1. A gadolinium samarium zirconium oxygen thermal barrier coating material is characterized in that: the chemical molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material is (Gd)_1-xSm_x)₂Zr₂O₇Wherein x is 0.10-0.90.

2. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:

step one, raw material Gd₂O₃、Sm₂O₃、ZrO₂Mixing according to the molecular formula ratio of the material, and synthesizing the gadolinium samarium zirconium oxide target material by a high-temperature solid phase method at the synthesis temperature of 1600-1800 ℃;

step two, preparing a NiCoCrAlYHf metal bottom layer as a thermal barrier coating by adopting vacuum arc plating equipment, wherein the voltage is 600-650V, and the current is 10-20A;

and step three, loading the gadolinium samarium zirconium oxygen target material into electron beam physical vapor deposition equipment, evaporating the gadolinium samarium zirconium oxygen target material through electron beams, and preparing a gadolinium samarium zirconium oxygen thermal barrier coating on a NiCoCrAlYHf bottom layer, wherein the beam intensity of the electron beams is 1.0-1.5A.

3. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: step one raw material Gd₂O₃、Sm₂O₃、ZrO₂The purity of the product is more than or equal to 99.9 percent.

4. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: in the first step, the raw material mixing is mechanical ball milling for more than or equal to 12 hours.

5. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: the synthesis time of the step I by a high-temperature solid phase method is more than or equal to 18 hours.

6. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: vacuum degree of vacuum arc plating equipment in the second step<1×10^-2Pa。

7. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: and in the second step, the deposition time of the vacuum arc plating equipment is more than or equal to 100 min.

8. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: vacuum degree of electron beam physical vapor deposition equipment in the third step<5×10^-2Pa。

9. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: in the third step, the evaporation time of the electron beam physical vapor deposition thermal barrier coating is more than or equal to 30 min.

10. The method for preparing a gadolinium samarium zirconium oxygen thermal barrier coating material coating according to claim 2, wherein the method comprises the following steps: and in the third step, the thermal barrier coating deposited by the electron beam physical vapor deposition is cooled to below 200 ℃ along with the furnace, and the cooling is natural cooling.

Background

At present, with the continuous improvement of the thrust and the working efficiency of the gas turbine, the gas inlet temperature is higher and higher, and the working temperature of the nickel-based high-temperature alloy used for the turbine blade and other hot-end components is gradually close to the service temperature limit. Thermal Barrier Coatings (TBCs) are a surface protection technology which combines ceramic materials with a metal substrate in the form of a coating by utilizing the high temperature resistance, scouring resistance, corrosion resistance and low Thermal conductivity of the ceramic materials, so as to improve the working temperature of metal components, enhance the high temperature resistance of hot end components, prolong the service life of the hot end components and improve the working efficiency of an engine. Currently, the YSZ (6-8 wt.% Y) is widely used₂O₃Partially stabilized ZrO₂) The thermal barrier coating material has high thermal conductivity and low ultra-high temperature service life. However, the next generation of high performance aircraft engine thermal barrier coating materials require better thermal insulation and service life. Therefore, the research on new thermal barrier coating materials has become a key issue for the development of the next generation of high performance aeroengines.

Disclosure of Invention

Aiming at the defects of the prior art, the invention designs and provides a gadolinium samarium zirconium oxygen thermal barrier coating material and a preparation method thereof, aiming at compounding rare earth samarium elements and solving the problems of short service life and high YSZ thermal conductivity of a single gadolinium zirconate thermal barrier coating.

The purpose of the invention is realized by the following technical measures:

a gadolinium samarium zirconium oxygen thermal barrier coating material is characterized in that: the chemical molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material is (Gd)_1-xSm_x)₂Zr₂O₇Wherein x is 0.10-0.90.

The preparation method of the gadolinium samarium zirconium oxygen thermal barrier coating material coating is characterized by comprising the following steps of: the method comprises the following steps:

in the first step of the method,gd as a raw material₂O₃、Sm₂O₃、ZrO₂Mixing according to the molecular formula ratio of the material, and synthesizing the gadolinium samarium zirconium oxide target material by a high-temperature solid phase method at the synthesis temperature of 1600-1800 ℃;

step two, preparing a NiCoCrAlYHf metal bottom layer as a thermal barrier coating by adopting vacuum arc plating equipment, wherein the voltage is 600-650V, and the current is 10-20A;

and step three, loading the gadolinium samarium zirconium oxygen target material into electron beam physical vapor deposition equipment, evaporating the gadolinium samarium zirconium oxygen target material through electron beams, and preparing a gadolinium samarium zirconium oxygen thermal barrier coating on a NiCoCrAlYHf bottom layer, wherein the beam intensity of the electron beams is 1.0-1.5A.

Step one raw material Gd₂O₃、Sm₂O₃、ZrO₂The purity of the product is more than or equal to 99.9 percent.

In the first step, the raw material mixing is mechanical ball milling for more than or equal to 12 hours.

The synthesis time of the step I by a high-temperature solid phase method is more than or equal to 18 hours.

Vacuum degree of vacuum arc plating equipment in the second step<1×10^-2Pa。

And in the second step, the deposition time of the vacuum arc plating equipment is more than or equal to 100 min.

Vacuum degree of electron beam physical vapor deposition equipment in the third step<5×10^-2Pa。

In the third step, the evaporation time of the electron beam physical vapor deposition thermal barrier coating is more than or equal to 30 min.

And in the third step, the thermal barrier coating deposited by the electron beam physical vapor deposition is cooled to below 200 ℃ along with the furnace, and the cooling is natural cooling.

The invention has the advantages and beneficial effects that the thermal barrier coating material as a novel thermal barrier coating material has a thermal expansion coefficient which is closer to that of YSZ and has lower thermal conductivity. Meanwhile, the gadolinium samarium zirconium oxide thermal barrier coating is prepared by utilizing an electron beam physical vapor deposition technology, so that the gadolinium samarium zirconium oxide thermal barrier coating has a unique columnar crystal structure and a longer service life; the invention can not only ensure to reduce the heat conductivity of the coating, but also improve the service temperature of the coating, and also improve the practical problems of short service life and low thermal expansion coefficient of the coating.

Drawings

FIG. 1 is a schematic view of thermal conductivity of example 2

FIG. 2 is a schematic view showing the thermal expansion coefficient in example 2

FIG. 3 is a schematic view of thermal life in example 2

FIG. 4 is a schematic view of a columnar crystal structure of the present invention

Detailed Description

The technical scheme of the invention is further detailed in the following by combining the drawings and the embodiment:

the chemical molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material is (Gd)_{1- x}Sm_x)₂Zr₂O₇Wherein x is 0.10-0.90.

The preparation method of the gadolinium samarium zirconium oxygen thermal barrier coating material coating comprises the following steps:

gd as a raw material₂O₃、Sm₂O₃、ZrO₂Mixing according to the molecular formula ratio of the material, wherein the purity of the raw material is more than or equal to 99.9 percent, the mixing mode is mechanical ball milling, and the time is more than or equal to 12 hours; synthesizing the gadolinium samarium zirconium oxide target material by a high-temperature solid phase method, wherein the synthesis temperature is 1600-1800 ℃, and the synthesis time is more than or equal to 18 hours; preparing NiCoCrAlYHf as a metal bottom layer of a thermal barrier coating by adopting vacuum arc plating equipment, wherein the vacuum degree<1×10^-2Pa, voltage of 600-650V, current of 10-20A, and deposition time of 100min or more; the prepared target material is loaded into electron beam physical vapor deposition equipment with vacuum degree<5×10^-2P, the beam intensity of the electron beam is 1.0-1.5A, the evaporation time is more than or equal to 30min, a thermal barrier coating is prepared, and the thermal barrier coating is naturally cooled to below 200 ℃ along with the furnace.

Example 1:

the method comprises the following steps of: weighing raw materials Gd2O3, Sm2O3 and ZrO2 according to the molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material (Gd0.3Sm0.7)2Zr2O 7.

The method comprises the following steps of: mechanically ball-milling the raw materials for 14h, and synthesizing the gadolinium samarium zirconium oxide target material by a 1600 ℃ high-temperature solid phase method for 26 h;

(3) preparing a bottom layer: preparing a NiCoCrAlYHf metal bottom layer serving as a thermal barrier coating by adopting vacuum arc plating equipment, wherein the vacuum degree is less than 1 multiplied by 10 < -2 > Pa, the voltage is 600V, the current is 10A, and the deposition time is 200 min;

(4) and preparing a thermal barrier coating: and (3) loading the gadolinium samarium zirconium oxygen target material into electron beam physical vapor deposition equipment. Deposition process parameters: the vacuum degree is less than 5 multiplied by 10 < -2 > Pa, the electron beam current intensity is 1.25A, the evaporation time is 50min, and after cooling to below 200 ℃, deposition equipment is opened to obtain the gadolinium samarium zirconium oxide thermal barrier coating.

The thermal conductivity of the prepared gadolinium samarium zirconium oxygen thermal barrier coating is 1.25W/(mK) at 1000 ℃; the thermal expansion coefficient is 10.82 multiplied by 10 < -6 > K < -1 >; the thermal life was 663 hours.

Example 2:

the method comprises the following steps of: weighing raw materials Gd2O3, Sm2O3 and ZrO2 according to the molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material (Gd0.5Sm05)2Zr2O 7.

The method comprises the following steps of: mechanically ball-milling the raw materials for 16h, and synthesizing the gadolinium samarium zirconium oxide target material by a 1700 ℃ high-temperature solid phase method for 22 h;

(3) preparing a bottom layer: preparing a NiCoCrAlYHf metal bottom layer serving as a thermal barrier coating by adopting vacuum arc plating equipment, wherein the vacuum degree is less than 1 multiplied by 10 < -2 > Pa, the voltage is 625V, the current is 15A, and the deposition time is 150 min;

(4) and preparing a thermal barrier coating: and (3) loading the gadolinium samarium zirconium oxygen target material into electron beam physical vapor deposition equipment. Deposition process parameters: the vacuum degree is less than 5 multiplied by 10 < -2 > Pa, the electron beam current intensity is 1.35A, the evaporation time is 40min, and after cooling to below 200 ℃, deposition equipment is opened to obtain the gadolinium samarium zirconium oxide thermal barrier coating.

The thermal conductivity of the prepared gadolinium samarium zirconium oxygen thermal barrier coating is 1.20W/(mK) at 1000 ℃; the thermal expansion coefficient is 11.19 multiplied by 10 < -6 > K < -1 >; the thermal life was 698 hours.

Example 3:

the method comprises the following steps of: weighing raw materials Gd2O3, Sm2O3 and ZrO2 according to the molecular formula of the gadolinium samarium zirconium oxygen thermal barrier coating material (Gd0.7Sm0.3)2Zr2O 7.

The method comprises the following steps of: mechanically ball-milling the raw materials for 16h, and synthesizing the gadolinium samarium zirconium oxide target material by a 1800 ℃ high-temperature solid phase method for 18 h;

(3) preparing a bottom layer: preparing a NiCoCrAlYHf metal bottom layer as a thermal barrier coating by adopting vacuum arc plating equipment, wherein the voltage is 650V, the current is 20A, and the deposition time is 100 min;

(4) and preparing a thermal barrier coating: and (3) loading the gadolinium samarium zirconium oxygen target material into electron beam physical vapor deposition equipment. Deposition process parameters: the vacuum degree is less than 5 multiplied by 10 < -2 > Pa, the electron beam current intensity is 1.45A, the evaporation time is 30min, and after cooling to below 200 ℃, deposition equipment is opened to obtain the gadolinium samarium zirconium oxide thermal barrier coating.

The thermal conductivity of the prepared gadolinium samarium zirconium oxygen thermal barrier coating is 1.35W/(mK) at 1000 ℃; the thermal expansion coefficient is 11.02 multiplied by 10 < -6 > K < -1 >; the thermal life was 678 hours.

As can be seen from the above embodiments, compared with the prior art, the technical scheme of the invention has the advantages that:

(1) in the preparation method, the thermal barrier coating is prepared by using the electron beam physical vapor deposition technology, so that the thermal barrier coating has a unique columnar crystal structure and a longer service life.

(2) In the design of the coating, samarium composite modification is adopted, so that the heat conductivity of the gadolinium zirconate coating can be reduced, and the practical problems of low thermal expansion coefficient and short service life of single gadolinium zirconate can be solved.