CN113072374A - Ytterbium-doped lanthanum phosphate ceramic and preparation method thereof - Google Patents
Ytterbium-doped lanthanum phosphate ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to ytterbium-doped lanthanum phosphate ceramic and a preparation method thereof, belonging to the field of preparation and application of inorganic non-metallic materials. The invention is obtained by doping Yb to La site according to the chemical formula La1‑ xYbxPO4Mixing materials, wherein x is more than or equal to 0.05 and less than or equal to 0.2; firstly, preparing mixed metal salt solution, performing complexation, esterification reaction and drying to obtain precursor powder, calcining for 1-6 hours at 1000-1300 ℃ to obtain original powder, performing compression molding on the original powder, and sintering the original powder into blocks at 1400-1600 ℃ to obtain the ytterbium-doped lanthanum phosphate ceramic. The invention has simple preparation process, regular appearance of the ceramic block and good thermophysical performance, and can be used as a candidate material of a thermal barrier coating of an aerospace engineAnd (5) feeding.
Description
Technical Field
The invention relates to ytterbium-doped lanthanum phosphate ceramic and a preparation method thereof, belonging to the field of preparation and application of inorganic non-metallic materials.
Background
Thermal Barrier Coatings (TBCs) are thermal protective coatings consisting of high temperature resistant, highly insulating, corrosion resistant ceramic and metal layers applied to hot end components of gas turbine engines. The most widely used ceramic layer material is 8YSZ (zirconia stabilized with 6-8 wt.% yttria), and the material can generate phase change at 1250 ℃, and the coating becomes brittle and falls off after being sintered, so that the requirement of higher service temperature cannot be met.
In the thermal barrier coating material researched aiming at the high-temperature service environment above 1300 ℃, rare earth phosphate becomes one of the most potential materials with high melting point, good high-temperature phase stability and low thermal conductivity, exists in two forms of a monazite structure Ln PO and a xenotime structure in the natural world, and has the monazite structure Ln PO4(Ln ═ La to Gd) is generally formed with relatively light rare earth ions having a relatively large radius, and the xenotime structure Ln PO4(Ln ═ Tb-Lu, + Y) is generally formed with relatively small radius, relatively heavy rare earth ions, of which lanthanum phosphate has received increasing attention as one of the candidates for TBCs. Although lanthanum phosphate has excellent thermophysical properties (thermal conductivity of 1.30W/(m.K), 80 ℃), the thermal expansion coefficient is lower than that of 8YSZ (10.5 multiplied by 10)-6 K -11000 deg.c) and thus is susceptible to the problem of spalling due to thermal expansion mismatch when it is used as a thermal barrier coating. Wei Pan (European ceramics, 2016) et al study La2Zr2O7And LaPO4The effect of compounding on the coefficient of thermal conductivity, but no study of the coefficient of thermal expansion was involved. The research of Zhijian Peng (materials science and technology, 2019) and the like finds that the high-entropy ceramic (La) is0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4Has low thermal conductivity (room temperature) and thermal expansion coefficient (8.9 × 10) close to that of alumina-6K-1，300～1000℃)。
The existing method for preparing rare earth phosphate ceramics mainly comprises a solid-phase reaction method, a sol-gel method, a coprecipitation method and a hydrothermal synthesis method. The solid phase method is a traditional preparation method with poor synthesis effect and low efficiency, and is mainly solid compound or solid solution powder which is prepared by fully mixing raw materials, grinding, sieving and calcining at high temperature. The sample powder obtained by the solid-phase reaction has the defects of nonuniform microstructure, easy introduction of foreign impurities, segregation of components and the like. The chemical coprecipitation method is a preparation method which comprises the steps of uniformly mixing required metal salt solutions in proportion, mixing the mixed solution with a precipitator through a titration method, and carrying out suction filtration, drying, calcination and other processes on the obtained colloid. The chemical coprecipitation method has the defects of easy agglomeration, low purity, large particle radius, difficult precipitation and suction filtration and the like during washing, filtering and drying. The sol-gel method is to take water as a medium to generate chemical reaction of a high-activity compound to obtain stable sol, to obtain gel through aging treatment, and to obtain usable powder through drying treatment. The method has the advantages of simple preparation process, fine synthesized powder, uniform granularity, easy control of reaction rate and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide ytterbium-doped lanthanum phosphate ceramic which has a monazite and xenotime structure, is regular in microstructure and compact in structure, is obtained by doping Yb to La site, and has the following structural formula: la1-xYbxPO4Wherein x is more than or equal to 0.05 and less than or equal to 0.2; the thermal expansion performance of the doped silicon carbide is improved.
The invention also provides a preparation method of the ytterbium-doped lanthanum phosphate ceramic, which comprises the following steps:
s1, preparing a mixed solution of lanthanum ions, ytterbium ions and phosphate ions, mixing the mixed solution with a complexing agent and a dispersing agent, heating and stirring in a water bath, adding nitric acid to obtain a colorless transparent solution, and further heating and stirring to obtain a sticky gel;
s2, drying the gel to obtain a solid precursor product;
s3, calcining the solid precursor product to obtain ytterbium-doped lanthanum phosphate ceramic powder;
s4, pressing the powder into a ceramic block;
and S5, sintering the ceramic block to obtain the ytterbium-doped lanthanum phosphate ceramic.
Further, in step S1, in the mixed solution, the concentrations of lanthanum ions, ytterbium ions, and phosphate ions are all 0.01 to 0.2mol/L, wherein the molar ratio of lanthanum ions to ytterbium ions is 4: 1-19: 1, and the molar ratio of phosphate ions to metal ions is 1: 1, the sources of the ionic solution are respectively lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate.
Further, in step S1, the complexing agent is citric acid, the dispersing agent is ethylene glycol, and the molar ratio of citric acid to ethylene glycol to metal ions is 1.2: 1.2: 1, the concentration of nitric acid is 14.4mol/L, and the molar ratio of nitric acid to metal ions is 5: 1.
further, in step S1, the complexing agent and the dispersing agent are slowly added into the mixed solution, and the mixture is heated in a water bath at 80 ℃, nitric acid is slowly added under the environment of stirring speed of 300rpm, so as to obtain a colorless transparent solution, and the mixture is continuously heated and stirred at 80 ℃ and 300rpm for 12 hours, so as to obtain an opaque and viscous gel.
Further, in step S2, the gel obtained in step S1 is dried in a drying oven at a temperature of 180 ℃ for 12-24 hours to obtain a solid precursor product.
Further, in step S3, grinding the solid precursor product with an agate mortar, placing the ground solid precursor product into a high-temperature furnace, calcining the solid precursor product at 1000-1300 ℃ for 1-6 hours, and sieving the calcined powder with a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate powder.
Further, in step S4, the ceramic powder is pressed and molded by a tablet press, wherein a mold used for pressing is 7-15 mm in diameter, the application pressure is 40MPa, and the pressure holding time is 60S.
Further, in step S5, sintering the obtained wafer in a high temperature furnace in an air atmosphere at 1400-1600 ℃ for 3-12 hours to obtain the ytterbium-doped lanthanum phosphate ceramic block.
The ytterbium-doped lanthanum phosphate ceramic is prepared by the method, and the ceramic material has the structural formula: la1- xYbxPO4Wherein x is more than or equal to 0.05 and less than or equal to 0.2.
The invention has the advantages that:
1. the ytterbium doped lanthanum phosphate ceramic provided by the invention is of a monazite and xenotime structure, and the measured thermal expansion coefficient of the block can reach 10.871 multiplied by 10 at the highest temperature of 1400 DEG C-6K-1The ytterbium-doped lanthanum phosphate ceramic material obtained by doping ytterbium at a lanthanum position effectively improves the thermophysical properties of the lanthanum phosphate ceramic material, and is suitable for the alternative material of the thermal barrier coating of the aerospace engine.
Drawings
Fig. 1 is a schematic diagram of a preparation method of ytterbium-doped lanthanum phosphate ceramic of the present invention.
Fig. 2 is an X-ray diffraction pattern of the ceramic powder obtained in example 1 in the preparation method of ytterbium-doped lanthanum phosphate ceramic of the present invention.
Fig. 3 is an X-ray diffraction pattern of the ceramic powder obtained in example 2 in the preparation method of ytterbium-doped lanthanum phosphate ceramic of the present invention.
Fig. 4 is an X-ray diffraction pattern of the ceramic powder obtained in example 3 in the method for preparing ytterbium-doped lanthanum phosphate ceramic of the present invention.
Fig. 5 is an X-ray diffraction pattern of the ceramic powder obtained in example 4 in the method for preparing ytterbium-doped lanthanum phosphate ceramic according to the present invention.
Fig. 6 is an SEM image of the ceramic bulk obtained in examples 1, 2, 3, 4 in the method of preparing ytterbium-doped lanthanum phosphate ceramic of the present invention.
Fig. 7 is a graph showing the thermal expansion coefficient of the ceramic blocks obtained in examples 1, 2, 3, and 4 in the method for preparing ytterbium-doped lanthanum phosphate ceramic according to the present invention as a function of temperature.
Fig. 8 is a graph showing the thermal expansion coefficient of the ceramic blocks obtained in examples 1, 2, 3, and 4 in the method for preparing ytterbium-doped lanthanum phosphate ceramic according to the present invention as a function of temperature.
Detailed Description
Example 1:
lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate solution with the concentration of 0.5mol/L are mixed to prepare a mixture with the molar ratio of lanthanum ions, ytterbium ions and phosphate ions of 19: 1: 20, and adding a solution of metal ions in a molar ratio of 1.2: 1, placing a beaker of the mixed solution into a water bath kettle, heating and stirring at 80 ℃ and at the stirring speed of about 300rpm, slowly adding the mixture of the complexing agent citric acid and the dispersing agent ethylene glycol, wherein the molar ratio of the mixture to the metal ions is 5: 1 to obtain a colorless transparent solution, and heating and stirring the solution for 12 hours under the conditions of 80 ℃ and 300rpm to obtain viscous gel. And placing the obtained gel in a drying oven at the temperature of 180 ℃ for drying for 24h to obtain a solid precursor product, grinding the solid precursor product by using an agate mortar, then placing the ground solid precursor product in a high-temperature furnace for calcining at the temperature of 1150 ℃ for 6h, sieving the calcined powder by using a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate ceramic powder, performing compression molding on the obtained powder by using a mold with the diameter of 7mm, wherein the pressure is 40MPa, the pressure maintaining time is 60s, then placing the obtained molded original sheet in the high-temperature furnace for calcining for 12h in the air atmosphere, and the sintering temperature is 1500 ℃ to obtain the ytterbium-doped lanthanum phosphate ceramic block.
XRD test is performed on the ytterbium-doped lanthanum phosphate powder prepared in example 1, SEM test and thermal expansion test are performed on the sintered ceramic block, and it can be analyzed from fig. 2(x is 0.05) that the obtained ceramic powder has a monazite structure, and a xenotime structure is not detected, indicating that ytterbium is completely dissolved in lanthanum phosphate; as can be seen from fig. 6(x ═ 0.05), the ceramic block has regular morphology and dense structure. The thermal expansion rate is calculated by analysis and is shown in fig. 7(x is 0.05), the thermal expansion rate increases along with the rise of the temperature, and the turning point is not changed suddenly, which indicates that the prepared ceramic material has better phase stability. The thermal expansion coefficient (150 ℃ C. to 1400 ℃ C.) is as shown in FIG. 8(x is 0.05)
Shown to be increased to 9.417 × 10-6K-1。
Example 2:
lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate solution with the concentration of 0.5mol/L are mixed to prepare lanthanum ions, ytterbium ions and phosphate ions with the molar ratio of 9: 1: 10, and adding a solution of metal ions in a molar ratio of 1.2: 1, placing a beaker of the mixed solution into a water bath kettle, heating and stirring at 80 ℃ and at the stirring speed of about 300rpm, slowly adding the mixture of the complexing agent citric acid and the dispersing agent ethylene glycol, wherein the molar ratio of the mixture to the metal ions is 5: 1 to obtain a colorless transparent solution, and heating and stirring the solution for 12 hours under the conditions of 80 ℃ and 300rpm to obtain viscous gel. And placing the obtained gel in a drying oven at the temperature of 180 ℃ for drying for 24h to obtain a solid precursor product, grinding the solid precursor product by using an agate mortar, then placing the ground solid precursor product in a high-temperature furnace for calcining at the temperature of 1150 ℃ for 6h, sieving the calcined powder by using a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate ceramic powder, performing compression molding on the obtained powder by using a mold with the diameter of 7mm, wherein the pressure is 40MPa, the pressure maintaining time is 60s, then placing the obtained molded original sheet in the high-temperature furnace for calcining for 12h in the air atmosphere, and the sintering temperature is 1500 ℃ to obtain the ytterbium-doped lanthanum phosphate ceramic block.
The ytterbium-doped lanthanum phosphate powder prepared in example 2 was subjected to XRD testing, and the sintered ceramic block was subjected to SEM testing and thermal expansion testing, and it was analyzed from fig. 3(x ═ 0.1) that the obtained ceramic powder had a monazite structure, and no xenotime structure was detected, while it was found from fig. 6(x ═ 0.1) that the block morphology was regular and the structure was dense, and a small amount of a second phase was generated in addition to the monazite structure, and the phase was a xenotime structure by analysis. The thermal expansion rate is calculated by analysis and is shown in fig. 7(x is 0.1), the thermal expansion rate increases along with the rise of the temperature, and the turning point is not changed suddenly, which indicates that the prepared ceramic material has better phase stability. The thermal expansion coefficient (150 ℃ C. to 1400 ℃ C.) was increased to 9.977X 10 as shown in FIG. 8(x ═ 0.1)-6K-1。
Example 3:
lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate solution with the concentration of 0.5mol/L are mixed to prepare a mixture with the molar ratio of lanthanum ions, ytterbium ions and phosphate ions being 17: 3: 20, and adding a solution of metal ions in a molar ratio of 1.2: 1, placing a beaker of the mixed solution into a water bath kettle, heating and stirring at 80 ℃ and at the stirring speed of about 300rpm, slowly adding the mixture of the complexing agent citric acid and the dispersing agent ethylene glycol, wherein the molar ratio of the mixture to the metal ions is 5: 1 to obtain a colorless transparent solution, and heating and stirring the solution for 12 hours under the conditions of 80 ℃ and 300rpm to obtain viscous gel. And placing the obtained gel in a drying oven at the temperature of 180 ℃ for drying for 24h to obtain a solid precursor product, grinding the solid precursor product by using an agate mortar, then placing the ground solid precursor product in a high-temperature furnace for calcining at the temperature of 1150 ℃ for 6h, sieving the calcined powder by using a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate ceramic powder, performing compression molding on the obtained powder by using a mold with the diameter of 7mm, wherein the pressure is 40MPa, the pressure maintaining time is 60s, then placing the obtained molded original sheet in the high-temperature furnace for calcining for 12h in the air atmosphere, and the sintering temperature is 1500 ℃ to obtain the ytterbium-doped lanthanum phosphate ceramic block.
The ytterbium-doped lanthanum phosphate powder prepared in example 3 was subjected to XRD testing, and the sintered ceramic block was subjected to SEM testing and thermal expansion testing, and it can be analyzed from fig. 4(x ═ 0.15) that the obtained ceramic powder was a monazite structure and a xenotime structure, and from fig. 6(x ═ 0.15) that the block morphology was regular and the structure was dense, the monazite phase grain size was gradually reduced, and the xenotime phase grain size was increased. The thermal expansion rate is calculated by analysis and is shown in fig. 7(x is 0.15), the thermal expansion rate increases along with the rise of the temperature, and the turning point is not changed suddenly, which indicates that the prepared ceramic material has better phase stability. The thermal expansion coefficient (150 ℃ C. to 1400 ℃ C.) was increased to 10.466X 10 as shown in FIG. 8(x ═ 0.15)-6K-1。
Example 4:
lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate solution with the concentration of 0.5mol/L are mixed to prepare a mixture with the molar ratio of lanthanum ions, ytterbium ions and phosphate ions being 4: 1: 5, and adding a solution of metal ions in a molar ratio of 1.2: 1, placing a beaker of the mixed solution into a water bath kettle, heating and stirring at 80 ℃ and at the stirring speed of about 300rpm, slowly adding the mixture of the complexing agent citric acid and the dispersing agent ethylene glycol, wherein the molar ratio of the mixture to the metal ions is 5: 1 to obtain a colorless transparent solution, and heating and stirring the solution for 12 hours under the conditions of 80 ℃ and 300rpm to obtain viscous gel. And placing the obtained gel in a drying oven at the temperature of 180 ℃ for drying for 24h to obtain a solid precursor product, grinding the solid precursor product by using an agate mortar, then placing the ground solid precursor product in a high-temperature furnace for calcining at the temperature of 1150 ℃ for 6h, sieving the calcined powder by using a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate ceramic powder, performing compression molding on the obtained powder by using a mold with the diameter of 7mm, wherein the pressure is 40MPa, the pressure maintaining time is 60s, then placing the obtained molded original sheet in the high-temperature furnace for calcining for 12h in the air atmosphere, and the sintering temperature is 1500 ℃ to obtain the ytterbium-doped lanthanum phosphate ceramic block.
The ytterbium-doped lanthanum phosphate powder prepared in example 4 was subjected to XRD testing, and the sintered ceramic block was subjected to SEM testing and thermal expansion testing, and it can be analyzed from fig. 5(x ═ 0.2) that the obtained ceramic powder was a monazite structure and a xenotime structure, and from fig. 6(x ═ 0.2) that the block morphology was regular, the structure was dense, and the grain size of the xenotime phase was further increased. The thermal expansion rate is calculated by analysis and is shown in fig. 7(x is 0.2), the thermal expansion rate increases along with the rise of the temperature, and the turning point is not changed suddenly, which indicates that the prepared ceramic material has better phase stability. The thermal expansion coefficient (150 ℃ C. to 1400 ℃ C.) was increased to 10.871X 10 as shown in FIG. 8(x ═ 0.2)-6K-1。
Claims (10)
1. The ytterbium-doped lanthanum phosphate ceramic is characterized by being of a monazite and xenotime structure, regular in microstructure and compact in structure, and being obtained by doping Yb to La position, so that the thermal expansion performance of the lanthanum phosphate ceramic is improved, and the structural formula is as follows: la1-xYbxPO4Wherein x is more than or equal to 0.05 and less than or equal to 0.2; the thermal expansion coefficient of the block can reach 10.871 x 10 at 1400 DEG C-6K-1。
2. The ytterbium-doped lanthanum phosphate ceramic of claim 1, wherein x is 0.2.
3. The method of preparing an ytterbium-doped lanthanum phosphate ceramic according to claim 1, comprising the steps of:
s1, preparing a mixed solution of lanthanum ions, ytterbium ions and phosphate ions, mixing the mixed solution with a complexing agent and a dispersing agent, heating and stirring in a water bath, adding nitric acid to obtain a colorless transparent solution, and further heating and stirring to obtain a sticky gel;
s2, drying the gel to obtain a solid precursor product;
s3, calcining the solid precursor product to obtain ytterbium-doped lanthanum phosphate ceramic powder;
s4, pressing the powder into a ceramic block;
and S5, sintering the ceramic block to obtain the ytterbium-doped lanthanum phosphate ceramic.
4. The method of claim 3, wherein in step S1, the concentrations of lanthanum ions, ytterbium ions and phosphate ions in the mixed solution are all 0.01-0.2 mol/L, and the molar ratio of lanthanum ions to ytterbium ions is 4: 1-19: 1, and the molar ratio of phosphate ions to metal ions is 1: 1, the sources of the ionic solution are respectively lanthanum nitrate, ytterbium nitrate and ammonium dihydrogen phosphate.
5. The method of claim 3, wherein in step S1, the complexing agent is citric acid, the dispersing agent is ethylene glycol, and the molar ratio of citric acid to ethylene glycol to metal ions is 1.2: 1.2: 1, the concentration of nitric acid is 14.4mol/L, and the molar ratio of nitric acid to metal ions is 5: 1.
6. the method of claim 3, wherein in step S1, the complexing agent and the dispersant are slowly added to the mixed solution, and the mixed solution is heated in a water bath at 80 ℃ and then nitric acid is slowly added under the stirring speed of 300rpm to obtain a colorless transparent solution, and the mixture is further heated and stirred at 80 ℃ and 300rpm for 12 hours to obtain an opaque viscous gel.
7. The method of claim 3, wherein in step S2, the gel obtained in step S1 is dried in a drying oven at 180 ℃ for 12-24 hours to obtain a solid precursor product.
8. The method for preparing ytterbium-doped lanthanum phosphate ceramic according to claim 3, wherein in step S3, the solid precursor product is ground by an agate mortar, the ground solid precursor product is placed in a high temperature furnace and calcined at 1000-1300 ℃ for 1-6 h, and the calcined powder is sieved by a 200-mesh sieve to obtain ytterbium-doped lanthanum phosphate powder.
9. The method of claim 3, wherein in step S4, the ceramic powder is pressed and molded by a tablet press, wherein the die diameter is 7-15 mm, the application pressure is 40MPa, and the dwell time is 60S.
10. The method of claim 3, wherein in step S5, the wafer is sintered in a high temperature furnace in an atmosphere of air at 1400-1600 ℃ for 3-12 h to obtain the Yb-doped lanthanum phosphate ceramic bulk.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007155548A (en) * | 2005-12-06 | 2007-06-21 | Hitachi Maxell Ltd | Quantitative analysis using infrared phosphor |
| CN101104805A (en) * | 2007-07-19 | 2008-01-16 | 东华大学 | Method for preparing rare-earth doped lanthanum phosphate nano luminous particles |
| CN104650911A (en) * | 2013-11-18 | 2015-05-27 | 海洋王照明科技股份有限公司 | Dysprosium-doped lanthanum ytterbium pentaphosphate up-conversion luminescent material, and preparation method and application thereof |
| CN110386595A (en) * | 2019-08-20 | 2019-10-29 | 淄博星澳新材料研究院有限公司 | High entropy RE phosphate powder and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007155548A (en) * | 2005-12-06 | 2007-06-21 | Hitachi Maxell Ltd | Quantitative analysis using infrared phosphor |
| CN101104805A (en) * | 2007-07-19 | 2008-01-16 | 东华大学 | Method for preparing rare-earth doped lanthanum phosphate nano luminous particles |
| CN104650911A (en) * | 2013-11-18 | 2015-05-27 | 海洋王照明科技股份有限公司 | Dysprosium-doped lanthanum ytterbium pentaphosphate up-conversion luminescent material, and preparation method and application thereof |
| CN110386595A (en) * | 2019-08-20 | 2019-10-29 | 淄博星澳新材料研究院有限公司 | High entropy RE phosphate powder and preparation method thereof |
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