CN114622153A - Glass modified cerium oxide stabilized zirconia thermal barrier coating and preparation method thereof - Google Patents

Abstract

The invention relates to a glass modified cerium oxide stabilized zirconia thermal barrier coating and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a mixed solution; dropwise adding excessive ammonia water into the mixed solution gradually and continuously stirring until mixed white precipitate is generated; mixing Na₂CO₃Adding the solution into the white precipitate; adding silica sol into the mixed solution obtained in the previous step; adding PVA aqueous solution into the mixture obtained in the previous step; placing the mixture in the previous step on a roller ball mill for ball milling; granulating the ball-milled slurry on a spray granulator, and removing water to obtain dry spherical mixed powder; placing the spherical feed into a powder feeder, and performing thermal spraying on the surface of the metal substrate in an atmosphere plasma spraying manner; and carrying out heat treatment on the coating in a muffle furnace to obtain the high-density nano cerium oxide stabilized zirconia coating. The invention can solve the problem of common ZrO₂Low density of thermal barrier coatingAnd uneven distribution.

Description

Glass modified cerium oxide stabilized zirconia thermal barrier coating and preparation method thereof

Technical Field

The invention belongs to the technical field of high-temperature protection, and relates to a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof.

Background

The thermal barrier coating is widely applied to the thermal protection of high-temperature metal parts such as advanced gas turbines, diesel engines and the like so as to improve the efficiency and the performance of the engines. By depositing the thermal barrier coating on the surface of the metal or alloy, the thermal barrier coating can play a role in insulating the substrate material, reduce the temperature of the substrate and enable the turbine blade to operate at high temperature.

ZrO₂Is a thermal barrier coating material which is widely used at present. But of a single ZrO₂The phase change is generated along with the change of temperature in the service process, and the peeling of the coating is accelerated along with the change of volume. Therefore, Sm is usually employed₂O₃、Sc₂O₃、Yb₂O₃、CeO₂、La₂O₃、Gd₂O₃、TiO₂Etc. into which one or more stabilizers are incorporated₂In the crystal lattice, to improve the stability and service life of the coating. At present, ZrO₂The coating is usually of spherical ZrO by means of compressed air₂The feeding material is blown into a high-temperature spray gun, is melted or semi-melted and then is beaten on the surface of a workpiece, and is cooled and solidified to form a coating. But due to ZrO₂Has a high melting point and a short residence time in the flame, which usually results in ZrO₂The particles are not completely melted, resulting in the production of ZrO₂The density of the thermal barrier coating is not high, and the distribution of particles is not uniform.

Disclosure of Invention

The invention aims to provide a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof. The high-density nano cerium oxide stabilized zirconia (CeSZ) thermal barrier coating is obtained by introducing a glass modifier and filling the inner pores of the coating, and the problem of common ZrO can be solved₂The density of the thermal barrier coating is low and the distribution is uneven.

The invention is realized by adopting the following technical scheme:

a preparation method of a glass modified cerium oxide stabilized zirconia thermal barrier coating comprises the following steps:

step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution;

step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2);

step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2;

step 4, preparing silica sol with a set proportion, and adding the silica sol into the mixed solution in the step 3;

step 5, adding a PVA aqueous solution into the mixture obtained in the step 4;

step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling;

step 7, granulating the ball-milled slurry obtained in the step 6 on a spray granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4);

step 8, placing the spherical feed obtained in the step 7 in a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying mode, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂Si₂O₅；

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is on the other hand₂Si₂O₅And filling pores in the coating after melting to obtain the high-density nano cerium oxide stabilized zirconia coating.

A further development of the invention is that in step 1 the mixture is mixedThe volume of the mixed solution is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂The mass fraction of O is 10-40 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 92: 8-97: 3.

the further improvement of the invention is that the concentration of the ammonia water in the step 2 is 20-40%.

A further improvement of the invention is that Na is added in step 3₂CO₃The concentration of the solution is 40-60 g/L, and the volume of the solution is 100-200 mL.

The invention is further improved in that the concentration of the silica sol in the step 4 is 30-40%, and the volume is 100-200 mL.

The invention is further improved in that the concentration of the PVA aqueous solution in the step 5 is 5-10%, and the addition amount is 200-300 mL.

The further improvement of the invention is that the rotating speed of the roller ball mill in the step 6 is 50-100 r/min, and the working time is 18-36 h.

The invention is further improved in that the parameters of the granulation in step 7 are: the inlet temperature of the spray granulator is 350-360 ℃, the outlet temperature is 130-150 ℃, the temperature in the cavity is 180-220 ℃, the nozzle speed is 30000-35000 r/min, and the feeding speed is 120-160 g/min.

The invention is further improved in that the parameters of plasma spraying in step 8 are as follows: current 260-280A, voltage 30-50V, primary gas (Ar + N)₂) A flow rate of 14.0-16.0L/min, a secondary gas (N)₂) The flow rate is 2.0-4.0L/min, the spraying distance is 90-110 mm, the flow rate of the powder carrier gas is 3.0-6.0L/min, and the powder feeding rate is 2.0-4.0 g/s;

the temperature of the heat treatment in the step 9 is 800-1000 ℃, and the time is 1-2 h.

A glass modified ceria stabilized zirconia thermal barrier coating prepared by the preparation method as claimed in claim.

The invention has at least the following beneficial technical effects:

1. the invention aims to provide a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof. By co-precipitation and sprayingGranulation preparation of Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder is subjected to plasma spraying to obtain cerium oxide stabilized zirconia (CeSZ) and Na₂Si₂O₅The composite coating is finally treated at high temperature to make Na₂Si₂O₅And filling the pores in the coating after melting to obtain the high-density coating.

2. The invention relates to a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof. Compared with the traditional plasma spraying process, the invention utilizes the nano-grade mixed powder as the spraying feed, and prepares CeSZ/Na by decomposing the mixed powder under the high-temperature action of the plasma spray gun₂Si₂O₅The two-phase components of the coating are uniformly distributed, and the agglomeration phenomenon is hardly caused.

3. The invention relates to a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof. By using Na₂Si₂O₅The fluidity of the glass generated after melting at high temperature is used for filling the pores between the coatings, and the compactness of the coating is improved by 50 percent compared with the coating without glass modification, thereby obtaining a more compact coating and being capable of prolonging the service life of the blade.

Drawings

FIG. 1 is an XRD pattern of a glass modified ceria stabilized zirconia (CeSZ) thermal barrier coating made in accordance with the present invention;

FIG. 2 is an SEM image of a glass modified ceria stabilized zirconia thermal barrier coating made in accordance with the present invention;

FIG. 3 shows the compactness of a glass-modified ceria-stabilized zirconia thermal barrier coating prepared according to the present invention.

Detailed Description

The present invention will be described in detail with reference to the following embodiments.

The invention relates to a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating and a preparation method thereof, which are specifically implemented according to the following steps:

step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution; solutions ofHas a volume of 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂The mass fraction of O is 10-40 wt.%, and Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 92: 8-97: 3

Step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2); the concentration of the ammonia water is 20-40%.

Step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2; na (Na)₂CO₃The concentration of the solution is 40-60 g/L, and the volume of the solution is 100-200 mL.

Step 4, preparing silica sol in a set proportion, and adding the silica sol into the mixed solution in the step 3; the concentration of the silica sol is 30-40%, and the volume is 100-200 mL.

Step 5, adding a certain amount of PVA aqueous solution into the mixture obtained in the step 4; the concentration of the PVA aqueous solution is 5-10%, and the addition amount is 200-300 mL.

Step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling; the rotating speed of the roller ball mill is 50-100 r/min, and the working time is 18-36 h.

Step 7, granulating the ball-milled slurry in the step 6 on a spray granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4); the inlet temperature of the spray granulator is 350-360 ℃, the outlet temperature is 130-150 ℃, the temperature in the cavity is 180-220 ℃, the nozzle speed is 30000-35000 r/min, and the feeding speed is 120-160 g/min;

step 8, placing the spherical feed obtained in the step 7 in a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying mode, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂SiO₃(ii) a Plasma processThe parameters of the sub-spraying are as follows: current of 260-280A, voltage of 30-50V, primary gas (Ar + N)₂) A flow rate of 14.0 to 16.0L/min, and a secondary gas (N)₂) The flow rate is 2.0-4.0L/min, the spraying distance is 90-110 mm, the flow rate of the powder carrier gas is 3.0-6.0L/min, and the powder feeding rate is 2.0-4.0 g/s.

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is on the other hand₂Si₂O₅Filling pores in the coating after melting to obtain a high-density nano cerium oxide stabilized zirconia (CeSZ) coating; wherein the temperature of the heat treatment is 800-1000 ℃ and the time is 1-2 h.

Example 1

Step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution; the volume of the solution is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂Mass fraction of O10 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 92: 8.

step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2); the concentration of ammonia was 20%.

Step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2; na (Na)₂CO₃The concentration of the solution was 40g/L, and the volume of the solution was 100 mL.

Step 4, preparing silica sol in a set proportion, and adding the silica sol into the mixed solution in the step 3; the silica sol had a concentration of 30% and a volume of 100 mL.

Step 5, adding a certain amount of PVA aqueous solution into the mixture obtained in the step 4; the concentration of the PVA aqueous solution was 5%, and the amount added was 200 mL.

Step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling; the rotating speed of the roller ball mill is 50r/min, and the working time is 18 h.

7, spraying the ball-milled slurry obtained in the step 6Granulating on a fog granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4); the inlet temperature of the spray granulator is 350 ℃, the outlet temperature is 130 ℃, the temperature in the cavity is 180 ℃, the nozzle speed is 30000r/min, and the feeding speed is 120 g/min;

step 8, placing the spherical feed obtained in the step 7 in a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying mode, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂Si₂O₅(ii) a The parameters of plasma spraying are as follows: current 260A, Voltage 30V, Primary gas (Ar + N)₂) Flow rate 14.0L/min, secondary gas (N)₂) The flow rate is 2.0L/min, the spraying distance is 90mm, the flow rate of the powder carrier gas is 3.0L/min, and the powder feeding rate is 2.0 g/s.

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is on the other hand₂Si₂O₅Filling pores in the coating after melting to obtain a high-density nano cerium oxide stabilized zirconia (CeSZ) coating; wherein the temperature of the heat treatment is 800 ℃ and the time is 2 h.

Example 2

Step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution; the volume of the solution is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂Mass fraction of O40 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 97: 3

Step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2); the concentration of ammonia was 40%.

Step 3, preparing Na with a set proportion₂CO₃The solution is added to the step 2In the white precipitate of (1); na (Na)₂CO₃The concentration of the solution was 60g/L, and the volume of the solution was 200 mL.

Step 4, preparing silica sol with a set proportion, and adding the silica sol into the mixed solution in the step 3; the silica sol had a concentration of 40% and a volume of 200 mL.

Step 5, adding a certain amount of PVA aqueous solution into the mixture obtained in the step 4; the concentration of the PVA aqueous solution was 10%, and the amount added was 300 mL.

Step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling; the rotating speed of the roller ball mill is 100r/min, and the working time is 36 h.

Step 7, granulating the ball-milled slurry obtained in the step 6 on a spray granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4); the inlet temperature of the spray granulator is 360 ℃, the outlet temperature is 150 ℃, the temperature in the cavity is 220 ℃, the nozzle speed is 35000r/min, and the feeding speed is 160 g/min;

step 8, placing the spherical feed obtained in the step 7 in a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying mode, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂SiO₃(ii) a The parameters of plasma spraying are as follows: current 280A, voltage 50V, primary gas (Ar + N)₂) Flow rate of 16.0L/min, secondary gas (N)₂) The flow rate is 4.0L/min, the spraying distance is 110mm, the flow rate of the powder carrier gas is 6.0L/min, and the powder feeding rate is 4.0 g/s.

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is added on the other hand₂Si₂O₅Filling pores in the coating after melting to obtain a high-density nano cerium oxide stabilized zirconia (CeSZ) coating; wherein the temperature of the heat treatment is 1000 ℃ and the time is 1 h.

Example 3

Step (ii) of1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution; the volume of the solution is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂Mass fraction of O20 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 95: 5.

step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2); the concentration of ammonia was 30%.

Step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2; na (Na)₂CO₃The concentration of the solution was 50g/L, and the volume of the solution was 150 mL.

Step 4, preparing silica sol in a set proportion, and adding the silica sol into the mixed solution in the step 3; the silica sol had a concentration of 35% and a volume of 150 mL.

Step 5, adding a certain amount of PVA aqueous solution into the mixture obtained in the step 4; the concentration of the PVA aqueous solution was 8%, and the amount added was 250 mL.

Step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling; the rotating speed of the roller ball mill is 70r/min, and the working time is 24 h.

Step 7, granulating the ball-milled slurry obtained in the step 6 on a spray granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4); the inlet temperature of the spray granulator is 350 ℃, the outlet temperature is 140 ℃, the temperature in the cavity is 200 ℃, the nozzle speed is 32000r/min, and the feeding speed is 140 g/min;

step 8, placing the spherical feed obtained in the step 7 in a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying mode, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂SiO₃(ii) a The parameters of plasma spraying are as follows: current 260A, Voltage 40V, Primary gas (Ar + N)₂) Flow rate 15.0L/min, secondary gas (N)₂) The flow rate is 3.0L/min, the spraying distance is 100mm, the flow rate of the powder carrier gas is 4L/min, and the powder feeding rate is 3.0 g/s.

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is on the other hand₂Si₂O₅Filling pores in the coating after melting to obtain a high-density nano cerium oxide stabilized zirconia (CeSZ) coating; wherein the temperature of the heat treatment is 900 ℃ and the time is 1.5 h.

Example 4

Step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution; the volume of the solution is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂Mass fraction of O30 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 94: 6.

step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2); the concentration of ammonia was 35%.

Step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2; na (Na)₂CO₃The concentration of the solution was 45g/L, and the volume of the solution was 160 mL.

Step 4, preparing silica sol with a set proportion, and adding the silica sol into the mixed solution in the step 3; the silica sol had a concentration of 35% and a volume of 180 mL.

Step 5, adding a certain amount of PVA aqueous solution into the mixture obtained in the step 4; the concentration of the PVA aqueous solution was 6%, and the amount added was 240 mL.

Step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling; the rotating speed of the roller ball mill is 80r/min, and the working time is 32 h.

7, putting the ball-milled slurry obtained in the step 6 on a spray granulatorGranulating to remove water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4); the inlet temperature of the spray granulator is 360 ℃, the outlet temperature is 140 ℃, the temperature in the cavity is 200 ℃, the nozzle speed is 33000r/min, and the feeding speed is 150 g/min;

step 8, placing the spherical feed obtained in the step 7 into a powder feeder, performing thermal spraying on the surface of the metal substrate in an atmospheric plasma spraying manner, and performing Zr (OH) under the condition of high-temperature flame₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂Si₂O₅(ii) a The parameters of plasma spraying are as follows: current 260A, Voltage 40V, Primary gas (Ar + N)₂) Flow rate 15.0L/min, secondary gas (N)₂) The flow rate is 2.5L/min, the spraying distance is 100mm, the flow rate of the powder carrier gas is 5.0L/min, and the powder feeding rate is 3.0 g/s.

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is added on the other hand₂Si₂O₅Filling pores in the coating after melting to obtain a high-density nano cerium oxide stabilized zirconia (CeSZ) coating; wherein the temperature of the heat treatment is 1000 ℃ and the time is 1.5 h.

The XRD pattern of the glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating prepared by the method of the invention is shown in figure 1, and the XRD pattern shows that only tetragonal-phase ZrO exists in the coating obtained after spraying₂Description of Ce after high temperature spraying⁴⁺Dissolved ZrO₂In the crystal lattice of (B), stabilized ZrO is obtained₂The function of the crystal form; in addition, a large amount of Na was detected₂Si₂O₅The diffraction peak of (1) indicates Na₂CO₃And SiO₂The reaction is successful to generate Na₂Si₂O₅A glassy phase;

an SEM image of a glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating prepared by the method of the invention is shown in figure 2, the prepared coating has an obvious layered structure, the powder has high melting degree, the coating is very compact, almost no obvious air holes exist, and the distribution is very uniform; a large amount of black glass phase is mixed in the coating, which is beneficial to filling air holes in the coating and improving the density, thereby reducing the contact between air and the substrate.

The density of the glass modified cerium oxide stabilized zirconia (CeSZ) thermal barrier coating prepared by the method is obviously improved as shown in figure 3, and compared with an unmodified coating, the density of the coating modified by the glass is improved by nearly 40 percent, so that a more compact coating is obtained, and the service life of a blade can be prolonged.

Claims (10)

1. A preparation method of a glass modified cerium oxide stabilized zirconia thermal barrier coating is characterized by comprising the following steps:

step 1, configuring ZrOCl according to a set proportion₂·8H₂O and Ce (NO)₃)₃·6H₂O, mixing the solution;

step 2, dropwise adding excessive ammonia water into the mixed solution in the step 1 step by step and continuously stirring until Zr (OH) is generated₄And Ce (OH)₃Mixed white precipitate of (2);

step 3, preparing Na with a set proportion₂CO₃Adding the solution into the white precipitate obtained in the step 2;

step 4, preparing silica sol with a set proportion, and adding the silica sol into the mixed solution in the step 3;

step 5, adding a PVA aqueous solution into the mixture obtained in the step 4;

step 6, placing the mixture obtained in the step 5 on a roller ball mill for ball milling;

step 7, granulating the ball-milled slurry obtained in the step 6 on a spray granulator, and removing water to obtain dry Zr (OH)₄、Ce(OH)₃、Na₂CO₃、SiO₂The spherical mixed powder of (4);

step 8, placing the spherical feed obtained in the step 7 into a powder feeder, and performing heat treatment on the surface of the metal substrate in an atmosphere plasma spraying mannerSpraying, Zr (OH) under high temperature flame condition₄And Ce (OH)₃After pyrolysis, cerium ions are incorporated into ZrO₂In the crystal lattice; further, Na₂CO₃After decomposition and SiO₂Reaction to form Na₂Si₂O₅；

Step 9, performing heat treatment on the coating obtained in the step 8 in a muffle furnace to ensure that the reaction is more sufficient on one hand and Na is on the other hand₂Si₂O₅And filling pores in the coating after melting to obtain the high-density nano cerium oxide stabilized zirconia coating.

2. The method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating as claimed in claim 1, wherein the volume of the mixed solution in step 1 is 2000mL, ZrOCl₂·8H₂O and Ce (NO)₃)₃·6H₂The mass fraction of O is 10-40 wt.%, Zr⁴⁺Ce of (1)³⁺The molar concentration ratio is 92: 8-97: 3.

3. the method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating as claimed in claim 1, wherein the concentration of ammonia in step 2 is 20-40%.

4. The method of claim 1, wherein in step 3 Na is added₂CO₃The concentration of the solution is 40-60 g/L, and the volume of the solution is 100-200 mL.

5. The method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating according to claim 1, wherein the concentration of the silica sol in step 4 is 30-40%, and the volume is 100-200 mL.

6. The method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating as claimed in claim 1, wherein the concentration of the PVA aqueous solution in step 5 is 5-10%, and the addition amount is 200-300 mL.

7. The method for preparing a glass modified ceria stabilized zirconia thermal barrier coating according to claim 1, wherein the rotation speed of the roll ball mill in step 6 is 50-100 r/min, and the working time is 18-36 h.

8. The method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating as claimed in claim 1, wherein the parameters of the granulation in step 7 are: the inlet temperature of the spray granulator is 350-360 ℃, the outlet temperature is 130-150 ℃, the temperature in the cavity is 180-220 ℃, the nozzle speed is 30000-35000 r/min, and the feeding speed is 120-160 g/min.

9. The method for preparing a glass-modified ceria-stabilized zirconia thermal barrier coating as claimed in claim 1, wherein the parameters of plasma spraying in step 8 are: current 260-280A, voltage 30-50V, primary gas (Ar + N)₂) A flow rate of 14.0 to 16.0L/min, and a secondary gas (N)₂) The flow rate is 2.0-4.0L/min, the spraying distance is 90-110 mm, the flow rate of the powder carrier gas is 3.0-6.0L/min, and the powder feeding rate is 2.0-4.0 g/s;

the temperature of the heat treatment in the step 9 is 800-1000 ℃, and the time is 1-2 h.

10. A glass modified ceria stabilized zirconia thermal barrier coating prepared by the method of any one of claims 1 to 9.

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