CN104478464B - The preparation method of zirconic acid lanthanum porous blocks - Google Patents
The preparation method of zirconic acid lanthanum porous blocks Download PDFInfo
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- CN104478464B CN104478464B CN201410781565.8A CN201410781565A CN104478464B CN 104478464 B CN104478464 B CN 104478464B CN 201410781565 A CN201410781565 A CN 201410781565A CN 104478464 B CN104478464 B CN 104478464B
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Abstract
The invention discloses the preparation method of a kind of zirconic acid lanthanum porous blocks, comprise the following steps: at room temperature, zirconium inorganic salt, lanthanum inorganic salt and separated derivant are dissolved in a solvent respectively, stirring is to obtaining transparent settled solution；It is subsequently adding drying control chemical additive stirring；Add the stirring of gel accelerator；The homogeneous solution of gained is put in sealing container, places 10～30min in 30 DEG C～80 DEG C, obtains wet gel；Wet gel is placed at 35～80 DEG C ageing 12～24h, uses coating material solution soaking again after the most first cleaning by low surface tension solvent, clean by low surface tension solvent the most again；After cleaning, wet gel is dried 24～72h in 30～90 DEG C；Then in 400～1300 DEG C of heat treatments 2～4h, zirconic acid lanthanum porous blocks is obtained.The zirconic acid lanthanum porous blocks using the method to prepare has co-continuous macroporous structure, porosity height and the medium feature of pore-size distribution collection.
Description
Technical field
The invention belongs to inorganic material preparation and the technical field of sol-gal process, being specifically related to a kind of is front with zirconium, lanthanum inorganic salt
Drive the method that body prepares zirconic acid lanthanum porous blocks.
Background technology
Zirconic acid lanthanum belongs to pyrochlore constitution, closely approximates fluorite structure, may be considered the fluorite knot of scarce anion to a certain extent
Structure.Unadulterated zirconic acid lanthanum, oxygen ion vacancy is ordered into, and some oxonium ions may exit off the lattice position of oneself and occupy hole
Position, produces ionic conduction.It is a kind of Open architecture, can increase structure intermediate ion row by the doping of other ions
The randomness of row, migrates offer hole, or increases hole concentration for oxonium ion, proton, thus improve ion conductivity.?
There is under different condition different carrier conductive catalytic combustion activities etc..Its special performance makes it answer apparatus in a lot of fields
Hold out broad prospects, such as: the actinides in the electrolyte nuke rubbish of catalytic combustion activity agent SOFC
Fixing base etc..
Meanwhile, the gas turbine used along with Aero-Space industry develops, in combustor to high inlet temperature, high thrust-weight ratio direction
The pressure of fuel gas temperature improve constantly, manufacture the material used by gas turbine and must possess high-melting-point, high thermal expansion coefficient, good
The performances such as good non-oxidizability and corrosion resistance.For meeting the operation at high temperature of high temperature insulating material, low thermal conductivity, anti-sintering
With requirements such as thermal deformations, it has been found that the zirconic acid lanthanum material of pyrochlore type structure has excellent high-temperature-phase stability, at fusing point
Before (2300 DEG C), crystal structure keeps constant.Compared with zirconium oxide, zirconic acid lanthanum is without phase in version between room temperature to fusing point, and heat is steady
Qualitative higher, heat conductivity, thermal coefficient of expansion and Young's modulus are lower, more anti-sintering.Above-described based on zirconic acid lanthanum material
Outstanding advantages, zirconic acid lanthanum has wider application prospect in high temperature insulating field.
CN103553596A provides a kind of method using sol-gal process to prepare zirconic acid lanthanum fiber, and CN103803973A provides
A kind of preparation method of pure dense phase zirconic acid lanthanum pottery.The preparation method that zirconic acid lanthanum powder is conventional includes solid reaction process, self-propagating
Combustion method, chemical coprecipitation, sol-gel process, sol-gel auto-combustion, hydro-thermal method etc..But about zirconic acid
The preparation method of lanthanum porous blocks there is not yet patent report.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of zirconic acid lanthanum porous blocks, uses the inventive method to prepare
Zirconic acid lanthanum porous blocks there is co-continuous macroporous structure, porosity is high and the medium feature of pore-size distribution collection.
For solving the problems referred to above, the present invention provides the preparation method of a kind of zirconic acid lanthanum porous blocks, comprises the following steps successively:
1), at room temperature, zirconium inorganic salt, lanthanum inorganic salt and separated derivant being dissolved in a solvent respectively, stirring is to obtaining thoroughly
Bright settled solution (mixing time is 0.5～4h, for example, 3～4h)；Described zirconium inorganic salt, lanthanum inorganic salt and separated derivant
Mol ratio be 1:0.8～1.2:0.0002～0.0006 (preferably 1:0.8～1.2:0.0002～0.0005)；
2), toward step 1) clear solution of gained is slowly added to (0.5～1min adds；I.e., about with 0.5～1.2ml/min
Speed adds) drying control chemical additive；Stirring 30～60min；
Drying control chemical additive is 0.5～0.9:1 with the mol ratio of zirconium inorganic salt；
3), to step 2) solution of gained is slowly added to (0.5～1min adds, i.e. about add with the speed of 0.6～3ml/min
Enter) gel accelerator, stirring 5～15min obtains homogeneous solution；
Gel accelerator is 1～1.4:1 with the mol ratio of zirconium inorganic salt；
4), by step 3) homogeneous solution of gained puts in sealing container, places 10～30min in 30 DEG C～80 DEG C (in baking oven)
(preferably placing 15～30min in 40 DEG C～60 DEG C), obtains wet gel；
5), by step 4) wet gel of gained is placed at 35～80 DEG C ageing 12～24h and (is preferably aged at 60～80 DEG C
12～24h)；Again with coating material solution soaking 2～5 times after the most first cleaning by low surface tension solvent, each soak time is
12～30h；Finally clean by low surface tension solvent again；
Remarks illustrate: " cleaning by low surface tension solvent " at above-mentioned 2 is: the gains of previous step are put into low table
Surface tension solvent carries out soaking thus realizes the purpose cleaned, general immersion 2～3 times, each 12～24h.
Whole step 5) in immersion the most only need to ensure that object is submerged can (this belongs to routine techniques).
6), by step 5) wet gel is dried 24～72h (preferably 40 DEG C are dried 50～60h) in 30～90 DEG C after the cleaning of gained；
Then in 400～1300 DEG C of heat treatments 2～4h (preferably 1000～1200 DEG C heat treatments 3～4h), zirconic acid lanthanum porous blocks is obtained.
Improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described step 1) in solvent be that deionized water is with anhydrous
The mixed liquor of ethanol composition, described deionized water is 1:0.8～4 (preferably 1:1～2) with the volume ratio of dehydrated alcohol.
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described zirconium inorganic salt is basic zirconium chloride, nitric acid
Oxygen zirconium, Zirconium tetrachloride. or zirconium nitrate, described lanthanum inorganic salt is lanthanum chloride or Lanthanum (III) nitrate.
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described separated derivant is described being separated
Derivant is polyoxyethylene (PEO) or polyvinylpyrrolidone (PVP).
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described drying control chemical additive is formyl
Amine, N-METHYLFORMAMIDE or Polyethylene Glycol.
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described gel accelerator be expoxy propane (PO),
Ammonia, carbamide.
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described coating material solution is volume fraction
Be 10～the ethanol solution of tetraethyl orthosilicate of 30%, the ethanol solution of trim,ethylchlorosilane, the ethanol solution of methyl trichlorosilane or
Person is the ethanol solution of trim,ethylchlorosilane.
Further improvement as the zirconic acid lanthanum porous blocks preparation method of the present invention: described low surface tension solvent be dehydrated alcohol,
Hexamethylene or acetone.
Step 1 in 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
All as presoma.
In the present invention, room temperature generally refers to 15～25 DEG C.
The invention provides the preparation method of a kind of zirconic acid lanthanum porous blocks material with co-continuous structure, and can be by adjusting
The relative scale of whole separated derivant and gel accelerator regulates sol-gel transition time and separated trend, thus convenient
Efficiently control aperture size and porosity.Due to the loose structure of its uniqueness, the zirconic acid lanthanum porous blocks of preparation is expected in catalysis
The fields such as agent carrier, solid fuel cell electrode material, high temperature insulating represent important application prospect.Meanwhile, this preparation method
Having organically combined sol gel processing and the theoretical features that is separated, had the high-purity preparation of wet-chemical, controlled construction porous is tied
Structure, the advantages such as raw material is cheap with equipment price, and technique is simple.
In sum, the present invention combines collosol and gel and the features being separated, and select suitably to be separated derivant and gel
Accelerator and respective consumption, it is possible to one-step synthesis zirconic acid lanthanum porous blocks (rather than the fiber described in prior art).The present invention
Use collosol and gel to prepare zirconic acid lanthanum porous blocks with phase detachment technique, there is cheap pollution-free, the preparation work of reaction raw materials
The advantages such as skill, reaction condition are 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.
Detailed description of the invention
Embodiment 1, the preparation method of a kind of zirconic acid lanthanum porous blocks, zirconium inorganic salt selects basic zirconium chloride, lanthanum inorganic salt selection chlorine
Changing lanthanum, expoxy propane (PO) is gel accelerator, and polyoxyethylene is the derivant that is separated, and Methanamide is that drying control chemistry adds
Adding agent, coating material solution is the ethanol solution (volume fraction of tetraethyl orthosilicate is 20%) of tetraethyl orthosilicate, and low surface is opened
Power solvent is dehydrated alcohol；The mol ratio of the most each material is as follows:
Basic zirconium chloride: lanthanum chloride: polyoxyethylene: Methanamide: expoxy propane=1:0.8:0.0002:0.5:1；
Follow the steps below the most successively:
1), basic zirconium chloride, lanthanum chloride and polyoxyethylene being dissolved in alcohol aqueous solvent, magnetic agitation 3h is to obtaining clear solution；Wherein alcohol
Aqueous solvent is that dehydrated alcohol is obtained by mixing according to the volume ratio of 1:1 with deionized water；The zirconium inorganic salt (basic zirconium chloride) of every 1mol
The alcohol aqueous solvent of adapted 1L；
2), toward step 1) clear solution of gained is slowly added to (0.5～1min adds) Methanamide, continue stirring 30min；
Finally it is slow added into (about 0.5～1min adds) expoxy propane, continues stirring 15min and obtain homogeneous solution；
3), stop stirring after, homogeneous solution is placed in 60 DEG C of baking ovens and becomes wet gel after 15min, then wet gel is placed in
The baking oven of 80 DEG C is aged 24h；The most first use soaked in absolute ethyl alcohol 2 times, each 12h；Then with the ethanol solution of tetraethyl orthosilicate
Middle immersion 2 times, each soak time is 24h；Use soaked in absolute ethyl alcohol 2 times the most again, 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 heat 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 (such as Fig. 1).
Embodiment 2, the preparation method of a kind of zirconic acid lanthanum porous blocks, zirconium inorganic salt selects zirconyl nitrate, lanthanum inorganic salt selection nitre
Acid lanthanum, expoxy propane is gel accelerator, and polyvinylpyrrolidone (PVP) is the derivant that is separated, and N-METHYLFORMAMIDE is dry
Controlling chemical addition agent, coating material solution is that (volume fraction of trim,ethylchlorosilane is for the ethanol solution of trim,ethylchlorosilane
15%), low surface tension solvent is hexamethylene；The mol ratio of the most each material is as follows:
Zirconyl nitrate: Lanthanum (III) nitrate: polyvinylpyrrolidone: N-METHYLFORMAMIDE: expoxy propane=1:1.2:0.0005:0.9:
1.4。
Follow the steps below the most successively:
1), zirconyl nitrate, Lanthanum (III) nitrate and polyvinylpyrrolidone being dissolved in alcohol aqueous solvent, magnetic agitation 4h is to clear solution；Its
Middle alcohol aqueous solvent is that dehydrated alcohol is obtained by mixing according to the volume ratio of 2:1 with deionized water；Zirconium inorganic salt (the nitric acid of every 1mol
Oxygen zirconium) the alcohol aqueous solvent of adapted 1L；
2), toward step 1) clear solution of gained is slowly added to (0.5～1min adds) N-METHYLFORMAMIDE, continue stirring
30min；Finally it is slow added into (0.5～1min adds) expoxy propane, continues stirring 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 of 60 DEG C is aged 12h；The most first soak 2 times with hexamethylene, each 12h；Then molten with the ethanol of trim,ethylchlorosilane
Soaking 3 times in liquid, each soak time is 24h；Last again with hexamethylene immersion 3 times, 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 heat 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 (such as Fig. 2).
Comparative example 1-1, by the basic zirconium chloride in embodiment 1: lanthanum chloride: polyoxyethylene: Methanamide: expoxy propane by " 1:
0.8:0.0002:0.5:1 " make " 1:0.8:0.0001:0.5:1 " into；Remaining is equal to embodiment 1.The method prepares institute
The zirconic acid lanthanum porous blocks porosity obtained is 48%, and pore-size distribution is 0.5～1 μm (such as Fig. 3).
Comparative example 1-2, by the basic zirconium chloride in embodiment 1: lanthanum chloride: polyoxyethylene: Methanamide: expoxy propane=" 1:
0.8:0.0002:0.5:1 " make " 1:0.8:0.0007:0.5:1 " into；Remaining is equal to embodiment 1.Prepared by the method
Zirconic acid lanthanum block be formed without loose structure (such as Fig. 4).
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, the present invention is not
It is limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation gone out or associate, are all considered as protection scope of the present invention.
Claims (4)
1. the preparation method of zirconic acid lanthanum porous blocks, its feature comprises the following steps successively:
1), at room temperature, zirconium inorganic salt, lanthanum inorganic salt and separated derivant being dissolved in a solvent respectively, stirring is to obtaining thoroughly
Bright settled solution；The mol ratio of described zirconium inorganic salt, lanthanum inorganic salt and separated derivant is 1:0.8～1.2:0.0002～0.0006；
Described solvent is the mixed liquor of deionized water and dehydrated alcohol composition, and described deionized water is 1 with the volume ratio of dehydrated alcohol:
0.8～4；Described zirconium inorganic salt is basic zirconium chloride, zirconyl nitrate, Zirconium tetrachloride. or zirconium nitrate, described lanthanum inorganic salt be lanthanum chloride or
Lanthanum (III) nitrate；Described separated derivant is polyoxyethylene or polyvinylpyrrolidone；
2), toward step 1) clear solution of gained is slowly added to drying control chemical additive, stir 30～60min；
Drying control chemical additive is 0.5～0.9:1 with the mol ratio of zirconium inorganic salt；
Described drying control chemical additive is Methanamide, N-METHYLFORMAMIDE or Polyethylene Glycol；
3), to step 2) solution of gained is slowly added to gel accelerator, stirring 5～15min obtains homogeneous solution；
Gel accelerator is 1～1.4:1 with the mol ratio of zirconium inorganic salt；
Described gel accelerator is expoxy propane, ammonia, carbamide；
4), by step 3) homogeneous solution of gained puts in sealing container, places 10～30min in 30 DEG C～80 DEG C, obtain wet gel；
5), by step 4) wet gel of gained is placed at 35～80 DEG C ageing 12～24h；The most first clean by low surface tension solvent
After again with coating material solution soaking 2～5 times, each soak time is 12～30h；Finally clean by low surface tension solvent again；
6), by step 5) wet gel is dried 24～72h in 30～90 DEG C after the cleaning of gained；Then in 400～1300 DEG C of heat treatments
2～4h, obtain zirconic acid lanthanum porous blocks.
The preparation method of zirconic acid lanthanum porous blocks the most according to claim 1, it is characterised in that: described coating material is molten
Liquid be volume fraction be 10～the ethanol solution of tetraethyl orthosilicate of 30%, the ethanol solution of methyl trichlorosilane or for trimethyl chlorine
The ethanol solution of silane.
The preparation method of zirconic acid lanthanum porous blocks the most according to claim 2, it is characterised in that: described low surface tension
Solvent is dehydrated alcohol, hexamethylene or acetone.
The preparation method of zirconic acid lanthanum porous blocks the most according to claim 3, it is characterised in that:
Zirconium inorganic salt is basic zirconium chloride, and lanthanum inorganic salt is lanthanum chloride, and gel accelerator is expoxy propane, and the derivant that is separated is poly-
Oxygen ethylene, Methanamide is drying control chemical additive；
Basic zirconium chloride: lanthanum chloride: polyoxyethylene: Methanamide: the mol ratio of expoxy propane=1:0.8:0.0002:0.5:1.
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| CN105622131A (en) * | 2015-12-25 | 2016-06-01 | 浙江大学 | Preparation method for yttria-stabilized zirconia porous bulks |
| CN108658574B (en) * | 2017-04-25 | 2021-01-29 | 天津唯元科技发展有限公司 | Anti-powder-dropping aerogel composite heat-insulating felt |
| CN111099909B (en) * | 2019-12-30 | 2020-12-29 | 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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| 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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