into a zirconia ball milling tank, then adding a certain amount of absolute ethyl alcohol to ensure that the solid content is 60%, and carrying out wet ball milling on the mixture for 48 hours to obtain a suspension of mixed oxide.
2) The suspension of the mixed oxide is conveyed to the flame center of low-temperature plasma jet of low-temperature plasma equipment with the voltage of 100V and the current of 350A through a peristaltic pump, so that the flame center is atomized, crushed, evaporated and sintered, and then the suspension is sprayed into a container filled with deionized water and stands for 12 hours to obtain powder.
3) Drying the powder at 110 ℃, and grinding the powder to obtain powder with the particle size of 0.2-2 mu m, namely the powder of the ZrO substituted and doped by the multiple rare earth element (Gd-Sc-Y)2A ceramic based thermal insulation material.
FIG. 1 is a schematic representation of the multiple rare earth element (Gd-Sc-Y) substituted doped ZrO prepared in example 12A base ceramic thermal insulation material and an XRD pattern thereof after being insulated for 10 hours at 1500 ℃. It can be found that no monoclinic phase peak is found after the heat treatment, i.e. high-temperature phase transformation is not generated, which indicates that the material still keeps a single tetragonal phase under the high-temperature condition and has excellent high-temperature phase structure stability.
Fig. 2 is a graph of thermal conductivity of example 1 and conventional YSZ materials predicted by molecular dynamics simulation based on open source platform LAMMPS, with the thermal conductivity decreasing with increasing temperature. The thermal conductivity of the ceramic thermal insulation material is predicted to be about 20% lower than that of the traditional YSZ material at 400-1600K.
Fig. 3 is a graph of thermal expansion coefficients of example 1 and conventional YSZ materials predicted by molecular dynamics simulation based on open source platform LAMMPS. The two thermal expansion coefficients are similar to each other, and the thermal expansion coefficient of example 1 rises faster at low temperature and gradually becomes stable (10.3-10.6 × 10) after reaching 800K-6K-1)。
Example 2
Preparing zirconium dioxide based ceramic heat insulating material substituted and doped by multi-element rare earth element by adopting original oxide suspension liquid, namely low-temperature plasma fast burning and water fast quenching collection, wherein the material composition is 3.0 mol% Gd2O3-2.0mol％Sc2O3-1.0mol％Y2O3-94.0mol％ZrO2Abbreviated as 6Gd4Sc2 YSZ.
The preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements comprises the following steps:
1) calculating the required oxide Gd according to the doping molar quantity2O3、Sc2O3、Y2O3And ZrO2The mass of (b) is 0.270816g, 0.135588g, 0.076602g and 3.02915g (Gd)2O3、Sc2O3、Y2O3And ZrO2In a molar ratio of 3: 2: 1: 94). Weighing Gd2O3、Sc2O3、Y2O3And ZrO2Mixing and placing the mixture into a zirconia ball milling tank, then adding a certain amount of absolute ethyl alcohol to ensure that the solid content is 50%, and carrying out wet ball milling on the mixture for 36 hours to obtain a suspension of the mixed oxide.
2) The suspension of the mixed oxide is conveyed to the flame center of low-temperature plasma jet of low-temperature plasma equipment with the voltage of 90V and the current of 320A through a peristaltic pump, so that the flame center is atomized, crushed, evaporated and sintered, and then the suspension is sprayed into a container filled with deionized water and stands for 12 hours to obtain powder.
3) Drying the powder at 110 ℃, and grinding the powder to obtain powder with the particle size of 0.2-2 mu m, namely the powder of the ZrO substituted and doped by the multiple rare earth element (Gd-Sc-Y)2A ceramic based thermal insulation material.
Example 2 preparation of a multinary rare earth element (Gd-Sc-Y) substituted doped ZrO2The base ceramic heat-insulating material does not have a monoclinic phase peak after being subjected to heat preservation at 1500 ℃ for 10 hours, namely, high-temperature phase change is not generated, which shows that the material still keeps a single tetragonal phase under the high-temperature condition and has excellent high-temperature phase stability.
Based on the open source platform LAMMPS, the trend of the thermal conductivity and the thermal expansion coefficient of the embodiment 2 along with the temperature change is predicted by utilizing molecular dynamics simulation, compared with the traditional YSZ material, the thermal conductivity (3.66-4.59W/mK, 400-1600K) can be reduced by about 18 percent, the thermal expansion coefficient is similar, the thermal conductivity rises faster at low temperature and then gradually increases slowly, and gradually becomes stable (10.2-10.5 multiplied by 10) after reaching 800K-6K-1)。
Example 3
Preparing zirconium dioxide based ceramic heat insulating material substituted and doped by multi-element rare earth element by adopting original oxide suspension liquid, namely low-temperature plasma fast burning and water fast quenching collection, wherein the material composition is 3.0 mol% Gd2O3-1.0mol％Sc2O3-1.0mol％Y2O3-95.0mol％ZrO2Abbreviated as 6Gd2Sc2 YSZ.
The preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements comprises the following steps:
1) calculating the required oxide Gd according to the doping amount2O3、Sc2O3、Y2O3And ZrO2The mass of (b) is 0.270816g, 0.067794g, 0.076602g and 3.06138g (Gd)2O3、Sc2O3、Y2O3And ZrO2In a molar ratio of 3: 1:1: 95, weighing Gd2O3、Sc2O3、Y2O3And ZrO2Mixing and placing the mixture into a zirconia ball milling tank, then adding a certain amount of absolute ethyl alcohol to ensure that the solid content is 40%, and carrying out wet ball milling on the mixture for 24 hours to obtain a suspension of mixed oxide.
2) The suspension of the mixed oxide is conveyed to the flame center of low-temperature plasma jet of low-temperature plasma equipment with the voltage of 80V and the current of 320A through a peristaltic pump, so that the flame center is atomized, crushed, evaporated and sintered, and then the suspension is sprayed into a container filled with deionized water and stands for 12 hours to obtain powder.
3) Drying the powder at 110 ℃, and grinding the powder to obtain powder with the particle size of 0.2-2 mu m, namely the powder of the ZrO substituted and doped by the multiple rare earth element (Gd-Sc-Y)2A ceramic based thermal insulation material.
Example 3 preparation of a multinary rare earth element (Gd-Sc-Y) substituted doped ZrO2The base ceramic heat-insulating material does not have a monoclinic phase peak after being subjected to heat preservation at 1500 ℃ for 10 hours, namely, high-temperature phase change is not generated, which shows that the material still keeps a single tetragonal phase under the high-temperature condition and has excellent high-temperature phase stability.
Based on the open source platform LAMMPS, the trend of the thermal conductivity and the thermal expansion coefficient of the embodiment 3 along with the temperature change is predicted by utilizing molecular dynamics simulation, compared with the traditional YSZ material, the thermal conductivity (3.75-4.72W/mK, 400-1600K) can be reduced by about 15 percent, and the thermal expansion coefficients are opposite to each otherIn the near, the temperature rises faster at low temperature and then gradually increases slowly, and gradually becomes stable (10.2-10.4 multiplied by 10) after reaching 800K-6K-1)。
Example 4
The preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements comprises the following steps:
1) calculating the required oxide Gd according to the doping amount2O3、Sc2O3、Y2O3And ZrO2The mass of (b) is 0.361088g, 0.135588g, 0.076602g and 2.98692g (Gd)2O3、Sc2O3、Y2O3And ZrO2In a molar ratio of 4: 2: 1: 93). Weighing Gd2O3、Sc2O3、Y2O3And ZrO2Mixing and placing the mixture into a zirconia ball milling tank, then adding a certain amount of absolute ethyl alcohol to ensure that the solid content is 30%, and carrying out wet ball milling on the mixture for 24 hours to obtain a suspension of mixed oxide.
2) The suspension of the mixed oxide is conveyed to the flame center of low-temperature plasma jet of low-temperature plasma equipment with the voltage of 90V and the current of 300A through a peristaltic pump, so that the flame center is atomized, crushed, evaporated and sintered, and simultaneously sprayed into a container filled with deionized water, and the mixture is kept stand for 12 hours to obtain powder.
3) Drying the powder at 110 ℃, and grinding the powder to obtain powder with the particle size of 0.2-2 mu m, namely the powder of the ZrO substituted and doped by the multiple rare earth element (Gd-Sc-Y)2A ceramic based thermal insulation material.
Example 5
The preparation method of the zirconium dioxide-based ceramic heat insulating material substituted and doped by the multi-element rare earth elements comprises the following steps:
1) calculating the required oxide Gd according to the doping amount2O3、Sc2O3、Y2O3And ZrO2The mass of (b) is 0.361088g, 0.135588g, 0.076602g and 2.98692g (Gd)2O3、Sc2O3、Y2O3And ZrO2In a molar ratio of 4:2: 1: 93). Weighing Gd2O3、Sc2O3、Y2O3And ZrO2Mixing and placing the mixture into a zirconia ball milling tank, then adding a certain amount of absolute ethyl alcohol to ensure that the solid content is 60%, and carrying out wet ball milling on the mixture for 48 hours to obtain a suspension of mixed oxide.
2) The suspension of the mixed oxide is conveyed to the flame center of low-temperature plasma jet with the voltage of 100V and the current of 310A through a peristaltic pump to be atomized, crushed, evaporated and sintered, and then is sprayed into a container filled with deionized water and stands for 12 hours to obtain powder.
3) Drying the powder at 110 ℃, and grinding the powder to obtain powder with the particle size of 0.2-2 mu m, namely the powder of the ZrO substituted and doped by the multiple rare earth element (Gd-Sc-Y)2A ceramic based thermal insulation material.
The invention utilizes rare earth ions to jointly substitute ZrO2Zr in (1)4+And completing doping, and preparing by a method combining original oxide suspension preparation-low-temperature plasma fast burning and water fast quenching collection. The ceramic thermal insulation material prepared by the invention is a single tetragonal phase structure with uniform components, and has lower thermal conductivity and better high-temperature phase stability than the yttrium oxide partially-stabilized zirconium dioxide (YSZ) coating which is widely applied at present. The ceramic thermal insulation material provided by the invention is applied to a thermal barrier coating, so that the working efficiency and the service life of high-end equipment metal hot end components such as an aircraft engine and a heavy-duty gas turbine can be greatly improved.
The above description is only exemplary of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes and modifications made within the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. The zirconium dioxide-based ceramic heat-insulating material substituted and doped by the multi-element rare earth elements is characterized by consisting of xGd2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3)；3mol％≤x≤4mol％，1mol≤y≤2mol％。
2. The multi-rare earth element substituted doped zirconia-based ceramic thermal insulation material of claim 1, wherein the ceramic thermal insulation material has a composition of 3.0 mol% Gd2O3-1.0mol％Sc2O3-95.0mol％ZrO2-1.0mol％Y2O3。
3. The multi-rare earth element substituted doped zirconia-based ceramic thermal insulation material of claim 1, wherein the ceramic thermal insulation material has a composition of 3.0 mol% Gd2O3-2.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
4. The multi-rare earth element substituted doped zirconia-based ceramic thermal insulation material of claim 1, wherein the ceramic thermal insulation material has a composition of 4.0 mol% Gd2O3-1.0mol％Sc2O3-94.0mol％ZrO2-1.0mol％Y2O3。
5. The multi-rare-earth-element-substituted-doped zirconium dioxide-based ceramic heat-insulating material according to claim 1, wherein the particle size of the multi-rare-earth-element-substituted-doped zirconium dioxide-based ceramic heat-insulating material is 0.2 to 2 μm.
6. A preparation method of a zirconium dioxide-based ceramic heat insulating material substituted and doped by multiple rare earth elements is characterized by comprising the following steps:
using absolute ethyl alcohol as solvent, according to stoichiometric ratio xGd2O3-ySc2O3-(1-x-y)(ZrO2-1mol％Y2O3) (ii) a X is more than or equal to 3 mol% and less than or equal to 4 mol%, y is more than or equal to 1 mol% and less than or equal to 2 mol%, and Gd is added2O3、Sc2O3、Y2O3And ZrO2And performing wet ball milling on the mixture to obtain a suspension, treating the suspension by using low-temperature plasma equipment to atomize, crush, evaporate and sinter the suspension, transferring the suspension into a container filled with deionized water, standing, drying and grinding to obtain the multi-rare earth element substituted and doped zirconium dioxide-based ceramic heat-insulating material.
7. The method of claim 6, wherein Gd is added to the zirconia-based ceramic thermal insulation material2O3、Sc2O3、Y2O3And ZrO2The particle diameters of the particles are all 20-40 nm.
8. The method of claim 6, wherein the suspension has a solid content of 30-60%.
9. The method for preparing zirconium dioxide-based ceramic heat insulating material substituted and doped with multiple rare earth elements according to claim 6, wherein the ball milling time is 24-48 h.
10. The method for preparing the zirconium dioxide-based ceramic thermal insulation material substituted and doped by multiple rare earth elements as claimed in claim 6, wherein the voltage of the low temperature plasma device is 80-100V, and the current is 300-350A.
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