CN102583538B - A kind of sol-gel process preparing potassium-sodium niobate nanometer rods - Google Patents
A kind of sol-gel process preparing potassium-sodium niobate nanometer rods Download PDFInfo
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Abstract
The invention discloses a kind of technique using sol-gal process to prepare potassium-sodium niobate nanometer rods.Weigh a certain amount of niobium hydroxide and sodium potassium tartrate tetrahydrate, according to mol ratio Nb (OH)5: oxalic acid=1: 3 weigh oxalic acid is dissolved in 90 DEG C of deionized waters, by Nb (OH)5Being dissolved in this solution and form Nb oxalic acid solution, reaction 1h becomes clarification to solution.According to molecular formula (Na0.5K0.5)NbO3Middle sodium potassium fully reacts 0.5h with the mol ratio addition sodium potassium tartrate tetrahydrate of niobium.After ammonia regulation solution ph to 2.5～3.5, in solution, add ethylene glycol, stir 2h, obtain pale yellow transparent precursor sol.In 90 DEG C of air dry ovens, freeze-day with constant temperature makes gelation and being dried of gel once complete for 24 hours, puts into and sinters 3h in sintering furnace at 750 DEG C, control different heating rates 0.5～3 DEG C/min to obtain mono-crystalline structures potassium-sodium niobate nanometer rods after grinding.
Description
Technical field
A kind of sol-gel process preparing potassium-sodium niobate nanometer rods.
Background technology
Potassium-sodium niobate leadless piezoelectric ceramics (K, Na) NbO3, referred to as KNN, is to have perovskite structure
ABO3Type lead-free piezoceramic material, near its quasi-homotype phase boundary point, potassium-sodium niobate
(K0.5Na0.5NbO3) base pottery, because it has good piezoelectricity, pyroelectric, dielectricity, photoelectricity
Property, ferroelectricity, and the plurality of advantages such as the easy doping vario-property of this system, good stability, heavy metal free pollution,
It it is considered as the leadless piezoelectric material material system being hopeful most to substitute PZT piezoceramic material.
In recent years, in potassium-sodium niobate powder body and film preparation, slender body dress and length have been prepared both at home and abroad
Strip KNN granule, Wang etc. is found that, at 600 DEG C in prepared by the citric acid method of KNN powder body
During sintering preparation KNN powder body, granule is slender body shape；Yan et al. is when sol-gel method prepares KNN thin film
It has also been found that when annealing at low temperatures, the granule of film surface is strip, and the XRD diffraction pattern of correspondence
In the relative altitude of (110) and (001) crystal face have certain corresponding relation.Liu etc. are in citric acid legal system
During standby KNN thin film, it has also been found that the length of surface particles length greatly 10-20 μm is excellent during annealing at 900 DEG C
Shape；But they all do not explain the reason causing these phenomenons, the most do not further investigate technological parameter pair
The impact of NKN pattern, additionally these reports are all to use citric acid as metal-complexing agent.
Summary of the invention
The goal of the invention of the present invention is to provide a kind of process simple, manageable, relies on and controls
Various process parameters in sol-gel technique, burn-in process, makes it specific controlling the pattern of powder body
Process conditions under can synthesize the KNN powder body of rodlike single-crystal structure, diameter 150-450nm, long
Degree 1-3 μm.The powder body of this special appearance is at the research of KNN leadless piezoelectric ceramics oriented growth and 1-3
The preparation of type piezo-electricity composite material is likely to be of preferable application prospect.
This method, is based on sol-gel process, with niobium hydroxide (Nb (OH)5), sodium potassium tartrate tetrahydrate
(C4H4KNaO6·4H2O) it is raw material, with ethylene glycol (C2H6O2) be esterifying agent, oxalic acid be that metal is joined
Position agent, the mol ratio of preparation solution is Na: K: Nb=1: 1: 2, obtained potassium-sodium niobate nano-powder
Composition is K(1-x)NaxNbO3(0.2≤x≤0.6), powder granule is bar-shaped；It is characterized in that, by preparation
During sol-gel process and the control of pre-sintering process parameter, prepare different with traditional square or ellipse
The rodlike single-crystal structure powder body of spheroid dress powder granule；The method is characterised by, preparation technology includes following step
Rapid:
1, according to mol ratio Nb (OH)5: oxalic acid=1: 3 weigh oxalic acid is dissolved in 90 DEG C of deionized waters, will
Nb (OH) 5 is dissolved in this solution and forms Nb-oxalic acid solution, and reaction 1h becomes clarification to solution；
2, according to molecular formula (Na0.5K0.5)NbO3Middle sodium potassium and the mol ratio of niobium, add sodium potassium tartrate tetrahydrate
Fully react 0.5h, it is thus achieved that the solution of transparent clarification；
3, by ammonia regulation solution ph to 2.5～3.5,15min is stablized, by n (oxalic acid): n (second two
Alcohol)=1: 2 in solution drip ethylene glycol, be stirred continuously 2h, obtain pale yellow transparent precursor sol；
4, in 90 DEG C of air dry ovens, freeze-day with constant temperature makes being dried once of gelation and gel for 24 hours
Complete, prepare presoma xerogel；
5, by xerogel with agate mortar grind, be placed in alumina crucible, put in sintering furnace
Sinter 3h at 750 DEG C, control different heating rates 0.5～3 DEG C/min, to obtain potassium-sodium niobate nanometer
Rod.
The present invention devises techniques below scheme for achieving the above object:
The raw material used is niobium hydroxide (Nb (OH)5), sodium potassium tartrate tetrahydrate (C4H4KNaO6·4H2O),
Ethylene glycol, oxalic acid, ammonia, wherein mol ratio is Na: K: Nb=1: 1: 2, niobium hydroxide: oxalic acid=3: 1.
Its concrete preparation technology is as follows:
1, according to mol ratio Nb (OH)5: oxalic acid=1: 3 weigh oxalic acid is dissolved in 90 DEG C of deionized waters, will
Nb (OH) 5 is dissolved in this solution and forms Nb-oxalic acid solution, and reaction 1h becomes clarification to solution.
2, according to molecular formula (Na0.5K0.5)NbO3Middle sodium/potassium fills with the mol ratio addition sodium potassium tartrate tetrahydrate of niobium
Divide reaction 0.5h, it is thus achieved that the solution of transparent clarification.
3, by ammonia regulation solution ph to 2.5～3.5,15min is stablized, by n (oxalic acid): n (second two
Alcohol)=1: 2 in solution drip ethylene glycol, be stirred continuously 2h, obtain pale yellow transparent precursor sol.
4, in 90 DEG C of air dry ovens, freeze-day with constant temperature makes being dried once of gelation and gel for 24 hours
Complete, prepare presoma xerogel.
5, by xerogel with agate mortar grind, be placed in alumina crucible, put in sintering furnace
Sinter 3h at 750 DEG C, control different heating rates 1～3 DEG C/min to obtain potassium-sodium niobate nanometer rods.
At present, domestic mostly employing solid phase method prepares KNN powder body, and its shortcoming is: synthesis temperature is high,
Easily cause a large amount of volatilizations of K/Na thus cause all kinds of atom to deviate original components.The nanometer of potassium niobate
Although the preparation of rod is seen in report, but the self assembly of potassium-sodium niobate nanometer rods preparation there is no report.This
Bright technical scheme realizes without KNN nanometer in the case of template with technological parameter in control sol-gel process
Prepared by the self assembly of rod.The niobium source being most frequently with when preparing NKN leadless piezoelectric ceramics the most both at home and abroad
For Nb2O5, ethanol niobium, NbCl5Deng, wherein Nb2O5Chemical property highly stable, be difficult to and its
Its material generation chemical reaction；The price of ethanol niobium is the most much more expensive, and easily hydrolyzes this and be accomplished by
It is dried and noble gas preserves, thus make it difficult to promote in the industry；NbCl5Use meeting
Inevitably introduce muriatic impurity, affect the electrical property of material.Freshly prepd niobium hydroxide ratio
Nb2O5Activity strong, can be relatively easy to be dissolved in the carboxylic acids such as oxalic acid, citric acid and tartaric acid.Mirror
In the shortcoming in any of the above conventional niobium source, intend herein utilizing Nb2O5First prepare fresh niobium hydroxide
As niobium source.Preparation flow: in 80 DEG C of water-baths, weighs Nb in proportion2O5It is dissolved in HF
Generating faint yellow, reaction 1h adds excess ammonium oxalate solution after being completely dissolved, and stirs at Electromagnetic Heating
In set, at 80 DEG C, heated and stirred 1h, fully reaction generate light green solution, to above-mentioned solution after 1h
Middle dropping excessive ammonia is to generating white Nb (OH) completely5Precipitation, regulates pH to 8～9.At 80 DEG C
Washing and filtering after ageing 2h, cyclic washing three times.Wet niobium hydroxide is put in air dry oven
It is dried 24h at 60 DEG C, grinds stand-by with agate mortar.The invention has the beneficial effects as follows: owing to using
Niobium hydroxide makes cost be substantially reduced and is avoided that the introducing of impurity, and employing adds freshly prepared in oxalic acid
Nb(OH)5With the process of sodium potassium tartrate tetrahydrate, new niobium hydroxide more solution dissolves, sodium potassium tartrate tetrahydrate
React with oxalic acid and can strengthen system complexing and make sol system more stable, being dried easily of gel
Completing, facilitate operation, in sintering process, the volatilization of K/Na composition has obtained more preferable suppression, protects
Demonstrate,prove the stability of synthesis.
Detailed description of the invention
Embodiment 1:
To prepare 11.00 grams of K0.5Na0.5NbO3As a example by nano-powder, required raw material be oxalic acid 24 grams,
Niobium hydroxide 11.5 grams, sodium potassium tartrate tetrahydrate 8.73 grams, ethylene glycol 15ml, ammonia are appropriate.Concrete behaviour
Make as follows:
1,24g oxalic acid is dissolved in the deionized water at 400ml 90 DEG C, by 11.5g Nb (OH)5Molten
Forming Nb-oxalic acid solution in this solution, reaction 1h becomes clarification to solution.
2,8.73g sodium potassium tartrate tetrahydrate is added in the above-mentioned solution of 90 DEG C and fully react 0.5h, it is thus achieved that thoroughly
The solution of bright clarification.
3, by ammonia regulation solution ph to 3.5, after stablizing 15min, at the reaction condition of 90 DEG C
Under dropwise in solution drip 15ml ethylene glycol, be stirred continuously 2h, obtain pale yellow transparent presoma
Colloidal sol.
4, in 90 DEG C of air dry ovens, freeze-day with constant temperature makes being dried once of gelation and gel for 24 hours
Complete, obtain faint yellow presoma xerogel.
5, xerogel agate mortar is ground, be placed in alumina crucible, the programming rate of 30min
It is warming up to 120 DEG C, constant temperature 0.5 hour；It is warming up to 450 DEG C again, constant temperature 2 with 3～5 DEG C of programming rates
Hour；It is warming up to 750 DEG C with 1 DEG C/min again, at 750 DEG C, is incubated furnace cooling after 3h, obtains 11.00g
K0.5Na0.5NbO3Nanometer rods.
Embodiment 2:
To prepare 5.50 grams of K0.5Na0.5NbO3As a example by nano-powder, required raw material be oxalic acid 12 grams,
Niobium hydroxide 5.8 grams, sodium potassium tartrate tetrahydrate 4.36 grams, ethylene glycol 8ml.Concrete operations are as follows:
1,12g oxalic acid is dissolved in the deionized water at 200ml 90 DEG C, by 5.8g Nb (OH)5Molten
Forming Nb-oxalic acid solution in this solution, reaction 1h becomes clarification to solution.
2,4.36g sodium potassium tartrate tetrahydrate is added in the above-mentioned solution of 90 DEG C and fully react 0.5h, it is thus achieved that thoroughly
The solution of bright clarification.
3, by ammonia regulation solution ph to 3, after stablizing 15min, under the reaction condition of 90 DEG C
In solution, dropwise drip 8ml ethylene glycol, be stirred continuously 2h, obtain pale yellow transparent precursor sol.
4, in 90 DEG C of air dry ovens, freeze-day with constant temperature 24h makes being dried of gelation and gel the completeest
Become, obtain faint yellow presoma xerogel.
5, xerogel agate mortar is ground, be placed in alumina crucible, the programming rate of 30min
It is warming up to 120 DEG C, constant temperature 0.5 hour；It is warming up to 450 DEG C again, constant temperature 2 with 3～5 DEG C of programming rates
Hour；It is warming up to 750 DEG C with 1 DEG C/min again, at 750 DEG C, is incubated furnace cooling after 3h, obtains 5.50g
K0.5Na0.5NbO3Nanometer rods.
Embodiment 3:
To prepare 2.80 grams of K0.5Na0.5NbO3As a example by nano-powder, required raw material be oxalic acid 8 grams,
Niobium hydroxide 2.9 grams, carbon sodium potassium tartrate tetrahydrate 2.44 grams, ethylene glycol 6ml.Concrete operations are as follows:
1,8g oxalic acid is dissolved in the deionized water at 200ml 90 DEG C, by 2.9g Nb (OH)5It is dissolved in
This solution forms Nb-oxalic acid solution, and reaction 1h becomes clarification to solution.
2,2.44g sodium potassium tartrate tetrahydrate is added in the above-mentioned solution of 90 DEG C and fully react 0.5h, it is thus achieved that thoroughly
The solution of bright clarification.
3, by ammonia regulation solution ph to 2.5, after stablizing 15min, at the reaction condition of 90 DEG C
Under dropwise in solution drip 6ml ethylene glycol, be stirred continuously 2h, obtain pale yellow transparent presoma molten
Glue.
4, in 90 DEG C of air dry ovens, freeze-day with constant temperature makes being dried once of gelation and gel for 24 hours
Complete, obtain faint yellow presoma xerogel.
5, xerogel agate mortar is ground, be placed in alumina crucible, the programming rate of 30min
It is warming up to 120 DEG C, constant temperature 0.5 hour；It is warming up to 450 DEG C again, constant temperature 2 with 3～5 DEG C of programming rates
Hour；It is warming up to 750 DEG C with 1 DEG C/min again, at 750 DEG C, is incubated furnace cooling after 3h, obtains 11.00g
K0.5Na0.5NbO3Nanometer rods.
Claims (1)
1. the method preparing potassium-sodium niobate nanometer rods, is based on sol-gel process, with niobium hydroxide Nb (OH)5, sodium potassium tartrate tetrahydrate C4H4KNaO6•4H2O is raw material, with ethylene glycol C2H6O2Being metal-complexing agent for esterifying agent, oxalic acid, the mol ratio of preparation solution is Na:K:Nb=1:1:2, and the composition of obtained potassium-sodium niobate is K( 1-x )NaxNbO3, wherein 0.2 x 0.6, powder granule is bar-shaped；It is characterized in that, by sol-gel process in preparation process and the control of pre-sintering process parameter, prepare different Yu traditional square or the rodlike single-crystal structure powder body of spheroid dress powder granule；The method is characterised by, preparation technology comprises the following steps:
(1) according to mol ratio Nb (OH)5: oxalic acid=1:3 weighs oxalic acid and is dissolved in 90 DEG C of deionized waters, by Nb (OH)5Being dissolved in this solution and form Nb-oxalic acid solution, reaction 1h becomes clarification to solution；
(2) it is Na:K:Nb=1:1:2 according to the mol ratio of sodium potassium Yu niobium, adds sodium potassium tartrate tetrahydrate and fully react 0.5h, it is thus achieved that the solution of transparent clarification；
(3) by ammonia regulation solution ph to 2.5 ~ 3.5,15min is stablized, by n oxalic acid: n ethylene glycol=1:2 drips ethylene glycol in solution, is stirred continuously 2h, obtains pale yellow transparent precursor sol；
(4) in 90 DEG C of air dry ovens, freeze-day with constant temperature makes gelation and being dried of gel once complete for 24 hours, prepares presoma xerogel；
(5) xerogel agate mortar is ground, be placed in alumina crucible, put into and sintering furnace sinters at 750 DEG C 3h, control different 0.5 ~ 3 DEG C/min of heating rate, it is thus achieved that potassium-sodium niobate nanometer rods product.
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| CN105461311B (en) * | 2016-01-15 | 2018-06-12 | 北京工业大学 | Sol-gel methods prepare NaNbO3The method that powder and sintering obtain monocrystalline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010116975A1 (en) * | 2009-04-09 | 2010-10-14 | 堺化学工業株式会社 | Method for producing alkali metal niobate particles, and alkali metal niobate particles |
| CN101921112A (en) * | 2010-07-06 | 2010-12-22 | 齐齐哈尔大学 | Sol-gel method for preparing potassium-sodium niobate nano-powder |
| CN102030531A (en) * | 2010-12-31 | 2011-04-27 | 中国科学院上海硅酸盐研究所 | Method for preparing potassium sodium niobate nano powder |
| CN102180672A (en) * | 2011-03-22 | 2011-09-14 | 南京航空航天大学 | Preparation method of potassium sodium niobate system lead-free piezoelectric ceramic film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010116975A1 (en) * | 2009-04-09 | 2010-10-14 | 堺化学工業株式会社 | Method for producing alkali metal niobate particles, and alkali metal niobate particles |
| CN101921112A (en) * | 2010-07-06 | 2010-12-22 | 齐齐哈尔大学 | Sol-gel method for preparing potassium-sodium niobate nano-powder |
| CN102030531A (en) * | 2010-12-31 | 2011-04-27 | 中国科学院上海硅酸盐研究所 | Method for preparing potassium sodium niobate nano powder |
| CN102180672A (en) * | 2011-03-22 | 2011-09-14 | 南京航空航天大学 | Preparation method of potassium sodium niobate system lead-free piezoelectric ceramic film |
Non-Patent Citations (1)
| Title |
|---|
| Study on synthesis and evolution of sodium potassium niobate ceramic powders by an oxalic acid-based sol–gel method;De-Qing Zhang等;《J Sol-Gel Sci Technol》;20100911;第32页2.1 Preparation of KNN powders以及第34页图6 * |
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