CN101200375A - Preparation method of nano zirconium-containing thermal barrier coating material - Google Patents

Abstract

A method for preparing a nano zirconium-containing series thermal barrier coating material. Use cheap zirconium oxychloride and ammonium carbonate or ammonium bicarbonate as raw materials to prepare zirconium carbonate or basic zirconium carbonate, and mix with alkaline earth metal, rare earth metal, titanium, aluminum hydroxide, carbonate precipitation or other compounds One or more of them are mixed, and after stirring ball milling, spray-drying granulation, and heat treatment processes, nano-zirconia ZrO ₂ doped with different substances or nano-rare earth zirconate RE ₂ Zr ₂ with a pyrochlore crystal structure are obtained. O ₇ agglomerated nano powder products. The agglomerated powder has low chloride ion content, easy control of the composition, strong adaptability of the preparation method, short process, easy scale, mild preparation technical conditions, low production cost, and good product quality, which is conducive to obtaining porous agglomerated zirconium-containing nanoparticles. The compound particle powder is suitable for the preparation material of thermal barrier coating.

Description

Preparation method of nano zirconium-containing thermal barrier coating material

[technical field]: the present invention belongs to the technical field of inorganic non-metallic materials. It relates to a preparation method of nano zirconium-containing series thermal barrier coating materials, in particular to a preparation method of nano materials such as doped zirconia and rare earth zirconate RE ₂ Zr ₂ O ₇ with a pyrochlore crystal structure.

[Background Technology]: In recent years, aero-engines have developed towards high flow ratio, high thrust-to-weight ratio, and high turbine air inlet temperature. The speed has reached or exceeded 4 times the speed of sound, and the air inlet temperature of the aero-engine has reached 1300°C. As the performance of the engine continues to improve, it is expected to reach 1700°C, and may even be 2000°C. Such high temperatures far exceed the melting points of existing alloys. Therefore, in order to achieve such a high gas temperature, corresponding measures must be taken, one is to improve the cooling technology to reduce the temperature of the combustion chamber wall in contact with the gas, such as the use of laminated structure, film cooling technology; the other is to use more advanced High-temperature alloy materials; the third is to spray thermal barrier coatings (Thermal Barrier Coatings, TBCs) on existing heat-resistant alloys. Using cooling technology No matter water cooling or film cooling technology, if too much internal and external cooling is used, the thermal efficiency of the engine will be reduced, which will undoubtedly increase energy consumption and lead to a decrease in engine performance.

At the same time, the potential to further tap the working temperature of superalloy materials is very limited. Therefore, the most feasible and economical way to increase the operating temperature of thermal engines is to further reduce the thermal conductivity of TBCs ceramic coating materials under the premise of using more advanced superalloy materials and cooling technologies.

Thermal barrier coating is one of the key technologies of modern aero-engines. Its basic principle is based on the high melting point and low thermal conductivity of ceramic coatings. In addition, ceramic coatings contain considerable porosity, so thermal barrier ceramic coatings Become a very good high temperature insulation material. It isolates hot components of jet engines and gas turbines from hot gases. Its main function is to reduce the working temperature of the hot-end parts, prevent high-temperature corrosion of the parts, improve the operating temperature and thermal efficiency of the aero-engine, reduce the exhaust volume, save fuel, and prolong the service life of the workpiece.

The application of thermal barrier coatings can reduce the operating temperature of materials such as turbine engine combustion chambers, thereby greatly improving their performance, life and reliability, and reducing engine fuel consumption. Now the research focus of various countries is on the research of thermal barrier coating materials. In the 1980s, the National Aeronautics and Space Administration (NASA) specifically listed the hot end technology of aero-engines as a key research project. Thermal barrier coatings have the advantages of easy manufacture of parts, less investment, low cost, safety and reliability, and easy refurbishment and replacement. TBCs have brought significant improvements and benefits to the aero-engine and gas turbine industries. Therefore, the world's aero-engine manufacturers attach great importance to the development of thermal barrier coating materials and preparation technologies.

A typical thermal barrier coating system consists of a corrosion-resistant bonding layer and a surface ceramic layer coated on a superalloy substrate. Zirconia (ZrO ₂ ) is one of the best performance and most commonly used surface layer ceramic materials, but the transformation of pure ZrO ₂ from high temperature to low temperature has obvious hysteresis effect, and the volume expansion of about 4% occurs during the transformation, resulting in ZrO ₂ Cracks and even bursting occur. Therefore, pure _ZrO2 has less applications. In order to prevent the transformation of low-temperature crystal form and high- _temperature crystal form, it is generally necessary to add some CaO, MgO, Y ₂ O ₃ , CeO, Yb ₂ O ₃ , Er _{2 O 3 , Dy 2 O 3} , Gd ₂ O ₃ , Eu ₂ O ₃ etc. as a crystal structure stabilizer. Among them, ZrO ₂ (P-YSZ) ceramic surface layer with 6-8%wt% Y ₂ O ₃ partial stabilization is most commonly used.

At present, in order to meet the use requirements of thermal barrier coatings at higher temperatures (greater than 1200 ° C), people are developing a new generation of thermal barrier coating materials, including zirconium with a pyrochlore crystal structure (A ₂ B ₂ O ₇ ). salt materials, such as rare earth zirconate RE ₂ Zr ₂ O ₇ (RE=Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Er, Yb, etc.).

Although the application of thermal barrier coatings on aero-engines is becoming more and more common, the actual thermal insulation effect of the surface ceramic layer and the problem of coating peeling have always affected the promotion and application of thermal barrier coatings on high-pressure turbine blades. Because once the ceramic heat insulation layer peels off, the blade alloy is exposed to high temperature gas, resulting in failure. In order to further improve the thermal insulation and anti-stripping properties of thermal barrier coatings, a lot of research work has been carried out at home and abroad in the past ten years. From the perspective of improving the microstructure of thermal barrier coatings, designs and developments such as continuous gradient coatings, two-dimensional Structural coatings, nano coatings and micro laminations, etc. Among them, nano-thermal barrier coatings have become one of the most potential development directions of high-performance thermal barrier coatings due to their excellent thermal insulation performance, high interface bonding strength, high strain tolerance and damage resistance. Nanostructured materials make it possible for thermal barrier coatings to obtain properties such as high plasticity and toughness, high strength and hardness, high thermal expansion coefficient, low density, low elastic modulus and low thermal conductivity. Although nano-thermal barrier coatings have good application prospects, the materials and cost of making coatings still limit its wide application.

The inventor Hou Shuen and others have applied for the preparation method of nano-zirconia powder. Adding an alkaline precipitating agent to an aqueous solution containing zirconium salt to obtain hydroxide precipitation, and then filtering, washing, dehydrating, drying, and calcining to obtain zirconia powder. The body is characterized in that the colloidal solution after dehydration by azeotropic distillation is dried in a distillation device, and is continuously stirred during dehydration and drying. For the content of the application, refer to "Preparation Method of Nano Zirconia Powder", the publication number is CN1397597A.

Inventors Hou Shuen, Wang Yanxin, Xiang Longbin, Song Zihong, Chen Hao, Wang Pingping have applied for nanostructured yttrium-stabilized zirconia agglomerated powder and its production method. The method is prepared by adding water into nano-zirconia particles containing yttrium oxide to obtain aqueous suspension colloid, and then spray drying, screening, heat treatment and plasma densification. The method comprises the following steps: mixing yttrium-stabilized nano-ZrO ₂ powder particles with water to prepare water-based nano-suspension colloid; using a spray drying process to make the water-based nano-suspension colloid into micron-sized agglomerated powder; heat-treating the agglomerated powder ; Use plasma technology to densify the heat-treated powder to obtain nanostructured yttrium-stabilized zirconia agglomerated powder. It is used to meet the needs of thermal spraying processes such as plasma spraying, flame spraying, and arc spraying. For the content of the application, please refer to "Yttrium-stabilized zirconia agglomerated powder with nanostructure and its production method", the publication number is CN1587062A.

Inventors Chen Dairong, Jiao Xiuling, etc. have applied for the preparation method of zirconia nanomaterials for thermal barrier coatings, using zirconia oxychloride, yttrium oxide or memnesium chloride as raw materials to prepare a mixed solution, and then adding ammonia water to the solution, washing and dispersing Finally, put it into the reactor and carry out hydrothermal reaction to obtain yttrium-stabilized or partially stabilized tetragonal phase ZrO ₂ nano-powders, and then separate, dry or granulate, or use alumina to coat the surface of the nano-powders, then carry out Drying or granulation, and finally heat treatment to obtain zirconia nanomaterials that can be used as thermal barrier coating materials. For the content of the application, please refer to "Preparation Method of Zirconia Nanomaterials for Thermal Barrier Coating", the publication number is CN1757605A.

The above-mentioned invention requires azeotropic distillation dehydration, colloid mill or hydrothermal treatment technology to prepare nano-sized zirconia powder and then reunite and granulate. The preparation process is long and requires complex or high-pressure equipment, etc., and the output is limited.

Zirconium oxychloride (ZrOCl ₂ 8H ₂ O) is the most basic chemical raw material for industrial production of various zirconium products. When producing nano-sized zirconia and zirconium-containing oxides, it is generally used to add ammonia water to the zirconium oxychloride aqueous solution As the preparation method of the precipitating agent, firstly, under the condition of pH 9-10, zirconium hydroxide precipitates with different water contents or precipitation mixtures containing various components are prepared. Because the precipitation mixture is difficult to wash and filter, it contains a large amount of impurities such as chloride ions and ammonium ions, which are difficult to wash and remove. When using these zirconia hydroxide precipitates (or hydrated zirconia) as precursors to prepare nano-zirconia powders, the heat treatment temperature should not be too high (generally less than 900°C), otherwise the nano-powders will grow or sinter into large particles, changing Properties of nanopowders. However, in order to ensure the obtaining of nano-powders, when the precursors are processed at this low temperature, the chloride ions, ammonium ions, especially the chloride ions are difficult to volatilize and remove, which seriously affects the quality of nano-zirconia and other products.

Zirconium carbonate (ZrOCO ₃ ·nH ₂ O) is an intermediate raw material for the preparation of zirconium compounds. It can be used as waterproofing agent, flame retardant, fiber treatment and paper surface additive, and is a raw material for textile, papermaking, coating and other industries. The composition of zirconium carbonate is relatively complex, and the composition of the product is not fixed under different conditions. Zirconium carbonate has the following forms: Zr ₂ O ₃ (OH) ₂ CO ₃ nH ₂ O (or ZrOCO ₃ ZrO(OH) ₂ ·xH ₂ O), Zr(OH) ₂ ·CO ₃ ·nH ₂ O, ZrO ₂ ·CO ₃ ·nH ₂ O, ZrOCO ₃ ·nH ₂ O, can also be called basic zirconium carbonate according to its structure and composition , generally refers to zirconium carbonate and basic zirconium carbonate are mixtures of the above-mentioned various forms. Nano-zirconium carbonate can be mixed with other nano-metal compounds, spray-dried and granulated, heat-treated in an electric furnace at 350-400°C for 3-5 hours, then heated to 700-850°C and kept for 12-16 hours for heat treatment. Nanometer zirconia ZrO ₂ or pyrochlore-type crystal structure nano-rare earth zirconate RE ₂ Zr ₂ O ₇ agglomerated powder with different substances and substance amounts. These nanostructured zirconium compound powders have a porous structure inside and are suitable for thermal barrier coating material.

The main production methods of industrial zirconium carbonate are as follows. One is to add carbonate to zirconium-containing hydrochloric acid solution to generate (ordinary) zirconium carbonate precipitate, then react it with ammonium bicarbonate to generate ammonium zirconium carbonate, add a dispersant to the ammonium zirconium carbonate solution and heat it to decompose to form superfine Or nano high activity zirconium carbonate. The zirconium carbonate produced by this process has good activity and low impurity content, but the process is long, the control is complicated, and the requirements for equipment performance are strict, so the production cost is high. The second is to adopt a step-by-step liquid phase precipitation process, that is, zirconium oxychloride → basic zirconium sulfate → suction filtration washing → zirconium carbonate → suction filtration washing. First make zirconium oxychloride into a solution, then introduce a certain amount of sulfuric acid (or sulfate) and catalyst in proportion, control the stirring speed after adding, raise the temperature of the system to a certain temperature, and keep the temperature of the system for a period of time, then take samples with a microscope Observe its morphological structure, stop the reaction after reaching the standard, wash the precipitate with deionized water, and then react the washed basic zirconium sulfate with carbonate at normal temperature and pressure to generate zirconium carbonate. The third is to adopt a one-step production process. For example, domestic zirconium carbonate manufacturers use zirconium oxychloride solution and sodium sulfate solution to react to form sodium zirconium sulfate double salt, and then react with sodium bicarbonate to produce zirconium carbonate.

According to the actual situation of the production process, using the relatively good filterability of zirconium carbonate and the characteristics that impurities are easily washed away, cheap zirconium oxychloride is used as raw material, and after being converted into precursors such as zirconium carbonate (or basic zirconium carbonate), After heat treatment, nano or ultrafine zirconia products with good performance can be obtained. At the same time, these precursors can be conveniently mixed with other materials to prepare various zirconium-containing nano or ultrafine compounds. The required production equipment is simple and the process conditions are mild.

[Content of the invention]: The purpose of the present invention is to solve the above-mentioned deficiencies in the prior art, and to provide a method for preparing agglomerated nano zirconium-containing thermal barrier coating materials.

The concrete preparation process of the inventive method is as follows:

First, using cheap zirconium oxychloride as a raw material, first prepare a mixture of zirconium carbonate or basic zirconium carbonate and other elements, the specific method is as follows:

Method 1: Zirconium oxychloride ZrOCl ₂ 8H ₂ O is formulated into a 0.5-2.5 mol/L aqueous solution, and ammonium carbonate or ammonium bicarbonate is used as a precipitating agent (the industrial product ammonium carbonate is both ammonium bicarbonate and ammonium carbamate) In addition, it is often customary in industry to call ammonium bicarbonate ammonium carbonate (abbreviated as ammonium bicarbonate), which is made into an aqueous solution with a concentration of 0.5-3mol/L, and the ammonium carbonate or ammonium bicarbonate aqueous solution is mixed according to the required amount of 100- 105% is added to the zirconium oxychloride aqueous solution, and the zirconium carbonate or basic zirconium carbonate precipitate that is easy to wash and has low chloride ion content is obtained by precipitation. After washing and filtering, until no chloride ion is detected with silver nitrate, Slurry the obtained zirconium carbonate or basic zirconium carbonate precipitate with water for later use; then mix with alkaline earth metals, rare earth metals, or aluminum oxides, hydroxides, carbonates or colloids, or one of aluminum ammonium carbonate or more mixed according to the total content of 0.1 to 21%, or,

Method 2: Prepare zirconium oxychloride ZrOCl ₂ 8H ₂ O into an aqueous solution with a concentration of 0.5-2.5 mol/L, and add the required alkaline earth metal or rare earth metal water-soluble salts into the zirconium oxychloride aqueous solution One or more of them, then add 20-50 ml of additive polyethylene glycol per liter of zirconium oxychloride aqueous solution, and finally use 0.5-3 mol/L ammonium carbonate or ammonium bicarbonate aqueous solution according to the required amount of 100 ～105% react with the above mixed solution, after fully washing and filtering, obtain a mixture of zirconium carbonate or basic zirconium carbonate and alkaline earth metal, rare earth metal carbonate precipitate; or,

Method 3: Prepare zirconium oxychloride ZrOCl ₂ ·8H ₂ O into an aqueous solution with a concentration of 0.5-2.5 mol/L, and add 100-105% of the required amount to the zirconium oxychloride ZrOCl ₂ ·8H ₂ O aqueous solution Ammonium carbonate or ammonium bicarbonate generates zirconium carbonate or basic zirconium carbonate precipitates, which are washed and filtered until no chloride ions are detected with silver nitrate, and the resulting zirconium carbonate or basic zirconium carbonate precipitates are slurried with water for subsequent use; then Then add excess ammonium bicarbonate to convert zirconium carbonate or basic zirconium carbonate precipitate into ammonium zirconium carbonate, add additive polyethylene glycol to the ammonium zirconium carbonate solution, and heat to 85-95°C to decompose to form zirconium carbonate or basic zirconium carbonate The weight ratio of the additive polyethylene glycol to zirconium carbonate or basic zirconium carbonate precipitate is 40 to 60:1000, and the filtered zirconium carbonate precipitate is slurried with deionized water; then mixed with alkaline earth metal, rare earth metal or aluminum One or more mixtures of oxides, hydroxides, carbonates, or ammonium aluminum carbonate;

Second, the mixture prepared above was stirred and ball milled for 30 to 60 minutes;

Third, spray drying and granulation; using centrifugal or pressure spray drying equipment, the inlet temperature of the heated air for spray drying is 180-300°C, and the outlet temperature is 105-220°C; the powder is collected in the spray drying tank and sieved Afterwards, it is sent for heat treatment, while the fine-grained dry powder is collected by a cyclone separator and a bag filter connected to the spray drying tank, and returned to the next process to be mixed with zirconium carbonate or basic zirconium carbonate, and then ball milled for batching. Spray drying granulation was performed again. The primary particles of the agglomerated powder are nanostructures, the particle size of the aggregates is micron, the main particle size ranges from 10 to 100 μm, and the shape is spherical or quasi-spherical.

Fourth, heat treatment: agglomerated spherical or quasi-spherical powders are heat-treated in an electric furnace at 350-400°C for 3-5 hours, then heated to 700-850°C and kept for 12-16 hours to obtain nano-zirconia ZrO doped with different substances ₂ or nano-rare earth zirconate RE ₂ Zr ₂ O ₇ agglomerated powder with pyrochlore crystal structure, wherein nano-rare earth zirconate RE ₂ Zr ₂ O ₇ only contains rare earth, but does not contain alkaline earth and aluminum elements, RE: The Zr molar ratio is controlled within the range of 1-1.05:1, and these nanostructured zirconium compound powders have a porous structure inside, which is suitable for thermal barrier coating materials.

The alkaline earth metals, rare earth metals and light metal elements doped in the above-mentioned nano-zirconia _ZrO2 are calcium Ca, magnesium Mg, yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium One or more of Er, ytterbium Yb, and aluminum Al.

In the nano-rare earth zirconate RE ₂ Zr ₂ O ₇ agglomerated powder, RE is yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb one or more of two.

When adding aluminum element, mix pseudo-boehmite and boehmite with water, and add 1:1 nitric acid aqueous solution drop by drop to adjust the pH value of the slurry until the pH value is 1.5-4 and becomes a colloid; or Ammonium aluminum carbonate is used as raw material, directly mixed with zirconium carbonate or basic zirconium carbonate, and the aluminum content is 0.5-5% calculated as alumina.

Advantage and positive effect of the present invention:

The present invention uses cheap zirconium oxychloride (ZrOCl ₂ 8H ₂ O) and ammonium carbonate or ammonium bicarbonate as raw materials to obtain zirconium carbonate or basic zirconium carbonate which is easy to wash and has low chloride ion content, and then mixes with alkaline earth metal , rare earth metal, aluminum colloidal hydroxide, carbonate precipitation or one or more of other compounds are mixed, and after stirring ball milling, spray drying granulation, and heat treatment processes, agglomerated nanostructured zirconium compound powder is obtained Products, such as nano zirconia ZrO ₂ doped with different substances or nano rare earth zirconate RE ₂ Zr ₂ O ₇ with pyrochlore crystal structure. These agglomerated nano-zirconium compound powders can also be further processed by plasma spherical densification process to meet different application requirements of materials. The product prepared by the preparation method can meet the requirements of low chloride ion content in the agglomerated powder, the primary particle size is nanometer particle size, and the composition is easy to control, etc., and realizes the low-cost and gentle preparation of the zirconium-containing nano-oxide.

The invention also has the characteristics of wide source of raw materials, strong adaptability of the preparation method, short process, easy scale, low production cost and good product quality. By controlling the decomposition of carbonate, _CO2 gas escapes and leaves fine holes, which is beneficial to obtain porous agglomerated zirconium-containing nano-compound particle powder, which is especially suitable for the preparation of thermal barrier coating materials.

【Detailed ways】:

Example 1:

Precipitate mixing method to prepare doped nano zirconia agglomerated powder. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ 8H ₂ O), dissolve it in 2 liters of distilled water to form a solution with a concentration of zirconium of about 0.75 mol/L, and heat the solution to reach a temperature of 80-85°C; Dissolve 240 g of ammonium bicarbonate in 2 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5 mol/L (or add 150 g of ammonium carbonate to 1 liter of distilled water to make a solution of about 1.5 mol/L ammonium carbonate), Heat it to 40-50°C, add it dropwise to the aqueous solution of zirconium oxychloride, and keep stirring to form a white precipitate of zirconium carbonate or basic zirconium carbonate, and add 15ml of 1:1 ammonia water (concentration about 12.5%), and filter by centrifugation , pulping and washing, repeated several times until no chloride ions are detected with silver nitrate, and the obtained zirconium carbonate or basic zirconium carbonate precipitate is pulped with water for subsequent use.

Weigh 13.5g of yttrium oxide, wet it with 80ml of distilled water in a beaker, heat and stir to 60°C, add 115ml of 12% dilute nitric acid to dissolve, after the dissolution, add 60ml of 1:1 ammonia water dropwise, keep stirring to completely precipitate the solution, and let it stand After 12 hours, the supernatant was sucked out, the sediment yttrium hydroxide was centrifugally filtered, and washed once with 200ml distilled water, after the centrifugal filtration, the yttrium hydroxide was added to the zirconium carbonate or basic zirconium carbonate precipitate water slurry obtained above, Stir and ball mill for 30 to 60 minutes, then send to spray drying for granulation. Centrifugal spray drying equipment is adopted, the inlet temperature of the heated air for spray drying is 260-280°C, and the outlet temperature is 110-125°C; the powder is collected in the spray drying tank, sieved and sent to heat treatment, and the fine-grained dry powder Then use the cyclone separation dust collector and bag dust collector connected to the spray drying tank to collect, return to mix with the next batch of materials, ball mill the ingredients, and spray dry and granulate again. The temperature is 110-120°C. The granulated material is heat-treated at 350-400°C for 3-5 hours in an electric furnace, then heated to 830°C and kept for 12-16 hours to obtain agglomerated nano-zirconia spherical powder doped with 7% yttrium oxide. According to the scanning electron microscope analysis, the original particles of the agglomerated powder are nanostructures, about 30-80nm, the particle size of the aggregates is micron, 90% of the particle size ranges from 10-100μm, and the shape is spherical or quasi-spherical. After screening, it becomes satisfactory. Products with different spraying processes.

Using the same method as above, one of alkaline earth metal calcium Ca or magnesium Mg, rare earth metal lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb One or more oxides, hydroxides, carbonates, according to the ratio of the amount of doping, take 13.5g according to the amount of oxides, replace yttrium oxide as the raw material for yttrium doping, and use the same method for preparing yttrium hydroxide, use nitric acid Dissolve, or directly prepare an aqueous solution with its nitrate, add ammonia water, ammonium carbonate or ammonium bicarbonate in an aqueous solution to obtain hydroxides and carbonates of alkaline earth metals or rare earth metals, and add the above prepared Put the zirconium carbonate or basic zirconium carbonate precipitate into the water slurry after withering the slurry with water, go through agitation and ball milling for 30-60 minutes, send it to spray drying and granulation, the temperature of the inlet of the heating air is 180-300°C, and the temperature of the outlet is 105-220°C. After the granular material is heat-treated at 350-400°C for 3-5 hours in an electric furnace, the temperature is raised to 830°C and kept for 12-16 hours to obtain agglomerated nano-zirconia spherical particles doped with a different alkaline earth metal and a rare earth metal content of 7%. Powder, or two or two of alkaline earth metal calcium Ca or magnesium Mg, rare earth metal lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb Above, 13.5g of the total weight of converted oxides is used as a raw material for doping, and the same method as above can be used to obtain doped alkaline earth metal calcium Ca or magnesium Mg, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, Two or more nanometer zirconia spherical powders of samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. In the prepared doped nano zirconia spherical powder, the weight ratio of one or more kinds of alkaline earth metals and rare earth metals to the weight ratio of the nano zirconia agglomerated powder can be adjusted in the range of 0.1-21% as required.

When adding aluminum elements, weigh 3.8g of pseudo-boehmite, pour it into a beaker, add 60ml of distilled water, stir and mix well, adjust the pH value of the water to 1.5-4 with 1:1 nitric acid solution, and become a jelly , and then poured into the water slurry of yttrium hydroxide and zirconium carbonate or basic zirconium carbonate precipitate prepared above, according to the same process parameters as above, after stirring ball milling, spray drying granulation, and heat treatment, aluminum-doped approx. 1.2%, nano zirconia agglomerated powder doped with yttrium oxide about 7%. The above-mentioned yttrium hydroxide can also be replaced or co-doped with other alkaline earth metals and rare earth metal compounds by the same method to prepare nano-zirconia agglomerated powder doped with one or more alkaline earth metals and rare earth metal elements. Pseudo-boehmite can be replaced by boehmite, aluminum hydroxide or aluminum ammonium carbonate raw materials to prepare aluminum-doped raw materials, and then mixed with zirconium carbonate or basic zirconium carbonate after slurrying with water and one of the above alkaline earth metals or rare earth metals One or more precipitation mixtures are mixed again, and after the same stirring ball milling, spray drying granulation, and heat treatment processes, the nano-zirconia agglomerated powder doped with one or more of alkaline earth metals, rare earth metals, and aluminum elements is prepared.

Example 2:

Precipitate mixing method to prepare doped nano RE ₂ Zr ₂ O ₇ agglomerated powder. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ 8H ₂ O), dissolve it in 2 liters of distilled water to form a solution with a concentration of zirconium of about 0.75 mol/L, and heat the solution to reach a temperature of 80-85°C; Dissolve 240 g of ammonium bicarbonate in 2 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5 mol/L (or add 150 g of ammonium carbonate to 1 liter of distilled water to make a solution of about 1.5 mol/L ammonium carbonate), Heat it to 40-50°C, add it dropwise to the aqueous solution of zirconium oxychloride, and keep stirring to form a white precipitate of zirconium carbonate or basic zirconium carbonate, and add 15ml of 1:1 ammonia water (concentration about 12.5%), and filter by centrifugation , pulping and washing, repeated several times until no chloride ions are detected with silver nitrate, and the obtained zirconium carbonate or basic zirconium carbonate precipitate is pulped with water for subsequent use.

Weigh 239g of lanthanum oxide, wet it with 1000ml of distilled water in a beaker, heat and stir to 65°C, add 2490ml of 12% dilute nitric acid to dissolve, after the dissolution, keep stirring and dropwise add 1:1 ammonia water until there is no precipitation, and make the solution Complete precipitation, stand still for 18 hours, suck out the supernatant, centrifugally filter the precipitated lanthanum hydroxide, and wash twice with distilled water, after centrifugal filtration, add the lanthanum hydroxide to the above-mentioned prepared zirconium carbonate or basic zirconium carbonate precipitate water slurry After stirring and ball milling for 120-180 minutes, it is spray-dried and granulated. The inlet temperature of the heating air is 180-300°C, and the outlet temperature is 105-220°C. After heat treatment at 350-400°C for 3-5 hours in an electric furnace, the temperature was raised to 800°C and kept for 12-16 hours to obtain agglomerated La ₂ Zr ₂ O ₇ nanometer zirconia spherical powder, in which La:Zr (molar ratio) controlled In the range of 1-1.05:1.

When 332g of cerium carbonate, 243g of neodymium oxide, 163g of yttrium oxide, 252g of samarium oxide, 254g of europium oxide, 262g of gadolinium oxide, 269g of dysprosium oxide, 276g of erbium oxide, or 285g of ytterbium oxide were used to replace lanthanum oxide respectively, the same method as above was used to prepare RE ₂ Zr ₂ O ₇ nanometer zirconia spherical powder of other rare earth elements is sieved to become a product, wherein the RE:Zr (molar ratio) is controlled within the range of 1-1.05:1. The raw materials used can also be rare earth hydroxides and rare earth carbonates, and according to the ratio of RE:Zr (molar ratio) of 1 to 1.05:1, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium can be doped at the same time Two or more of Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. If La:Y:Ce=7:2:1 ratio is mixed with three rare earth element oxides of lanthanum La, yttrium Y, and cerium Ce at the same time, then use 167.7g of lanthanum oxide, 32.6g of yttrium oxide, and 33.2g of cerium carbonate to mix, Instead of the lanthanum oxide raw material, the same method as above was used to obtain agglomerated La _0.7 Y _0.2 Ce _0.1 Zr ₂ O ₇ nanometer zirconia spherical powder doped with oxide. RE in RE ₂ Zr ₂ O ₇ does not include alkaline earth metals calcium Ca, magnesium Mg, and aluminum Al.

Example 3

Preparation of doped nano zirconia agglomerated powder by co-precipitation. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ 8H ₂ O), dissolve it in 2 liters of distilled water to form a solution containing zirconium with a concentration of about 0.75 mol/L, heat the solution to a temperature of 60-65 °C; Take 239g of lanthanum oxide, wet it with 1000ml of distilled water in a beaker, heat and stir to 65°C, add 2490ml of 12% dilute nitric acid to dissolve, after the dissolution, keep stirring and dropwise add 1:1 ammonia water until there is no precipitation, so that the solution is completely Precipitate, stand still for 18 hours, suck out the supernatant, centrifugally filter the precipitated lanthanum hydroxide, and wash twice with distilled water, add the lanthanum hydroxide to the zirconium carbonate or basic zirconium carbonate precipitate water slurry prepared above after centrifugal filtration , after stirring and ball milling for 120-180 minutes, it is sent to spray drying for granulation. The inlet temperature of the heating air is 260-280°C, and the outlet temperature is 130-140°C. , heating up to 780° C. and keeping it warm for 12-16 hours to obtain agglomerated La ₂ Zr ₂ O ₇ nanometer zirconia spherical powder, wherein La:Zr (molar ratio) is controlled within the range of 1-1.05:1.

Add dropwise 1:1 ammonia water to adjust the pH value of the yttrium nitrate solution to 1-1.5, then add it to the zirconium oxychloride aqueous solution, heat the solution to a temperature of 60-80°C, then add 50ml polyethylene glycol (PEG), Stir evenly, and take 240g of ammonium bicarbonate and dissolve it in 2 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5mol/L (or add 150g of ammonium carbonate to one liter of distilled water to prepare a portion of about 1.5mol/L ammonium carbonate solution), heated to 40-50°C, quickly pour the ammonium carbonate (or ammonium bicarbonate) solution into the mixed solution of zirconium oxychloride and yttrium nitrate to produce zirconium carbonate or basic zirconium carbonate and yttrium hydroxide white Precipitate the mixture, stand still for 24 hours, suck out the supernatant, and after the lower sediment is fully washed and filtered, the filter residue is transferred to a ball mill, added water to adjust the slurry, stirred and ball milled for 30-60 minutes, and sent to spray drying for granulation. The temperature of the heating air inlet is 230～260℃, the outlet temperature is 130～140℃, the granulated material is first heat-treated in the electric furnace at 350～400℃ for 3～5 hours, then the temperature is raised to 800℃ and kept for 12～16 hours to obtain agglomerated yttrium-doped nano-zirconia , become the product after sieving.

The metal yttrium element in the above method can also be replaced by other metal elements, such as calcium Ca, magnesium Mg in alkaline earth metals or rare earth metals, or lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium One or more oxides, hydroxides, or carbonates of Gd, dysprosium Dy, erbium Er, and ytterbium Yb, measured according to the weight of 13.5g of oxides, dissolved in nitric acid or directly with its nitrates, added dropwise 1: 1 ammonia water to adjust the pH value of the yttrium nitrate solution to 1-1.5, then add it to the zirconium oxychloride aqueous solution, and use the same method as above to obtain one or more of the above-mentioned alkaline earth metals and rare earth metals. Nano zirconia agglomerated powder of alkaline earth metals and rare earth metals, the weight ratio of one or more kinds of alkaline earth metals and rare earth metals to the weight ratio of nano zirconia agglomerated powder can be adjusted from 0.1 to 21% according to needs.

When adding aluminum elements, weigh 4.9g of aluminum hydroxide, pour it into a beaker, add 80ml of distilled water, stir and mix, add dropwise 12% dilute nitric acid aqueous solution until the aluminum hydroxide is completely dissolved to form an aluminum nitrate solution, and then use 1 : 1 dilute ammonia solution to adjust the pH value of the aluminum nitrate solution to about 1.5, then pour it into the water slurry of the above-mentioned prepared yttrium hydroxide and zirconium carbonate or basic zirconium carbonate precipitate, press the above-mentioned same process parameters, through After stirring ball milling, spray drying and granulation, and heat treatment, the nano-zirconia agglomerated powder doped with about 1.2% of aluminum and about 7% of yttrium oxide is obtained. The above-mentioned yttrium hydroxide can also be replaced or co-doped with other alkaline earth metals and rare earth metal compounds by the same method to prepare nano-zirconia agglomerated powder doped with one or more alkaline earth metals and rare earth metal elements. Aluminum hydroxide can be replaced by pseudo-boehmite, boehmite, aluminum hydroxide or aluminum ammonium carbonate raw materials to prepare aluminum-doped raw materials, and then mixed with zirconium carbonate or basic zirconium carbonate after slurrying with water and the above alkaline earth metals or rare earth One or more precipitation mixtures in the metal are mixed again, and after the same stirring ball milling, spray drying granulation, and heat treatment processes, the nano-zirconia aggregates doped with one or more of alkaline earth metals, rare earth metals and aluminum elements are prepared. powder.

Example 4

Co-precipitation method to prepare nano RE ₂ Zr ₂ O ₇ agglomerated powder. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ 8H ₂ O), dissolve it in 2 liters of distilled water to form a solution containing zirconium with a concentration of about 0.75 mol/L, and heat the solution to reach a temperature of 80-85 °C; Weigh 239g of lanthanum oxide, moisten it with 1000ml of distilled water in a beaker, add 2490ml of 12% dilute nitric acid to dissolve, heat and stir to 65°C after dissolution, add 1:1 ammonia water dropwise until the pH of the solution is about 1.2, and form an aqueous solution of lanthanum nitrate , mixed with an aqueous solution of zirconium oxychloride. In addition, dissolve 480 g of ammonium bicarbonate in 4 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5 mol/L (or add 300 g of ammonium carbonate to 2 liters of distilled water to prepare a solution of about 1.5 mol/L ammonium carbonate) , heated to 40-50°C, add it dropwise to the aqueous solution of zirconium oxychloride and lanthanum nitrate, stir continuously to make the precipitation uniform, and generate a white precipitate mixture of zirconium carbonate or basic zirconium carbonate and lanthanum hydroxide, stand still for 24 After hours, suck out the supernatant, and after the lower sediment is fully washed and filtered, the filter residue is transferred to a ball mill, mixed with water, stirred and ball milled for 30-60 minutes, and then sent to spray drying for granulation. The temperature of the heating air inlet is 210-250°C. The outlet temperature is 105-115°C. The granulated material is first heat-treated in an electric furnace at 350-400°C for 5 hours, then heated to 780°C and kept for 14 hours to obtain agglomerated nano La ₂ Zr ₂ O ₇ agglomerated powder. According to scanning electron microscope analysis, the original particles of the agglomerated powder are nanostructures, about 35-75nm, and the particle size of the agglomerates is micron, with 95% of the particle size ranging from 10-100μm. After sieving, it becomes a product. Wherein La:Zr (molar ratio) is controlled in the range of 1～1.05:1.

When 332g of cerium carbonate, 243g of neodymium oxide, 163g of yttrium oxide, 252g of samarium oxide, 254g of europium oxide, 262g of gadolinium oxide, 269g of dysprosium oxide, 276g of erbium oxide, or 285g of ytterbium oxide were used to replace lanthanum oxide respectively, the same method as above was used to prepare RE ₂ Zr ₂ O ₇ nanometer zirconia spherical powder of other rare earth elements is sieved to become a product, wherein the RE:Zr (molar ratio) is controlled within the range of 1-1.05:1. The raw materials used can also be rare earth hydroxides and rare earth carbonates, and according to the ratio of RE:Zr (molar ratio) of 1 to 1.05:1, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium can be doped at the same time Two or more of Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. If the three rare earth element oxides of lanthanum La, gadolinium Gd and neodymium Gd are mixed at the same time according to the ratio of La:Gd:Nd=80:15:5, then 191.7g of lanthanum oxide, 39.3g of gadolinium oxide and 12.2g of neodymium oxide are mixed. Instead of the lanthanum oxide raw material, the same method as above was used to obtain agglomerated nano La _0.8 Gd _0.15 Nd _0.05 Zr ₂ O ₇ spherical powder containing multiple rare earth elements. RE in RE ₂ Zr ₂ O ₇ does not include alkaline earth metals calcium Ca, magnesium Mg, and aluminum Al.

Example 5

The ammonium zirconium carbonate pyrolysis method is used to prepare zirconium carbonate precipitate, and then doped with nanometer zirconium oxide agglomerated powder. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ ·8H ₂ O), dissolve in 2 liters of distilled water to prepare a solution containing zirconium with a concentration of about 0.75 mol/L, and heat the solution to reach a temperature of 75-80°C. In addition, dissolve 240g of ammonium bicarbonate in 2 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5mol/L (or add 150g of ammonium carbonate to 1 liter of distilled water to prepare a solution of about 1.5mol/L ammonium carbonate) , heated to 40-50°C, added dropwise to an aqueous solution of zirconium oxychloride, and kept stirring to generate white zirconium carbonate or basic zirconium carbonate precipitate, and added H into 15ml of 1:1 ammonia water (concentration about 12.5%), Centrifugal filtration, pulping and washing are repeated several times until no chloride ion is detected with silver nitrate, and the obtained zirconium carbonate or basic zirconium carbonate precipitate is pulped with water for later use. After the obtained zirconium carbonate or basic zirconium carbonate precipitate is slurried with water, add a solution of ammonium bicarbonate with a concentration of 1.5mol/L, and keep stirring to make the solid particle solution in the water slurry react to form an ammonium zirconium carbonate solution. Add the additive polyethylene glycol (according to the ratio of 1000g zirconium carbonate or basic zirconium carbonate precipitate adding 50g) to the zirconium ammonium solution, heat to 95°C and decompose to generate zirconium carbonate, after standing still for 24 hours, suck out the supernatant and centrifugal filter The sediment at the bottom is washed with distilled water at 75-80° C., and the precipitate is obtained after repeated centrifugal filtration and washing twice. The zirconium carbonate precipitate is slurried with distilled water (the solid content is maintained at 15-25%).

Weigh 13.5g of gadolinium oxide, wet it with 80ml of distilled water in a beaker, heat and stir to 60°C, add 85ml of 12% dilute nitric acid to dissolve, after the dissolution, add 40ml of 1:1 ammonia water dropwise, keep stirring to completely precipitate the solution, and let it stand After 16 hours, suck out the supernatant, centrifugally filter the precipitate gadolinium hydroxide, and wash once with 200ml distilled water. zirconium carbonate water slurry, stirred and ball milled for 50 minutes, and sent to spray drying for granulation. The pressure type spray drying equipment is adopted, the inlet temperature of the heated air for spray drying is 280-300°C, and the outlet temperature is 105-115°C; the powder is collected in the spray drying tank, sieved and sent to heat treatment, and the fine-grained dry powder Then use the cyclone separation dust collector and bag dust collector connected to the spray drying tank to collect, return to mix with the next batch of materials, ball mill the ingredients, and spray dry and granulate again. The granulated material is heat-treated at 350-400°C for 3 hours in an electric furnace, then heated to 800-820°C and kept for 15 hours to obtain agglomerated nano-zirconia spherical powder doped with 7% gadolinia. According to the scanning electron microscope analysis, the original particles of the agglomerated powder are nanostructures, about 40-70nm, the particle size of the aggregates is micron, 92% of the particle size ranges from 10-100μm, and the shape is spherical or quasi-spherical. After screening, it becomes satisfactory Products with different spraying processes.

Using the same method as above, one or A variety of oxides, hydroxides, carbonates, according to the ratio of the amount of addition, get 13.5g according to the amount of oxides, and replace yttrium oxide as the raw material for yttrium doping, and use the same method for preparing yttrium hydroxide to dissolve with nitric acid, Or directly prepare an aqueous solution with its nitrate, add an aqueous solution of ammonia, ammonium carbonate or ammonium bicarbonate to obtain hydroxides and carbonates of alkaline earth metals or rare earth metals, add the prepared water to adjust The zirconium carbonate or basic zirconium carbonate precipitate water slurry after the slurry is stirred and ball-milled for 30-60 minutes, and sent to spray drying for granulation. After heat treatment at 350-400°C for 3-5 hours in an electric furnace, the temperature is raised to 800-820°C and kept for 12-16 hours to obtain agglomerated nano-zirconia doped with a different oxidized alkaline earth metal and a rare earth metal content of 7%. Spherical powder, or two or two of alkaline earth metal calcium Ca or magnesium Mg, rare earth metal lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb Above, 13.5g of the total weight of converted oxides is used as a raw material for doping, and the same method as above can be used to obtain doped alkaline earth metal calcium Ca or magnesium Mg, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, Two or more nanometer zirconia spherical powders of samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. In the prepared doped nano zirconia spherical powder, the weight ratio of one or more kinds of alkaline earth metals and rare earth metals to the weight ratio of the nano zirconia agglomerated powder can be adjusted in the range of 0.1-21% as required. According to scanning electron microscope analysis, the original particles of the agglomerated powder are nanostructures, about 30-80nm, and the particle size of the agglomerates is micron, 91% of which are in the range of 10-100μm, and the shape is spherical or quasi-spherical. Products with different spraying processes.

When adding aluminum elements, weigh 3.8g of pseudo-boehmite, pour it into a beaker, add 60ml of distilled water, stir and mix well, adjust the pH value of the water to 1.5-4 with 1:1 nitric acid solution, and become a jelly , and then poured into the water slurry of gadolinium hydroxide and zirconium carbonate or basic zirconium carbonate precipitate prepared above, according to the same process parameters as above, after stirring ball milling, spray drying granulation, and heat treatment, aluminum-doped approx. 1.2%, nanometer zirconia agglomerated powder doped with gadolinia about 7%. The above-mentioned gadolinium hydroxide can also be replaced or co-doped with other alkaline earth metals and rare earth metal compounds to prepare nano-zirconia agglomerated powder doped with one or more alkaline earth metals and rare earth metal elements. Pseudo-boehmite can be replaced by boehmite, aluminum hydroxide or aluminum ammonium carbonate raw materials to prepare aluminum-doped raw materials, and then mixed with zirconium carbonate or basic zirconium carbonate after slurrying with water and one of the above alkaline earth metals or rare earth metals One or more precipitation mixtures are mixed again, and after the same stirring ball milling, spray drying granulation, and heat treatment processes, the nano-zirconia agglomerated powder doped with one or more of alkaline earth metals, rare earth metals, and aluminum elements is prepared.

Example 6

The ammonium zirconium carbonate pyrolysis method is used to prepare zirconium carbonate precipitate, and then doped with nanometer zirconium oxide agglomerated powder. Weigh 520 g of zirconium oxychloride (ZrOCl ₂ ·8H ₂ O), dissolve in 2 liters of distilled water to prepare a solution containing zirconium with a concentration of about 0.75 mol/L, and heat the solution to reach a temperature of 75-80°C. In addition, dissolve 240g of ammonium bicarbonate in 2 liters of distilled water to make a solution containing ammonium bicarbonate with a concentration of about 1.5mol/L (or add 150g of ammonium carbonate to 1 liter of distilled water to prepare a solution of about 1.5mol/L ammonium carbonate) , heated to 40-50°C, added dropwise to an aqueous solution of zirconium oxychloride, and kept stirring to form a white precipitate of zirconium carbonate or basic zirconium carbonate, and added 15ml of 1:1 ammonia water (concentration about 12.5%), centrifuged Filtration, pulping and washing are repeated several times until no chloride ion is detected with silver nitrate, and the obtained zirconium carbonate or basic zirconium carbonate precipitate is pulped with water for later use. After the obtained zirconium carbonate or basic zirconium carbonate precipitate is slurried with water, add a solution of ammonium bicarbonate with a concentration of 1.5mol/L, and keep stirring to make the solid particle solution in the water slurry react to form an ammonium zirconium carbonate solution. Add the additive polyethylene glycol (according to the ratio of 1000g zirconium carbonate or basic zirconium carbonate precipitate adding 50g) to the zirconium ammonium solution, heat to 95°C and decompose to generate zirconium carbonate, after standing still for 24 hours, suck out the supernatant and centrifugal filter The sediment at the bottom is washed with distilled water at 75-80° C., and the precipitate is obtained after repeated centrifugal filtration and washing twice. The zirconium carbonate precipitate is slurried with distilled water (the solid content is maintained at 15-25%).

Weigh 252g of samarium oxide, moisten it with 1000ml of distilled water in a beaker, heat and stir to 65°C, add 2490ml of 12% dilute nitric acid to dissolve, after the dissolution, keep stirring and dropwise add 1:1 ammonia water until there is no precipitation, and make the solution Precipitate completely, stand still for 18 hours, suck out the supernatant, centrifugally filter the precipitated samarium hydroxide, wash twice with distilled water, add samarium hydroxide to the above prepared zirconium carbonate or basic zirconium carbonate precipitate water slurry after centrifugal filtration After stirring and ball milling for 120-180 minutes, it is spray-dried and granulated. The inlet temperature of the heating air is 220-260°C, and the outlet temperature is 110-120°C. The granulated material is heat-treated in an electric furnace at 350-400°C for 3-5 hours. Afterwards, the temperature is raised to 800° C. and kept for 12 to 16 hours to obtain agglomerated Sm ₂ Zr ₂ O ₇ nanometer zirconia spherical powder, wherein the Sm:Zr (molar ratio) is controlled within the range of 1 to 1.05:1.

When respectively using 332g of cerium carbonate, 243g of neodymium oxide, 163g of yttrium oxide, 239g of lanthanum oxide, 254g of europium oxide, 262g of gadolinium oxide, 269g of dysprosium oxide, 276g of erbium oxide, or 285g of ytterbium oxide instead of samarium oxide, the same method as above was used to prepare RE ₂ Zr ₂ O ₇ nanometer zirconia spherical powder of other rare earth elements is sieved to become a product, wherein the RE:Zr (molar ratio) is controlled within the range of 1-1.05:1. The raw materials used can also be rare earth hydroxides and rare earth carbonates, and according to the ratio of RE:Zr (molar ratio) of 1 to 1.05:1, lanthanum La, yttrium Y, cerium Ce, neodymium Nd, samarium can be doped at the same time Two or more of Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. If the three rare earth element oxides of lanthanum La, yttrium Y, and cerium Ce are mixed at the same time according to the ratio of Sm:La:Y=80:1:1, 202g of samarium oxide, 23.9g of lanthanum oxide, and 16.3g of yttrium oxide are used to replace As for the samarium oxide raw material, use the same method as above to obtain agglomerated Sm _0.8 Y _0.1 Ce _0.1 Zr ₂ O ₇ nanometer zirconia spherical powder doped with oxides. According to scanning electron microscope analysis, the original particles of the agglomerated powder are nanostructures, about 35-90nm, and the particle size of the agglomerates is micron, 93% of which are in the range of 10-100μm, and the shape is spherical or quasi-spherical. After screening, it becomes satisfactory Products with different spraying processes. RE in RE ₂ Zr ₂ O ₇ does not include alkaline earth metals calcium Ca, magnesium Mg, and aluminum Al.

Claims (4)

1. A method for preparing a nanometer zirconium-containing thermal barrier coating material, characterized in that the method is through the following steps: First, using cheap zirconium oxychloride as a raw material, first prepare a mixture of zirconium carbonate or basic zirconium carbonate and other elements, the specific method is as follows: Method 1: Prepare zirconium oxychloride ZrOCl ₂ ·8H ₂ O into an aqueous solution with a concentration of 0.5-2.5 mol/L, and use ammonium carbonate or ammonium bicarbonate as a precipitating agent to prepare an aqueous solution with a concentration of 0.5-3 mol/L. Ammonium carbonate or ammonium bicarbonate aqueous solution is added to the zirconium oxychloride aqueous solution according to the required amount of 100-105%, and the zirconium carbonate or basic zirconium carbonate precipitate which is easy to wash and has low chloride ion content is obtained by precipitation. Wash and filter until no chloride ions can be detected with silver nitrate, then mix the obtained zirconium carbonate or basic zirconium carbonate precipitate with water for later use; then mix with alkaline earth metal, rare earth metal or aluminum oxide, hydroxide, Salt, or one or more of ammonium aluminum carbonate mixed at a total content of 0.1 to 21%; or, Method 2: Prepare zirconium oxychloride ZrOCl ₂ 8H ₂ O into an aqueous solution with a concentration of 0.5-2.5 mol/L, and add the required alkaline earth metal or rare earth metal water-soluble salts into the zirconium oxychloride aqueous solution One or more of them, then add 20-50ml of additive polyethylene glycol per liter of zirconium oxychloride aqueous solution, and finally use ammonium carbonate or ammonium bicarbonate aqueous solution with a concentration of 0.5-3mol/L according to the required amount of 100-50ml 105% react with the above mixed solution, after fully washing and filtering, obtain a mixture of zirconium carbonate or basic zirconium carbonate and alkaline earth metal, rare earth metal carbonate precipitate; or, Method 3: Prepare zirconium oxychloride ZrOCl ₂ ·8H ₂ O into an aqueous solution with a concentration of 0.5-2.5 mol/L, and add 100-105% of the required amount to the zirconium oxychloride ZrOCl ₂ ·8H ₂ O aqueous solution Ammonium carbonate or ammonium bicarbonate generates zirconium carbonate or basic zirconium carbonate precipitate, which is washed and filtered until no chloride ion is detected with silver nitrate, and the resulting zirconium carbonate or basic zirconium carbonate precipitate is slurried with water for subsequent use; Then add excess ammonium bicarbonate to convert zirconium carbonate or basic zirconium carbonate precipitate into ammonium zirconium carbonate, add additive polyethylene glycol to the ammonium zirconium carbonate solution, heat to 85-95°C to decompose to generate zirconium carbonate or basic zirconium carbonate Zirconium, the weight ratio of the additive polyethylene glycol to zirconium carbonate or basic zirconium carbonate precipitate is 40-60:1000, and the filtered zirconium carbonate precipitate is slurried with deionized water; then mixed with alkaline earth metal, rare earth metal or aluminum One or more mixtures of oxides, hydroxides, carbonates, or ammonium aluminum carbonate; Second, the mixture prepared above was stirred and ball milled for 30 to 60 minutes; Third, spray drying and granulation; using centrifugal or pressure spray drying equipment, the inlet temperature of the heated air for spray drying is 180-300°C, and the outlet temperature is 105-220°C; the powder is collected in the spray drying tank and sieved Afterwards, heat treatment is sent, while the fine-grained dry powder is collected by the cyclone separator and bag filter connected to the spray drying tank, returned to mix with the next batch of materials, ball milled for batching, and then spray-dried and granulated again; The primary particle of the agglomerated powder is nano-structure, the particle size of the aggregate is micron, the main particle size ranges from 10 to 100 μm, and the shape is spherical or quasi-spherical; Fourth, heat treatment. After heat treatment at 350-400°C for 3-5 hours in an electric furnace, the temperature is raised to 700-850°C and kept for 12-16 hours to obtain nano-zirconia ZrO ₂ or pyrochlore crystals doped with different substances Nano-structured rare earth zirconate RE ₂ Zr ₂ O ₇ agglomerated powder, wherein the nano-rare earth zirconate RE ₂ Zr ₂ O ₇ only contains rare earth, but does not contain alkaline earth and aluminum elements, and the molar ratio of RE:Zr is controlled at 1~ Within the range of 1.05:1, these nanostructured zirconium compound powders have a porous structure inside and are suitable for thermal barrier coating materials. 2. preparation method according to claim 1 is characterized in that the alkaline earth metal, rare earth metal and light metal element of doping in the nanometer zirconia _ZrO are calcium Ca, magnesium Mg, yttrium Y, lanthanum La, cerium Ce, neodymium Nd , samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, ytterbium Yb, and one or more of aluminum Al. 3. The preparation method according to claim 1, characterized in that in the nano-rare earth zirconate RE ₂ Zr ₂ O ₇ agglomerated powder, RE is yttrium Y, lanthanum La, cerium Ce, neodymium Nd, samarium Sm, europium One or more of Eu, gadolinium Gd, dysprosium Dy, erbium Er, or ytterbium Yb. 4. The preparation method according to claim 1, characterized in that when the aluminum element is added, the pseudo-boehmite, boehmite, and aluminum hydroxide are mixed with water, and the aqueous nitric acid solution of 1:1 is added dropwise Adjust the pH value of the slurry until it becomes colloidal when the pH value is 1.5-4; or use ammonium aluminum carbonate as a raw material and directly mix it with zirconium carbonate or basic zirconium carbonate, and the aluminum content is 0.5-5% calculated as alumina.