CN102992764A - Rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material and preparation method thereof - Google Patents

Rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material and preparation method thereof Download PDF

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CN102992764A
CN102992764A CN2012103346229A CN201210334622A CN102992764A CN 102992764 A CN102992764 A CN 102992764A CN 2012103346229 A CN2012103346229 A CN 2012103346229A CN 201210334622 A CN201210334622 A CN 201210334622A CN 102992764 A CN102992764 A CN 102992764A
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barrier coating
ceramic material
thermal
ball
earth modified
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张红松
陈晓鸽
杨树森
张政
李斌
李刚
李振军
耿向前
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Henan Institute of Engineering
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Henan Institute of Engineering
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Abstract

The invention discloses a rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material. The chemical formula of the rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material is (Sm[1-x]Lnx)2Ce2O7, wherein Ln is La, Gd, Nd, Er, Dy or Yb, and x is more than 0 and less than 1. Compared with the partial stabilized zirconia containing 7-8% of yttrium oxide, the ceramic material for the (Sm[1-x]Lnx)2Ce2O7 series thermal barrier coating has the advantages that the thermal conductivity is lower and the heat expansion coefficient is higher under the high temperature; under the high temperature (800-1000 DEG C), the thermal conductivity of the two types of materials is about 1.2-1.6W/m.K, the thermal expansion coefficient (1000DEG C) is about 11.4-13.9 multiplied by 10-6/K, and the rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material has the complete potential for being used as a novel thermal-barrier coating ceramic material. The rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material has the advantages that the preparation process is simple, the cost is low, the product can not generate phase change under high temperature, the thermal conductivity is low and the thermal expansion coefficient is high.

Description

Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material and preparation method thereof
Technical field
The present invention mainly relates to trivalent rare earth element Sm 2Ce 2O 7Carry out the thermal barrier coating stupalith that mixes in the A position, the trivalent rare earth element that is used for the doping of A position comprises La,, Nd, Gd, Dy, Er and Yb, its doping all can between 0-1mol.
Technical background
In advanced aero-turbine, the key metallic components such as the engine blade of working under the high temperature for protection, combustion chamber also improves fuel economy, need to prepare ceramic coating above the key metallic components at these, and this layer ceramic coating just is called thermal barrier coating.Typical thermal barrier coating mainly comprises three parts, outside in is followed successively by ceramic layer on surface, metal bonding coating and metallic matrix.Wherein ceramic layer on surface mainly plays heat-blocking action, and the metal bonding coating major function is that alleviation ceramic layer on surface and metallic matrix do not mate the thermal stresses that produces because of thermal expansion, can also protect metallic matrix not oxidized simultaneously.At present, the preparation method of thermal barrier coating mainly contains plasma spraying method and electro beam physics vapour deposition technology, any preparation method no matter, and thermal barrier coating wants better to bring into play its heat-blocking action, must firmly be attached on the metallic matrix.In existing thermal barrier coating, because yttrium oxide PSZ (Y 2O 3Stabilized zirconia is called for short YSZ) pottery has lower thermal conductivity (on average being about 2.3W/m.K), higher thermal expansivity (9 * 10 -6/ ℃) and good high-temperature-phase stability (＜1200 ℃), and become the most widely used thermal barrier coating of active service.
Yet, along with aircraft engine to high flow capacity ratio, high thrust-weight ratio, high turbine intake temperature future development, the working temperature of the crucial hot-end component in its combustion chamber will be above 1500 ℃.Under such high temperature, the YSZ thermal barrier coating of active service, because its top layer stupalith YSZ at high temperature can occur to change mutually, and sintering shrinkage seriously waits series of problems, the heat-proof quality of coating is descended, and the also sharply reduction of the working life of coating, this type coating has been difficult to satisfy the needs of aero engine technology development.For this reason, must manage to overcome this defective of active service YSZ thermal barrier coating.That generally acknowledges at present on this question, has three kinds of approach: (1) adopts technique for cooling blades, such as the geometrical shape of ingehious design hollow blade or the cold air film design of blade etc.; (2) superalloy of employing vacuum melting and precision casting technology development of new is such as directional freeze and single crystal blade; (3) thermal barrier coating ceramic material of development of new.With regard to (1), along with the improvement of blade design and manufacturing technology, the benefit rate of rise that people obtain descends, and it is degree centigrade exceedingly difficult to want at present to make the engine blade working temperature improve hundreds of by the design of single cooling structure again; And for high temperature alloy, should have high strength to satisfy the requirement of allowable design stress, possess again higher chemical stability (being high temperature oxidation resisting, corrosion resistance) in long-term running, the requirement of this two aspect is difficult to reach simultaneously.Best approach is under the prerequisite that adopts advanced cooling technology and exploitation superalloy, and the thermal barrier coating ceramic material of development of new is to substitute the YSZ pottery.
Novel thermal barrier coating need satisfy following some major requirement with stupalith: (1) lower thermal conductivity (＜2.0W/m.K); (2) higher thermal expansivity (〉 9 * 10 -6/ ℃); (3) good high temperature is thought 1200 ℃ of stabilities (〉).At present, the novel thermal barrier coating ceramic material of having reported mainly contains three classes, the ZrO of rare earth doping 2Base ceramic material, Equations of The Second Kind are that chemical formula is Ln 2Zr 2O 7The rare earth zirconate of (Ln represents trivalent rare earth element); The 3rd class is other new ceramics of reporting among the nearly 3-5, mainly contains Nd 2Ce 2O 7, La 2Ce 2O 7, rare earth modified Ba 1-xLn xNd 2(Ti 1-yLn y) 3O 10The class pottery, barium lanthanum titanium Ba 1-xLn xSm 2(Ti 1-yLn y) 3O 10, barium neodymium titanium Ba 1-xLn xNd 2(Ti 1-yLn y) 3O 10, Lanthanum Chromite La 2.0～3.0Cr 2.0～2.5O 6.0～7.5, and InFeZnO 4Deng, but the Sm that domestic relevant trivalent rare earth element is mixed 2Ce 2O 7It is blank that the research of stupalith still belongs to.
Summary of the invention
The present invention will solve, and technical problem provides a kind of have higher thermal expansivity and lower thermal conductivity.Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material and preparation method thereof.
Technical scheme of the present invention is: rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 1-xLn x) 2Ce 2O 7, wherein Ln is La, Gd, Nd, Er, Dy or Yb, 0＜x＜1.
Described rare earth modified Sm 2Ce 2O 7The preparation method of thermal barrier coating ceramic material, its step is as follows:
(1) takes by weighing 1-x mole Sm 2O 3, x mole Ln 2O 3, 2 moles of CeO 2
(2) with Ln 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 60 ~ 80% of ball grinder volume, agate ball and Ln 2O 3Mass ratio be 1.5-2.5, on planetary ball mill, wet mixing 6-10 hour, after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the evaporation after powder in baking oven in 120 ℃ of dry 16-24 hours, with artificial mistake 200 ~ 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1600 ~ 1650 ℃ normal pressure-sintered 8 ~ 12 hours obtain (Sm 1-xLn x) 2Ce 2O 7The thermal barrier coating stupalith.
The invention has the beneficial effects as follows: (the Sm of the present invention's development 1-xLn x) 2Ce 2O 7The thermal barrier coating stupalith of series is compared with the zirconium white that the 7-8% yttrium oxide is partially stabilized, and material of the present invention has the more thermal expansivity of lower thermal conductivity and Geng Gao when high temperature.At high temperature (800-1000 ℃), the thermal conductivity of this two classes material is about 1.2-1.6W/m.K, and its thermal expansion system (1000 ℃) number is about 11.4-13.9 * 10 -6/ K, fully potential as Novel hot barrier coating upper layer stupalith.Preparation technology of the present invention is simple, and cost is low, and product does not at high temperature have phase transformation, and thermal conductivity is low, and thermal expansivity is high.
Description of drawings
Fig. 1 is (Sm 1-x-Gd x) 2Ce 2O 7The thermal conductivity of stupalith;
Fig. 2 is (Sm 1-xGd x) 2Ce 2O 7The thermal expansivity of sosoloid;
Fig. 3 is (Sm 1-xLa x) 2Ce 2O 7The thermal conductivity of sosoloid;
Fig. 4 is (Sm 1-xLa x) 2Ce 2O 7The thermal expansivity of sosoloid;
Fig. 5 is (Sm 1-xNd x) 2Ce 2O 7The thermal conductivity of sosoloid.
Embodiment
Embodiment 1
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, chemical formula are (Sm 0.9Gd 0.1) 2Ce 2O 7, preparation process is as follows:
(1) takes by weighing 0.9 mole of Sm 2O 3, 0.1 mole of Ln 2O 3, 2 moles of CeO 2
(2) with Gd 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 60% of ball grinder volume, agate ball and Gd 2O 3Mass ratio be 2.5, on planetary ball mill, wet mixing 6 hours is after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the powder after the evaporation in baking oven in 120 ℃ of dryings 16 hours, with artificial mistake 200 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1600 ℃ normal pressure-sintered 8 ~ 12 hours obtain (Sm 0.9Gd 0.1) 2Ce 2O 7The thermal barrier coating stupalith.
Embodiment 2
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 0.8La 0.2) 2Ce 2O 7, preparation process is as follows:
(1) takes by weighing 0.8 mole of Sm 2O 3, 0.2 mole of La 2O 3, 2 moles of CeO 2
(2) with La 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 60% of ball grinder volume, agate ball and La 2O 3Mass ratio be 1.5, on planetary ball mill, wet mixing 10 hours is after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the powder after the evaporation in baking oven in 150 ℃ of dryings 24 hours, with artificial mistake 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1650 ℃ normal pressure-sintered 12 hours obtain (Sm 0.8La 0.2) 2Ce 2O 7The thermal barrier coating stupalith.
Embodiment 3
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 0.7Nd 0.3) 2Ce 2O 7, preparation process is as follows:
(1) takes by weighing 0.7 mole of Sm 2O 3, 0.3 mole of Ln 2O 3, 2 moles of CeO 2
(2) with Nd 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 70% of ball grinder volume, agate ball and Nd 2O 3Mass ratio be 2, on planetary ball mill, wet mixing 8 hours is after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the evaporation after powder in baking oven in 140 ℃ of dry 16-24 hours, with artificial mistake 200 ~ 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1620 ℃ normal pressure-sintered 10 hours obtain (Sm 0.7Nd 0.3) 2Ce 2O 7The thermal barrier coating stupalith.
Embodiment 4
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 0.5Er 0.5) 2Ce 2O 7, preparation process is as follows:
(1) takes by weighing 0.5 mole of Sm 2O 3, 0.5 mole of Ln 2O 3, 2 moles of CeO 2
(2) with Er 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 80% of ball grinder volume, agate ball and Er 2O 3Mass ratio be 2.5, on planetary ball mill, wet mixing 10 hours is after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the powder after the evaporation in baking oven in 120 ℃ of dryings 24 hours, with artificial mistake 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1650 ℃ normal pressure-sintered 12 hours obtain (Sm 0.5Er 0.5) 2Ce 2O 7The thermal barrier coating stupalith.
Embodiment 5
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 0.3Dy 0.7) 2Ce 2O 7, preparation process is as follows:
(1) takes by weighing 0.7 mole of Sm 2O 3, 0.3 mole of Ln 2O 3, 2 moles of CeO 2
(2) with Dy 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 80% of ball grinder volume, agate ball and Dy 2O 3Mass ratio be 2, on planetary ball mill, wet mixing 6-10 hour, after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the powder after the evaporation in baking oven in 120 ℃ of dryings 22 hours, with artificial mistake 220 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1600 ℃ normal pressure-sintered 8 hours obtain (Sm 0.3Dy 0.7) 2Ce 2O 7The thermal barrier coating stupalith.
Embodiment 6
Rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material, described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 1-xLn x) 2Ce 2O 7, wherein Ln is La, Gd, Nd, Er, Dy or Yb, 0＜x＜1.
Described rare earth modified Sm 2Ce 2O 7The preparation method of thermal barrier coating ceramic material, its step is as follows:
(1) takes by weighing 1-x mole Sm 2O 3, x mole Ln 2O 3, 2 moles of CeO 2
(2) with Ln 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 60 ~ 80% of ball grinder volume, agate ball and Ln 2O 3Mass ratio be 1.5-2.5, on planetary ball mill, wet mixing 6-10 hour, after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the evaporation after powder in baking oven in 120 ℃ of dry 16-24 hours, with artificial mistake 200 ~ 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1600 ~ 1650 ℃ normal pressure-sintered 8 ~ 12 hours obtain (Sm 1-xLn x) 2Ce 2O 7The thermal barrier coating stupalith.

Claims (2)

1. rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material is characterized in that: described rare earth modified Sm 2Ce 2O 7The chemical formula of thermal barrier coating ceramic material is (Sm 1-xLn x) 2Ce 2O 7, wherein Ln is La, Gd, Nd, Er, Dy or Yb, 0＜x＜1.
2. rare earth modified Sm as claimed in claim 1 2Ce 2O 7The preparation method of thermal barrier coating ceramic material is characterized in that, its step is as follows:
(1) takes by weighing 1-x mole Sm 2O 3, x mole Ln 2O 3, 2 moles of CeO 2
(2) with Ln 2O 3Put into the ball grinder that tetrafluoroethylene is made, take ethanol or deionized water as ball-milling medium, add simultaneously agate ball, ethanol or deionized water consumption account for 60 ~ 80% of ball grinder volume, agate ball and Ln 2O 3Mass ratio be 1.5-2.5, on planetary ball mill, wet mixing 6-10 hour, after the wet mixing, agate ball is taken out from the ball milling jar, remove ethanol or deionized water with rotatory evaporator, with the evaporation after powder in baking oven in 120 ℃ of dry 16-24 hours, with artificial mistake 200 ~ 240 mesh sieves of dried powder, powder after sieving is pressed into preform blank in mould, put into corundum crucible, at 1600 ~ 1650 ℃ normal pressure-sintered 8 ~ 12 hours obtain rare earth modified Sm 2Ce 2O 7Thermal barrier coating ceramic material.
CN2012103346229A 2012-09-12 2012-09-12 Rare-earth modified Sm2Ce2O7 thermal-barrier coating ceramic material and preparation method thereof Pending CN102992764A (en)

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CN112062566A (en) * 2019-05-22 2020-12-11 北京理工大学 Cerate composite material and preparation method and application thereof
CN114751744A (en) * 2021-01-19 2022-07-15 厦门稀土材料研究所 Ceric acid rare earth based high-entropy ceramic material and preparation method thereof
CN116425542A (en) * 2023-03-02 2023-07-14 河南工程学院 Method for preparing rare earth tantalate powder for spraying by adopting solid-phase ball milling method

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CN112062566A (en) * 2019-05-22 2020-12-11 北京理工大学 Cerate composite material and preparation method and application thereof
CN112062566B (en) * 2019-05-22 2022-04-15 北京理工大学 Cerate composite material and preparation method and application thereof
CN114751744A (en) * 2021-01-19 2022-07-15 厦门稀土材料研究所 Ceric acid rare earth based high-entropy ceramic material and preparation method thereof
CN116425542A (en) * 2023-03-02 2023-07-14 河南工程学院 Method for preparing rare earth tantalate powder for spraying by adopting solid-phase ball milling method

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