CN104478464A - Method for preparing porous lanthanum zirconate block - Google Patents
Method for preparing porous lanthanum zirconate block Download PDFInfo
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Abstract
The invention discloses a method for preparing a porous lanthanum zirconate block. The method comprises the following steps: at room temperature, dissolving inorganic salt of zirconium, inorganic salt of lanthanum and a phase separation inducer in a solvent and stirring until a transparent and clarified solution is obtained; adding a drying control chemical additive and stirring; adding a gel accelerator and stirring to obtain a homogeneous solution; placing the homogeneous solution into a sealed container and standing for 10-30 minutes at 30 DEG C-80 DEG C to obtain wet gel; aging the wet gel for 12-24 hours at 35-80 DEG C, firstly cleaning the wet gel with a solvent with a low surface tension and then soaking the wet gel with a surface modifier solution, and finally cleaning with the solvent with the low surface tension; drying the cleaned wet gel for 24-72 hours at 30-90 DEG C; and then carrying out heat treatment on the dried wet gel for 2-4 hours at 400-1300 DEG C to obtain the porous lanthanum zirconate block. The porous lanthanum zirconate block, which is prepared by the method, has the characteristics of co-continuous macroporous structure, high porosity, centralized distribution of pore sizes and the like.
Description
Technical field
The invention belongs to the technical field of inorganic materials preparation and sol-gel method, be specifically related to a kind of method being precursor power zirconic acid lanthanum porous blocks with zirconium, lanthanum inorganic salt.
Background technology
Zirconic acid lanthanum belongs to pyrochlore constitution, is very similar to fluorite structure, can think the fluorite structure of scarce negatively charged ion to a certain extent.Unadulterated zirconic acid lanthanum, oxygen ion vacancy is orderly, and the crystallographic site that some oxonium ions can leave oneself occupies VOID POSITIONS, produces ionic conduction.It is a kind of Open architecture, by the doping of other ions, can increase the randomness of structure intermediate ion arrangement, for oxonium ion, proton shifting provide hole, or increase hole concentration, thus improve ion conductivity.There is different current-carrying electronic conduction ﹑ catalytic combustion activity etc. at different conditions.Its special performance makes it have broad prospects in the application of a lot of fields, as: the actinides fixing base etc. in the electricity Xie Zhi ﹑ nuke rubbish of catalytic combustion activity Ji ﹑ Solid Oxide Fuel Cell.
Simultaneously, the internal combustion turbine used along with aerospace industry is to high inlet temperature, high thrust-weight ratio future development, the pressure of the fuel gas temperature in combustion chamber improves constantly, and the material manufacturing internal combustion turbine used must possess the performances such as high-melting-point, high thermal expansion coefficient, good oxidation-resistance and erosion resistance.For meeting the operation at high temperature of high temperature insulating material, low thermal conductivity, the requirement such as anti-sintering and thermal distortion, it is found that the zirconic acid lanthanum material of pyrochlore type structure has excellent high-temperature-phase stability, before fusing point (2300 DEG C), crystalline structure remains unchanged.Compared with zirconium white, zirconic acid lanthanum is without phase in version between room temperature to fusing point, and thermostability is higher, and thermal conductivity, thermal expansivity and Young's modulus are lower, more anti-sintering.Based on the above-described outstanding advantages of zirconic acid lanthanum material, zirconic acid lanthanum has application prospect widely in high temperature insulating field.
CN103553596A provides a kind of method adopting sol-gel method to prepare zirconic acid lanthanum fiber, and CN103803973A provides a kind of preparation method of fine and close pure phase zirconic acid lanthanum pottery.The preparation method that zirconic acid lanthanum powder is conventional comprises solid reaction process, self-propagating combustion, chemical coprecipitation, sol-gel method, sol-gel auto-combustion, hydrothermal method etc.But there is not yet patent report about the preparation method of zirconic acid lanthanum porous blocks.
Summary of the invention
The features such as the technical problem to be solved in the present invention is to provide a kind of preparation method of zirconic acid lanthanum porous blocks, adopts the zirconic acid lanthanum porous blocks prepared of the inventive method to have altogether macroporous structure continuously, and the high and pore size distribution of porosity is concentrated.
For solving the problem, the invention provides a kind of preparation method of zirconic acid lanthanum porous blocks, comprising the following steps successively:
1), at room temperature, respectively zirconium inorganic salt, lanthanum inorganic salt and the inductor that is separated are dissolved in a solvent, be stirred to obtain transparent settled solution (churning time is 0.5 ~ 4h, such as, be 3 ~ 4h); The mol ratio of described zirconium inorganic salt, lanthanum inorganic salt and the inductor that is separated is 1:0.8 ~ 1.2:0.0002 ~ 0.0006 (being preferably 1:0.8 ~ 1.2:0.0002 ~ 0.0005);
2), toward step 1) slowly add that (0.5 ~ 1min adds in the clear solution of gained; That is, about add with the speed of 0.5 ~ 1.2ml/min) drying control chemical additive; Stir 30 ~ 60min;
The mol ratio of drying control chemical additive and zirconium inorganic salt is 0.5 ~ 0.9:1;
3), to step 2) slowly add (0.5 ~ 1min adds, that is, about add with the speed of 0.6 ~ 3ml/min) gel promotor in the solution of gained, stir 5 ~ 15min and obtain homogeneous solution;
The mol ratio of gel promotor and zirconium inorganic salt is 1 ~ 1.4:1;
4), by step 3) homogeneous solution of gained puts into sealed vessel, and place 10 ~ 30min (be preferably and place 15 ~ 30min in 40 DEG C ~ 60 DEG C) in 30 DEG C ~ 80 DEG C (in baking oven), obtain wet gel;
5), by step 4) wet gel of gained be placed in 35 ~ 80 DEG C at ageing 12 ~ 24h (being preferably ageing 12 ~ 24h at 60 ~ 80 DEG C); Then first use coating materials solution soaking again 2 ~ 5 times with after low surface tension solvent cleaning, each soak time is 12 ~ 30h; Finally clean by low surface tension solvent again;
Remarks illustrate: " the cleaning by low surface tension solvent " at above-mentioned 2 places is: the gains of previous step are put into low surface tension solvent and carry out soaking thus the object realizing cleaning, generally soak 2 ~ 3 times, each 12 ~ 24h.
Whole step 5) in immersion all only need ensure that object is submerged can (this belongs to routine techniques).
6), by step 5) after the cleaning of gained wet gel in 30 ~ 90 DEG C of drying 24 ~ 72h (being preferably 40 DEG C of drying 50 ~ 60h); Then in 400 ~ 1300 DEG C of thermal treatment 2 ~ 4h (being preferably 1000 ~ 1200 DEG C of thermal treatment 3 ~ 4h), zirconic acid lanthanum porous blocks is obtained.
Improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described step 1) in solvent be the mixed solution that deionized water and dehydrated alcohol form, the volume ratio of described deionized water and dehydrated alcohol is 1:0.8 ~ 4 (being preferably 1:1 ~ 2).
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described zirconium inorganic salt are basic zirconium chloride, Zircosol ZN, zirconium tetrachloride or zirconium nitrate, and described lanthanum inorganic salt are Lanthanum trichloride or lanthanum nitrate.
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described in be separated inductor for described in the inductor that is separated be polyoxyethylene (PEO) or polyvinylpyrrolidone (PVP).
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described drying control chemical additive is methane amide, N-METHYLFORMAMIDE or polyoxyethylene glycol.
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described gel promotor is propylene oxide (PO), ammoniacal liquor, urea.
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: the ethanolic soln of described finishing agent solution to be volume fraction the be tetraethoxy of 10 ~ 30%, the ethanolic soln of trimethylchlorosilane, the ethanolic soln of METHYL TRICHLORO SILANE or the ethanolic soln for trimethylchlorosilane.
Further improvement as zirconic acid lanthanum porous blocks preparation method of the present invention: described low surface tension solvent is dehydrated alcohol, hexanaphthene or acetone.
In step 1 of the present invention) in, the solvent of the zirconium inorganic salt adapted 1 ~ 1.5L of every 1mol; Zirconium inorganic salt and lanthanum inorganic salt are all as presoma.
In the present invention, room temperature generally refers to 15 ~ 25 DEG C.
The invention provides a kind of preparation method with the zirconic acid lanthanum porous blocks material of common continuous structure, and sol-gel transition time and the trend that is separated can be regulated by the relative proportion adjusting be separated inductor and gel promotor, thus easily and effectively control aperture size and porosity.Due to the vesicular structure of its uniqueness, the zirconic acid lanthanum porous blocks of preparation is expected to represent important application prospect in fields such as support of the catalyst, solid fuel cell electrode materials, high temperature insulatings.Meanwhile, this preparation method has organically combined sol gel processing and the theoretical features that is separated, and has the high-purity preparation of wet-chemical, controlled construction vesicular structure, raw material and equipment price cheap, the advantages such as technique is simple.
In sum, the present invention, in conjunction with collosol and gel and the features that is separated, selects suitable inductor and gel promotor and the respective consumption of being separated, can one-step synthesis zirconic acid lanthanum porous blocks (but not the fiber described in prior art).The present invention adopts collosol and gel to prepare zirconic acid lanthanum porous blocks with phase detachment technique, has the advantages such as reaction raw materials cheap pollution-free, preparation technology, reaction conditions be gentle.
Accompanying drawing explanation
Fig. 1 is the internal microstructure figure of the porous blocks that embodiment 1 obtains;
Fig. 2 is the internal microstructure figure of the porous blocks that embodiment 2 obtains;
Fig. 3 is the internal microstructure figure of the porous blocks that embodiment 1-1 obtains;
Fig. 4 is the internal microstructure figure of the porous blocks that embodiment 1-2 obtains.
Embodiment
The preparation method of embodiment 1, a kind of zirconic acid lanthanum porous blocks, zirconium inorganic salt select basic zirconium chloride, lanthanum inorganic salt select Lanthanum trichloride, propylene oxide (PO) is gel promotor, polyoxyethylene is the inductor that is separated, methane amide is drying control chemical additive, and finishing agent solution is the ethanolic soln (volume fraction of tetraethoxy is 20%) of tetraethoxy, and low surface tension solvent is dehydrated alcohol; Wherein the mol ratio of each material is as follows:
Basic zirconium chloride: Lanthanum trichloride: polyoxyethylene: methane amide: propylene oxide=1:0.8:0.0002:0.5:1;
Carry out following steps successively again:
1), by basic zirconium chloride, Lanthanum trichloride and polyoxyethylene be dissolved in alcohol water solvent, magnetic agitation 3h is to obtaining clear solution; Wherein alcohol water solvent is that dehydrated alcohol and deionized water are obtained by mixing according to the volume ratio of 1:1; The alcohol water solvent of zirconium inorganic salt (basic zirconium chloride) the adapted 1L of every 1mol;
2), toward step 1) slowly add (0.5 ~ 1min adds) methane amide in the clear solution of gained, continue to stir 30min; Finally slowly add (about 0.5 ~ 1min adds) propylene oxide again, continue to stir 15min and obtain homogeneous solution;
3), stop stir after, become wet gel after homogeneous solution being placed in 60 DEG C of baking oven 15min, then wet gel be placed in the baking oven ageing 24h of 80 DEG C; First use soaked in absolute ethyl alcohol 2 times again, each 12h; Then soak 2 times with in the ethanolic soln of tetraethoxy, each soak time is 24h; Finally use soaked in absolute ethyl alcohol again 2 times, each 24h;
4), by step 3) gel constant pressure and dry 50h at 40 DEG C after the cleaning of gained;
5), by step 4) xerogel of gained at 1200 DEG C of thermal treatment 3h, obtain zirconic acid lanthanum porous blocks.
Zirconic acid lanthanum porous blocks porosity prepared by the method is 64%, and pore size distribution is 1 ~ 3 μm (as Fig. 1).
The preparation method of embodiment 2, a kind of zirconic acid lanthanum porous blocks, zirconium inorganic salt select Zircosol ZN, lanthanum inorganic salt select lanthanum nitrate, propylene oxide is gel promotor, polyvinylpyrrolidone (PVP) is the inductor that is separated, N-METHYLFORMAMIDE is drying control chemical additive, and finishing agent solution is the ethanolic soln (volume fraction of trimethylchlorosilane is 15%) of trimethylchlorosilane, and low surface tension solvent is hexanaphthene; Wherein the mol ratio of each material is as follows:
Zircosol ZN: lanthanum nitrate: polyvinylpyrrolidone: N-METHYLFORMAMIDE: propylene oxide=1:1.2:0.0005:0.9:1.4.
Carry out following steps successively again:
1), by Zircosol ZN, lanthanum nitrate and polyvinylpyrrolidone be dissolved in alcohol water solvent, magnetic agitation 4h is to clear solution; Wherein alcohol water solvent is that dehydrated alcohol and deionized water are obtained by mixing according to the volume ratio of 2:1; The alcohol water solvent of zirconium inorganic salt (Zircosol ZN) the adapted 1L of every 1mol;
2), toward step 1) slowly add (0.5 ~ 1min adds) N-METHYLFORMAMIDE in the clear solution of gained, continue to stir 30min; Finally slowly add (0.5 ~ 1min adds) propylene oxide again, continue to stir 15min; Obtain homogeneous solution.
3), stop stirring after, homogeneous solution is placed in 40 DEG C of baking ovens after 30min becomes wet gel, then wet gel is placed in the baking oven ageing 12h of 60 DEG C; Then first 2 times are soaked with hexanaphthene, each 12h; Then soak 3 times with in the ethanolic soln of trimethylchlorosilane, each soak time is 24h; Finally soak 3 times with hexanaphthene again, each 24h;
4), by step 3) gel constant pressure and dry 60h at 40 DEG C after the cleaning of gained;
5), by step 4) xerogel of gained at 1000 DEG C of thermal treatment 4h, obtain zirconic acid lanthanum porous blocks.
Zirconic acid lanthanum porous blocks porosity prepared by the method is 52%, and pore size distribution is 1 ~ 3 μm (as Fig. 2).
Comparative example 1-1, by the basic zirconium chloride in embodiment 1: Lanthanum trichloride: polyoxyethylene: methane amide: propylene oxide is made into " 1:0.8:0.0001:0.5:1 " by " 1:0.8:0.0002:0.5:1 "; All the other are equal to embodiment 1.The zirconic acid lanthanum porous blocks porosity that the method prepares gained is 48%, and pore size distribution is 0.5 ~ 1 μm (as Fig. 3).
Comparative example 1-2, by the basic zirconium chloride in embodiment 1: Lanthanum trichloride: polyoxyethylene: methane amide: propylene oxide=" 1:0.8:0.0002:0.5:1 " makes into " 1:0.8:0.0007:0.5:1 "; All the other are equal to embodiment 1.Zirconic acid lanthanum block prepared by the method does not form vesicular structure (as Fig. 4).
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (9)
1. the preparation method of zirconic acid lanthanum porous blocks, its feature comprises the following steps successively:
1), at room temperature, respectively zirconium inorganic salt, lanthanum inorganic salt and the inductor that is separated are dissolved in a solvent, be stirred to obtain transparent settled solution; The mol ratio of described zirconium inorganic salt, lanthanum inorganic salt and the inductor that is separated is 1:0.8 ~ 1.2:0.0002 ~ 0.0006;
2), toward step 1) slowly add drying control chemical additive in the clear solution of gained, stir 30 ~ 60min;
The mol ratio of drying control chemical additive and zirconium inorganic salt is 0.5 ~ 0.9:1;
3), to step 2) slowly add gel promotor in the solution of gained, stir 5 ~ 15min and obtain homogeneous solution;
The mol ratio of gel promotor and zirconium inorganic salt is 1 ~ 1.4:1;
4), by step 3) homogeneous solution of gained puts into sealed vessel, and place 10 ~ 30min in 30 DEG C ~ 80 DEG C, obtain wet gel;
5), by step 4) wet gel of gained be placed in 35 ~ 80 DEG C at ageing 12 ~ 24h; Then first use coating materials solution soaking again 2 ~ 5 times with after low surface tension solvent cleaning, each soak time is 12 ~ 30h; Finally clean by low surface tension solvent again;
6), by step 5) after the cleaning of gained wet gel in 30 ~ 90 DEG C of drying 24 ~ 72h; Then in 400 ~ 1300 DEG C of thermal treatment 2 ~ 4h, zirconic acid lanthanum porous blocks is obtained.
2. the preparation method of zirconic acid lanthanum porous blocks according to claim 1, is characterized in that: described step 1) in solvent be the mixed solution that deionized water and dehydrated alcohol form, the volume ratio of described deionized water and dehydrated alcohol is 1:0.8 ~ 4.
3. the preparation method of zirconic acid lanthanum porous blocks according to claim 2, it is characterized in that: described zirconium inorganic salt are basic zirconium chloride, Zircosol ZN, zirconium tetrachloride or zirconium nitrate, described lanthanum inorganic salt are Lanthanum trichloride or lanthanum nitrate.
4. the preparation method of zirconic acid lanthanum porous blocks according to claim 3, is characterized in that: described in the inductor that is separated be polyoxyethylene or polyvinylpyrrolidone.
5. the preparation method of zirconic acid lanthanum porous blocks according to claim 4, is characterized in that: described drying control chemical additive is methane amide, N-METHYLFORMAMIDE or polyoxyethylene glycol.
6. the preparation method of zirconic acid lanthanum porous blocks according to claim 5, is characterized in that: described gel promotor is propylene oxide, ammoniacal liquor, urea.
7. the preparation method of zirconic acid lanthanum porous blocks according to claim 6, is characterized in that: the ethanolic soln of described finishing agent solution to be volume fraction the be tetraethoxy of 10 ~ 30%, the ethanolic soln of trimethylchlorosilane, the ethanolic soln of METHYL TRICHLORO SILANE or the ethanolic soln for trimethylchlorosilane.
8. the preparation method of zirconic acid lanthanum porous blocks according to claim 7, is characterized in that: described low surface tension solvent is dehydrated alcohol, hexanaphthene or acetone.
9. the preparation method of zirconic acid lanthanum porous blocks according to claim 8, is characterized in that:
Zirconium inorganic salt are basic zirconium chloride, and lanthanum inorganic salt are Lanthanum trichloride, and gel promotor is propylene oxide, and the inductor that is separated is polyoxyethylene, and methane amide is drying control chemical additive;
Basic zirconium chloride: Lanthanum trichloride: polyoxyethylene: methane amide: the mol ratio of propylene oxide=1:0.8:0.0002:0.5:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105622131A (en) * | 2015-12-25 | 2016-06-01 | 浙江大学 | Preparation method for yttria-stabilized zirconia porous bulks |
| CN108610000A (en) * | 2017-04-25 | 2018-10-02 | 郑善 | A kind of preparation method of anti-shedding aeroge complex heat-preservation felt |
| CN111099909A (en) * | 2019-12-30 | 2020-05-05 | 浙江大学 | High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof |
| CN112864353A (en) * | 2021-04-01 | 2021-05-28 | 清华大学深圳国际研究生院 | Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery |
| CN113275017A (en) * | 2021-05-28 | 2021-08-20 | 内蒙古大学 | Preparation method and application of composite pyrochlore catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896620A (en) * | 2014-03-11 | 2014-07-02 | 中国人民解放军国防科学技术大学 | Hierarchic porous La2Zr2O7 ceramic and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896620A (en) * | 2014-03-11 | 2014-07-02 | 中国人民解放军国防科学技术大学 | Hierarchic porous La2Zr2O7 ceramic and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105622131A (en) * | 2015-12-25 | 2016-06-01 | 浙江大学 | Preparation method for yttria-stabilized zirconia porous bulks |
| CN108610000A (en) * | 2017-04-25 | 2018-10-02 | 郑善 | A kind of preparation method of anti-shedding aeroge complex heat-preservation felt |
| CN108610000B (en) * | 2017-04-25 | 2021-04-30 | 天津朗华睿博科技有限公司 | Preparation method of anti-falling powder aerogel composite heat-preservation felt |
| CN111099909A (en) * | 2019-12-30 | 2020-05-05 | 浙江大学 | High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof |
| CN112864353A (en) * | 2021-04-01 | 2021-05-28 | 清华大学深圳国际研究生院 | Positive electrode material, preparation method thereof, positive electrode and all-solid-state lithium ion battery |
| CN113275017A (en) * | 2021-05-28 | 2021-08-20 | 内蒙古大学 | Preparation method and application of composite pyrochlore catalyst |
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