CN108640151B - Aluminum-containing zirconium oxide hollow microsphere and preparation method thereof - Google Patents
Aluminum-containing zirconium oxide hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aluminum-containing zirconia hollow microsphere, which comprises an aluminum element and a zirconium element in a molar ratio of (1-4) to 8, wherein the diameter of the aluminum-containing zirconia hollow microsphere is 0.1-10 mu m. The invention also discloses a method for preparing the aluminum-containing zirconium oxide hollow microspheres, which comprises the following steps: uniformly mixing an aluminum precursor, a zirconium precursor, urea and strong acid in ethanol to form a clear solution; placing the clear solution in a closed reaction kettle, carrying out solvothermal reaction for 6-18 h at 160-200 ℃, cooling, collecting white precipitate in a product, washing and drying; calcining for 1-4 h at 800-1000 ℃. The aluminum element is introduced into the zirconia hollow microspheres, so that the diffusion rate of the zirconia at high temperature is effectively reduced, the hollow microspheres are still stable at the temperature of over 1300 ℃, the introduction process of the aluminum element is simple, the cost of raw materials is low, and the prepared aluminum-containing zirconia hollow microspheres have stable structures and good dispersibility.
Description
Technical Field
The invention belongs to the field of heat insulation materials, and particularly relates to an aluminum-containing zirconium oxide hollow microsphere and a preparation method thereof.
Background
The zirconia hollow sphere has the characteristics of low density, high specific surface area, low thermal conductivity, good chemical stability, good heat resistance and the like, and has wide application prospect in the field of heat insulation. The zirconia hollow sphere is mostly applied to preparing raw materials of thermal barrier coatings or block porous ceramics in the field of thermal insulation, and the prepared thermal insulation materials all show excellent thermal insulation performance.
The particle size and temperature resistance of the zirconia hollow sphere seriously affect the heat insulation performance of the final product. Generally, when the porosity of the thermal barrier coating or the bulk porous ceramic is constant, the smaller the diameter of the zirconia hollow sphere used as the raw material is, the lower the thermal conductivity of the product is. This is because when the porosity of the material is constant, the reduction of the diameter of the zirconia hollow spheres will result in an increase of the total internal interfacial area. The increase of the internal interface area can reduce the heat radiation of the material, greatly prolong the total transmission route of the heat in the solid phase and reduce the heat conduction of the material. Therefore, the smaller the diameter of the zirconia hollow sphere is, the better the heat insulation performance of the prepared heat insulation material is. However, the heat resistance of the zirconia hollow spheres with small particle size is generally poor, and as shown in patent applications with publication numbers of CN103086700A and CN1259453C, zirconia hollow microspheres with the diameter of 10-150 μm are used as raw materials to prepare thermal barrier coatings, and the prepared thermal barrier coatings meet basic performance requirements. The patent application with publication number CN107805065A uses zirconia hollow microspheres with the diameter of 1-5 μm as raw materials to prepare the porous ceramic with high porosity, low density and excellent heat-insulating property by the gel injection molding technology. The heat insulation material prepared by the two processes has good heat insulation performance, but the used zirconia hollow microspheres have poor high temperature resistance which is usually lower than 1200 ℃, so the use of the zirconia hollow microspheres in a higher temperature environment is limited. Therefore, the research on the high-temperature resistant zirconia hollow microspheres is particularly important for the application of the high-temperature resistant zirconia hollow microspheres in the field of high-temperature heat insulation.
Disclosure of Invention
The invention aims to provide the aluminum-containing zirconia hollow microsphere with stable structure and excellent high temperature resistance.
The invention also aims to provide a method for preparing the aluminum-containing zirconia hollow microspheres, which has low raw material cost and simple process.
The technical scheme is as follows: the invention provides an aluminum-containing zirconia hollow microsphere, which comprises an aluminum element and a zirconium element in a molar ratio of (1-4) to 8, wherein the diameter of the aluminum-containing zirconia hollow microsphere is 0.1-10 mu m.
Preferably, the aluminum-containing zirconia hollow microsphere consists of alumina and zirconia, the diameter is 0.1-5 μm, and the wall thickness is 150-250 nm. The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
1) uniformly mixing an aluminum precursor, a zirconium precursor, urea and strong acid in ethanol to form a clear solution;
2) placing the clear solution prepared in the step 1) in a closed reaction kettle, carrying out solvothermal reaction for 6-18 h at 160-200 ℃, cooling, collecting white precipitate in a product, washing and drying;
3) calcining the product dried in the step 2) at 800-1000 ℃ for 1-4 h.
The invention also provides a method for preparing the aluminum-containing zirconia hollow microspheres, which comprises the following steps:
1) uniformly mixing an aluminum precursor, a zirconium precursor, urea and strong acid in ethanol to form a clear solution;
2) placing the clear solution prepared in the step 1) in a closed reaction kettle, carrying out solvothermal reaction for 6-18 h at 160-200 ℃, cooling, collecting white precipitate in a product, washing and drying;
3) calcining the product dried in the step 2) at 800-1000 ℃ for 1-4 h.
In the process of solvothermal reaction, urea can be hydrolyzed to release hydroxide ions, so that the pH of a reaction system is adjusted, the strong acid catalyzes ethanol for dehydration to generate tiny ether oil drops in situ, and an aluminum precursor and a zirconium precursor are selectively deposited on the surfaces of the tiny ether oil drops to form hollow spheres consisting of the aluminum precursor and the zirconium precursor; removing organic matters and adsorbed water in the hollow sphere by calcination, and converting an aluminum precursor and a zirconium precursor into aluminum oxide and zirconium oxide to obtain the stable aluminum-containing zirconium oxide hollow microsphere.
In the step 1), the molar ratio of an aluminum precursor, a zirconium precursor and urea is (1-4) to 8 to (12-24), the aluminum precursor is one or a mixture of more of aluminum nitrate, aluminum chloride, aluminum silicate, aluminum sulfate and aluminum sol, the zirconium precursor is one or a mixture of more of zirconium oxychloride, n-butyl zirconium and basic zirconium carbonate, the volume ratio of ethanol and strong acid is (2-8) to 1, the strong acid is one or a mixture of more of hydrochloric acid, nitric acid and sulfuric acid, the concentration of hydrogen ions in the strong acid is 10-15 mol/L, the ethanol is used as a reaction solvent, the adding amount of the ethanol is enough to fully dissolve the aluminum precursor, the zirconium precursor and the urea, preferably, the concentration of the zirconium precursor in a clear solution is 0.05-0.15 mol/L, and in addition, the dissolution of the aluminum precursor, the zirconium precursor and the urea in the ethanol can be accelerated by ultrasonic and/or heating and stirring at 60-80 ℃ to form the clear solution.
In the step 2), the washing liquid used for washing is water or absolute ethyl alcohol, and the drying is carried out for 24-48 h at the temperature of 60-100 ℃.
Has the advantages that: according to the invention, aluminum element is introduced into the zirconia hollow microsphere, and the introduction of the aluminum element effectively reduces the diffusion rate of the zirconia at high temperature, so that the hollow microsphere is still stable at the temperature of more than 1300 ℃, and the problem that the zirconia hollow microsphere prepared by the prior art is not high-temperature resistant is solved. In addition, the method has the advantages of simple introduction process of the aluminum element and low cost of raw materials, and the prepared aluminum-containing zirconium oxide hollow microspheres have stable structures and good dispersibility, thereby realizing breakthrough for the use of the zirconium oxide hollow microspheres in higher temperature environments.
Drawings
FIG. 1(a) is an SEM image of aluminum-containing zirconia hollow microspheres prepared in example 2; FIG. 1(b) is an SEM photograph of aluminum-containing zirconia hollow microspheres prepared in example 2 after high temperature treatment at 1300 ℃;
FIG. 2 is an EDS diagram of aluminum-containing zirconia hollow microspheres prepared in example 2;
FIG. 3(a) is an SEM image of zirconium oxide hollow microspheres without aluminum oxide prepared by a comparative example; FIG. 3(b) is an SEM image of aluminum-free zirconia hollow microspheres prepared in the comparative example after high temperature treatment at 1300 ℃.
Detailed Description
Example 1
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.008mol of aluminum nitrate, 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in a 160 ℃ oven for 12h, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 2
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.004mol of aluminum nitrate, 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle for 12h in a 160 ℃ oven, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 3
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.002mol of aluminum nitrate, 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in a 160 ℃ oven for 12h, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 4
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.004mol of aluminum nitrate, 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle for 18h in a 160 ℃ oven, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 5
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.004mol of aluminum nitrate, 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in a 200 ℃ oven for 18h, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 6
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.004mol of aluminum chloride, 0.016mol of n-butyl zirconium and 0.024mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of sulfuric acid (the concentration of hydrogen ions in the sulfuric acid is 10 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clear solution, pouring the prepared clear solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in a 200 ℃ oven for 6h, naturally cooling after the reaction is finished, filtering out precipitates generated by the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 1h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Example 7
The preparation method of the aluminum-containing zirconium oxide hollow microsphere comprises the following steps:
adding 0.002mol of aluminum sulfate, 0.008mol of basic zirconium carbonate and 0.048mol of urea into 200ml of absolute ethyl alcohol, slowly adding 60ml of nitric acid (the concentration of hydrogen ions in the nitric acid is 15 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the stainless steel reaction kettle, heating the stainless steel reaction kettle in a 180 ℃ oven for 10h after sealing, naturally cooling the reaction product after the reaction is finished, filtering out precipitates generated by the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the precipitates into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 800 ℃ for 4h to obtain aluminum-containing zirconium oxide hollow microspheres, and taking a part of the aluminum-containing zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
Comparative example
The preparation method of the zirconia hollow microsphere comprises the following steps:
adding 0.016mol of zirconium oxychloride and 0.032mol of urea into 200ml of absolute ethyl alcohol, slowly adding 50ml of concentrated hydrochloric acid (the concentration of hydrogen ions in the concentrated hydrochloric acid is 12 mol/L) in the stirring process, magnetically stirring the mixture in a water bath environment at 60 ℃ to obtain a clarified solution, pouring the prepared clarified solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle for 12h in a 160 ℃ oven, naturally cooling after the reaction is finished, filtering out precipitates generated in the reaction, washing the precipitates with absolute ethyl alcohol for three times, putting the reaction kettle into the 60 ℃ oven for 24h until the precipitates are completely dried, calcining the dried powder at 1000 ℃ for 2h to obtain aluminum-free zirconium oxide hollow microspheres, and taking a part of the aluminum-free zirconium oxide hollow microspheres to perform high-temperature treatment at 1300 ℃ for 2 h.
To summarize:
(1) the main difference between the embodiments 1 and 3 lies in that the added aluminum content is different, and the aluminum-containing zirconium oxide hollow microspheres prepared in the molar ratio of the aluminum element to the zirconium element of (1-4) to 8 all show excellent high temperature resistance. FIG. 1(a) is an SEM photograph of aluminum-containing zirconia hollow microspheres prepared in example 2, which were kept intact and had smooth surfaces. FIG. 1(b) is an SEM image of the aluminum-containing zirconia hollow microsphere prepared in example 2 after high temperature treatment at 1300 ℃, and the hollow microsphere after high temperature treatment has no obvious change and shows excellent high temperature resistance. Fig. 2 is an EDS diagram of the aluminum-containing zirconia hollow microspheres prepared in example 2, and the molar ratio of aluminum element to zirconium element was 1: 4, which also confirmed that the aluminum element in the precursor was completely incorporated into the zirconia hollow microspheres.
(2) The main difference between the example 2 and the examples 4 to 7 lies in the different conditions of reaction time, temperature and the like, and the change of hydrothermal conditions has little influence on the temperature resistance of the hollow sphere in the comparative examples 2, 4 and 5.
(3) The comparative example was aluminum-free zirconia hollow microspheres, and FIG. 3(a) is an SEM image of the aluminum-free zirconia hollow microspheres prepared in the comparative example, which were kept intact and had smooth surfaces. FIG. 3(b) is an SEM image of the zirconia hollow microsphere without aluminum added prepared by the comparative example after high temperature treatment at 1300 ℃, the hollow microsphere without aluminum added after high temperature treatment is seriously damaged, the surface is hollow, and the temperature resistance is much poorer than that of the zirconia hollow microsphere with aluminum added in example 2. Therefore, the high temperature resistance of the zirconia hollow microsphere is obviously improved by adding aluminum.
Claims (3)
1. The method for preparing the aluminum-containing zirconia hollow microspheres is characterized in that the aluminum-containing zirconia hollow microspheres comprise the following components in a molar ratio of (1-4): 8, the diameter of the aluminum-containing zirconia hollow microsphere is 0.1-10 mu m, and the preparation method of the aluminum-containing zirconia hollow microsphere comprises the following steps:
1) adding an aluminum precursor, a zirconium precursor and urea into absolute ethyl alcohol, slowly adding strong acid in the stirring process, and uniformly mixing to form a clear solution, wherein the strong acid is sulfuric acid, the concentration of hydrogen ions in the strong acid is 10-15 mol/L, the molar ratio of the aluminum precursor to the zirconium precursor to the urea is (1-4): 8, (12-24), and the volume ratio of the ethyl alcohol to the strong acid is (2-8): 1;
2) placing the clear solution prepared in the step 1) in a closed reaction kettle, carrying out solvothermal reaction for 6-18 h at 160-200 ℃, cooling, collecting white precipitate in a product, washing and drying;
3) calcining the product dried in the step 2) at 800-1000 ℃ for 1-4 h.
2. The method for preparing the aluminum-containing zirconia hollow microspheres according to claim 1, wherein in the step 1), the concentration of the zirconium precursor in the clarified solution is 0.05-0.15 mol/L.
3. The method for preparing the aluminum-containing zirconia hollow microspheres according to claim 1, wherein in the step 2), the washing solution used for washing is water or absolute ethyl alcohol, and the drying is performed at 60-100 ℃ for 24-48 h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263868A (en) * | 1999-02-15 | 2000-08-23 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1780791A (en) * | 2003-04-30 | 2006-05-31 | 镁电子有限公司 | Process for preparing zirconium oxides and zirconium-based mixed oxides |
| CN1913961A (en) * | 2004-02-06 | 2007-02-14 | 千年无机化学公司 | Nano-structured particles with high thermal stability |
| EP2545990A1 (en) * | 2011-07-14 | 2013-01-16 | SASOL Germany GmbH | Method for producing composites out of aluminium oxide and cerium/zirconium mixed oxides |
| CN102923771A (en) * | 2012-11-06 | 2013-02-13 | 石家庄铁道大学 | Method for preparing zirconia hollow microsphere |
| CN103570027A (en) * | 2013-11-08 | 2014-02-12 | 蚌埠玻璃工业设计研究院 | Preparation method of SiO2/ZrO2/Al2O3 composite hollow nanospheres |
| CN105585035A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of alumina hollow microspheres |
| CN106430304A (en) * | 2016-07-31 | 2017-02-22 | 包头稀土研究院 | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution |
| CN106587148A (en) * | 2016-12-21 | 2017-04-26 | 蚌埠中恒新材料科技有限责任公司 | Preparation method of uniform-size spherical yttrium-stabilized zirconia nano powder |
| CN106964332A (en) * | 2011-07-01 | 2017-07-21 | 特莱巴赫工业有限公司 | Cerium oxide zirconia alumina composition with enhanced heat endurance |
-
2018
- 2018-06-11 CN CN201810599788.0A patent/CN108640151B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263868A (en) * | 1999-02-15 | 2000-08-23 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1780791A (en) * | 2003-04-30 | 2006-05-31 | 镁电子有限公司 | Process for preparing zirconium oxides and zirconium-based mixed oxides |
| CN1913961A (en) * | 2004-02-06 | 2007-02-14 | 千年无机化学公司 | Nano-structured particles with high thermal stability |
| CN106964332A (en) * | 2011-07-01 | 2017-07-21 | 特莱巴赫工业有限公司 | Cerium oxide zirconia alumina composition with enhanced heat endurance |
| EP2545990A1 (en) * | 2011-07-14 | 2013-01-16 | SASOL Germany GmbH | Method for producing composites out of aluminium oxide and cerium/zirconium mixed oxides |
| CN102923771A (en) * | 2012-11-06 | 2013-02-13 | 石家庄铁道大学 | Method for preparing zirconia hollow microsphere |
| CN103570027A (en) * | 2013-11-08 | 2014-02-12 | 蚌埠玻璃工业设计研究院 | Preparation method of SiO2/ZrO2/Al2O3 composite hollow nanospheres |
| CN105585035A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of alumina hollow microspheres |
| CN106430304A (en) * | 2016-07-31 | 2017-02-22 | 包头稀土研究院 | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution |
| CN106587148A (en) * | 2016-12-21 | 2017-04-26 | 蚌埠中恒新材料科技有限责任公司 | Preparation method of uniform-size spherical yttrium-stabilized zirconia nano powder |
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