CN102583538A - Sol-gel method for preparation of nanometer potassium sodium niobate rod - Google Patents

Sol-gel method for preparation of nanometer potassium sodium niobate rod Download PDF

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CN102583538A
CN102583538A CN2012100477543A CN201210047754A CN102583538A CN 102583538 A CN102583538 A CN 102583538A CN 2012100477543 A CN2012100477543 A CN 2012100477543A CN 201210047754 A CN201210047754 A CN 201210047754A CN 102583538 A CN102583538 A CN 102583538A
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oxalic acid
solution
sol
potassium
potassium sodium
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CN102583538B (en
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张德庆
杨秀英
朱厚彬
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Qiqihar University
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Abstract

The invention discloses a process for preparation of a nanometer potassium sodium niobate rod by using a sol-gel method. The process comprises the following steps: weighing a certain amount of niobium hydroxide and potassium sodium tartrate, weighing oxalic acid according to a mol ratio of Nb(OH)5 to oxalic acid of 1: 3, dissolving oxalic acid in deionized water with a temperature of 90 DEG C, dissolving Nb(OH)5 in an obtained solution so as to obtain a Nb-oxalic acid solution and allowing the Nb-oxalic acid solution to undergo a reaction for 1 h until the Nb-oxalic acid solution becomes clear; adding potassium sodium tartrate according to the mol ratio of sodium-potassium to niobium in the molecular formula (Na0.5K0.5)NbO3 and allowing potassium sodium tartrate and the clarified Nb-oxalic acid solution to fully react for 0.5 h; adjusting the pH value of the solution to be 2.5 to 3.5 with aqueous ammonia, adding glycol into the solution and carrying out stirring for 2 h so as to obtain light yellow transparent precursor sol; drying the precursor sol at a constant temperature for 24 h in an air blowing drying box with a temperature of 90 DEG C so as to finish gelation and drying of gel in one step, sintering the gel at a temperature of 750 DEG C for 3 h in a sintering furnace after grinding and controlling different heating rates to be in a range of 0.5 to 3 DEG C/min so as to obtain nanometer potassium sodium niobate rods with a single crystal structure.

Description

A kind of sol-gel process for preparing the potassium-sodium niobate nanometer rod
Technical field
A kind of sol-gel process for preparing the potassium-sodium niobate nanometer rod.
Background technology
Potassium-sodium niobate leadless piezoelectric ceramics (K, Na) NbO 3, abbreviate KNN as, be ABO with calcium titanium ore structure 3The type lead-free piezoceramic material, near its accurate homotype phase boundary point, potassium-sodium niobate (K 0.5Na 0.5NbO 3) the base pottery; Because of it has good piezoelectricity, pyroelectricity property, dielectricity, photo, ferroelectricity; And this system is prone to plurality of advantages such as doping vario-property, good stability, heavy metal free pollution, is considered to be hopeful most to substitute the leadless piezoelectric material material system of PZT piezoceramic material.
In recent years, in potassium-sodium niobate powder and film preparation, prepared slender body dress and strip KNN particle both at home and abroad, Wang etc. have found that particle is the slender body shape when 600 ℃ of following sintering prepare the KNN powder in the citric acid method preparation of KNN powder; The particle of film surface was strip when people such as Yan also found to anneal at low temperatures when the sol-gel legal system is equipped with the KNN film, and the relative height of (110) and (001) crystal face has certain corresponding relation in the corresponding XRD diffractogram.When Liu etc. prepare the KNN film in citric acid method, 900 ℃ also find during annealing down surface particles grow up for the length of 10-20 μ m bar-shaped; But they all do not explain the reason that causes these phenomenons, do not further investigate the influence of processing parameter to the NKN pattern yet, and these reports all are to use Hydrocerol A as the metal-complexing agent in addition.
Summary of the invention
Goal of the invention of the present invention provides a kind of simple, manageable process method; Rely on each item processing parameter in control sol-gel technology, the pre-burning process; Pattern with the control powder makes it under specific processing condition, can synthesize the KNN powder of bar-like single crystal structure; Diameter 150-450nm, length 1-3 μ m.The powder of this special appearance possibly have application promise in clinical practice in research of KNN leadless piezoelectric ceramics oriented growth and the preparation of 1-3 type piezo-electricity composite material.
Present method is to be the basis with the sol-gel method, with niobium hydroxide (Nb (OH) 5), Seignette salt (C 4H 4KNaO 64H 2O) be raw material, with terepthaloyl moietie (C 2H 6O 2) for esterifying agent, oxalic acid are the metal-complexing agent, the mol ratio of obtain solution is Na: K: Nb=1: 1: 2, the composition of resulting potassium-sodium niobate nano-powder was K (1-x)Na xNbO 3(0.2≤x≤0.6), powder granule are bar-shaped; It is characterized in that,, prepare the bar-like single crystal structure powder of different and traditional square or spheroid dress powder granule through sol-gel method in the preparation process and pre-sintering process parameter control; This method feature is that preparation technology may further comprise the steps:
1, according to mol ratio Nb (OH) 5: oxalic acid=1: 3 takes by weighing oxalic acid and is dissolved in 90 ℃ of deionized waters, Nb (OH) 5 is dissolved in this solution forms the Nb-oxalic acid solution, and reaction 1h clarifies to solution becomes;
2, according to molecular formula (Na 0.5K 0.5) NbO 3The mol ratio of middle sodium potassium and niobium adds Seignette salt and fully reacts 0.5h, obtains transparent clear soln;
3, with ammoniacal liquor regulator solution pH value to 2.5～3.5, stablize 15min,, constantly stir 2h, obtain faint yellow transparent precursor sol by n (oxalic acid): n (terepthaloyl moietie)=in solution, drip terepthaloyl moietie at 1: 2;
4, freeze-day with constant temperature made gelation and Drying of gels once accomplish in 24 hours in 90 ℃ of air dry ovens, prepared the presoma xerogel;
5, xerogel is ground with agate mortar, place alumina crucible, put into sintering oven, control different 0.5～3 ℃/min of temperature rise rate, to obtain the potassium-sodium niobate nanometer rod at 750 ℃ of following sintering 3h.
The present invention has designed following technical scheme for realizing the foregoing invention purpose:
The raw material that is adopted is niobium hydroxide (Nb (OH) 5), Seignette salt (C 4H 4KNaO 64H 2O), terepthaloyl moietie, oxalic acid, ammoniacal liquor, wherein mol ratio is Na: K: Nb=1: 1: 2, niobium hydroxide: oxalic acid=3: 1.
Its concrete preparation technology is following:
1, according to mol ratio Nb (OH) 5: oxalic acid=1: 3 takes by weighing oxalic acid and is dissolved in 90 ℃ of deionized waters, Nb (OH) 5 is dissolved in this solution forms the Nb-oxalic acid solution, and reaction 1h clarifies to solution becomes.
2, according to molecular formula (Na 0.5K 0.5) NbO 3The mol ratio of middle sodium/potassium and niobium adds Seignette salt and fully reacts 0.5h, obtains transparent clear soln.
3, with ammoniacal liquor regulator solution pH value to 2.5～3.5, stablize 15min,, constantly stir 2h, obtain faint yellow transparent precursor sol by n (oxalic acid): n (terepthaloyl moietie)=in solution, drip terepthaloyl moietie at 1: 2.
4, freeze-day with constant temperature made gelation and Drying of gels once accomplish in 24 hours in 90 ℃ of air dry ovens, prepared the presoma xerogel.
5, xerogel is ground with agate mortar, place alumina crucible, put into sintering oven, control different 1～3 ℃/min of temperature rise rate to obtain the potassium-sodium niobate nanometer rod at 750 ℃ of following sintering 3h.
At present, the domestic solid phase method that mostly adopts prepares the KNN powder, and its shortcoming is: synthesis temperature is high, thereby is prone to cause a large amount of volatilizations of K/Na to cause all kinds of atoms to depart from original components.Though the preparation of the nanometer rod of potassium niobate is seen in report, the self-assembly of potassium-sodium niobate nanometer rod preparation does not still have report.Realize that with processing parameter in the control sol-gel method self-assembly of KNN nanometer rod under the no template situation prepares in the technical scheme of the present invention.The niobium source of the most often adopting when preparing the NKN leadless piezoelectric ceramics both at home and abroad at present is Nb 2O 5, ethanol niobium, NbCl 5Deng, Nb wherein 2O 5Chemical property highly stable, be difficult to and other material generation chemical reaction; The price of ethanol niobium is very expensive again, and very easily hydrolysis this just need in dry and rare gas element, preserve, be difficult in industry, promote with regard to feasible like this; NbCl 5Use can introduce muriatic impurity inevitably, influence the electrical property of material.Freshly prepd niobium hydroxide compares Nb 2O 5Active strong, can be relatively easy to be dissolved in carboxylic acids such as oxalic acid, Hydrocerol A and tartrate.In view of more than the shortcoming in various niobiums commonly used source, this paper intends and utilizes Nb 2O 5Prepare fresh niobium hydroxide earlier as the niobium source.Preparation flow: in 80 ℃ of water-baths, take by weighing Nb in proportion 2O 5Be dissolved among the HF generate faint yellow; Reaction 1h is to adding excessive ammonium oxalate solution after the dissolving fully; At 80 ℃ of following heated and stirred 1h, fully reaction generates light green solution in electromagnetism heated and stirred cover, in above-mentioned solution, drips excessive ammonia behind the 1h to generating white Nb (OH) fully 5Deposition is regulated pH to 8～9.80 ℃ of following ageing 2h after scouring filter repetitive scrubbing three times.Wet niobium hydroxide is put into 60 ℃ of following dry 24h of air dry oven, grind for use with agate mortar.The invention has the beneficial effects as follows:, adopt in oxalic acid, to add new preparation Nb (OH) owing to use niobium hydroxide to make cost reduce and can avoid the introducing of impurity greatly 5Process method with Seignette salt; The more solution dissolving of new niobium hydroxide; Seignette salt and oxalic acid react and can strengthen the system complexing action and make sol system more stable, and Drying of gels is accomplished easily, has made things convenient for operation; The volatilization of K/Na composition has obtained better inhibition in the sintering process, has guaranteed synthetic stability.
Embodiment
Embodiment 1:
To prepare 11.00 gram K 0.5Na 0.5NbO 3Nano-powder is an example, and required raw material is that oxalic acid 24 grams, niobium hydroxide 11.5 grams, Seignette salt 8.73 grams, terepthaloyl moietie 15ml, ammoniacal liquor are an amount of.Concrete operations are following:
1,24g oxalic acid is dissolved in the deionized water under 90 ℃ of the 400ml, with 11.5g Nb (OH) 5Be dissolved in this solution and form the Nb-oxalic acid solution, reaction 1h clarifies to solution becomes.
2, with fully reacting 0.5h in the above-mentioned solution of 90 ℃ of 8.73g Seignette salt addings, obtain transparent clear soln.
3, with ammoniacal liquor regulator solution pH value to 3.5, stablize 15min after, under 90 ℃ reaction conditions, dropwise in solution, drip 15ml terepthaloyl moietie, constantly stir 2h, obtain faint yellow transparent precursor sol.
4, freeze-day with constant temperature made gelation and Drying of gels once accomplish in 24 hours in 90 ℃ of air dry ovens, obtained faint yellow presoma xerogel.
5, xerogel is ground with agate mortar, place alumina crucible, the heat-up rate of 30min is warming up to 120 ℃, constant temperature 0.5 hour; Be warming up to 450 ℃ with 3～5 ℃ of heat-up rates again, constant temperature 2 hours; Be warming up to 750 ℃ with 1 ℃/min again, furnace cooling behind insulation 3h under 750 ℃ gets 11.00gK 0.5Na 0.5NbO 3Nanometer rod.
Embodiment 2:
To prepare 5.50 gram K 0.5Na 0.5NbO 3Nano-powder is an example, and required raw material is oxalic acid 12 grams, niobium hydroxide 5.8 grams, Seignette salt 4.36 grams, terepthaloyl moietie 8ml.Concrete operations are following:
1,12g oxalic acid is dissolved in the deionized water under 90 ℃ of the 200ml, with 5.8g Nb (OH) 5Be dissolved in this solution and form the Nb-oxalic acid solution, reaction 1h clarifies to solution becomes.
2, with fully reacting 0.5h in the above-mentioned solution of 90 ℃ of 4.36g Seignette salt addings, obtain transparent clear soln.
3, with ammoniacal liquor regulator solution pH value to 3, stablize 15min after, under 90 ℃ reaction conditions, dropwise in solution, drip 8ml terepthaloyl moietie, constantly stir 2h, obtain faint yellow transparent precursor sol.
4, freeze-day with constant temperature 24h once accomplishes gelation and Drying of gels in 90 ℃ of air dry ovens, obtains faint yellow presoma xerogel.
5, xerogel is ground with agate mortar, place alumina crucible, the heat-up rate of 30min is warming up to 120 ℃, constant temperature 0.5 hour; Be warming up to 450 ℃ with 3～5 ℃ of heat-up rates again, constant temperature 2 hours; Be warming up to 750 ℃ with 1 ℃/min again, furnace cooling behind insulation 3h under 750 ℃ gets 5.50gK 0.5Na 0.5NbO 3Nanometer rod.
Embodiment 3:
To prepare 2.80 gram K 0.5Na 0.5NbO 3Nano-powder is an example, and required raw material is oxalic acid 8 grams, niobium hydroxide 2.9 grams, carbon Seignette salt 2.44 grams, terepthaloyl moietie 6ml.Concrete operations are following:
1,8g oxalic acid is dissolved in the deionized water under 90 ℃ of the 200ml, with 2.9g Nb (OH) 5Be dissolved in this solution and form the Nb-oxalic acid solution, reaction 1h clarifies to solution becomes.
2, with fully reacting 0.5h in the above-mentioned solution of 90 ℃ of 2.44g Seignette salt addings, obtain transparent clear soln.
3, with ammoniacal liquor regulator solution pH value to 2.5, stablize 15min after, under 90 ℃ reaction conditions, dropwise in solution, drip 6ml terepthaloyl moietie, constantly stir 2h, obtain faint yellow transparent precursor sol.
4, freeze-day with constant temperature made gelation and Drying of gels once accomplish in 24 hours in 90 ℃ of air dry ovens, obtained faint yellow presoma xerogel.
5, xerogel is ground with agate mortar, place alumina crucible, the heat-up rate of 30min is warming up to 120 ℃, constant temperature 0.5 hour; Be warming up to 450 ℃ with 3～5 ℃ of heat-up rates again, constant temperature 2 hours; Be warming up to 750 ℃ with 1 ℃/min again, furnace cooling behind insulation 3h under 750 ℃ gets 11.00gK 0.5Na 0.5NbO 3Nanometer rod.

Claims (1)

1. a method for preparing the potassium-sodium niobate nanometer rod is to be the basis with the sol-gel method, with niobium hydroxide (Nb (OH) 5), Seignette salt (C 4H 4KNaO 64H 2O) be raw material, with terepthaloyl moietie (C 2H 6O 2) for esterifying agent, oxalic acid are the metal-complexing agent, the mol ratio of obtain solution is Na: K: Nb=1: 1: 2, the composition of resulting potassium-sodium niobate nano-powder was K (1-x)Na xNbO 3(0.2≤x≤0.6), powder granule are bar-shaped; It is characterized in that,, prepare the bar-like single crystal structure powder of different and traditional square or spheroid dress powder granule through sol-gel method in the preparation process and pre-sintering process parameter control; This method feature is that preparation technology may further comprise the steps:
(1) according to mol ratio Nb (OH) 5: oxalic acid=1: 3 takes by weighing oxalic acid and is dissolved in 90 ℃ of deionized waters, Nb (OH) 5 is dissolved in this solution forms the Nb-oxalic acid solution, and reaction 1h clarifies to solution becomes;
(2) according to molecular formula (Na 0.5K 0.5) NbO 3The mol ratio of middle sodium potassium and niobium adds Seignette salt and fully reacts 0.5h, obtains transparent clear soln;
(3) with ammoniacal liquor regulator solution pH value to 2.5～3.5, stablize 15min,, constantly stir 2h, obtain faint yellow transparent precursor sol by n (oxalic acid): n (terepthaloyl moietie)=in solution, drip terepthaloyl moietie at 1: 2;
(4) freeze-day with constant temperature made gelation and Drying of gels once accomplish in 24 hours in 90 ℃ of air dry ovens, prepared the presoma xerogel;
(5) xerogel is ground with agate mortar, place alumina crucible, put into sintering oven, control different 0.5～3 ℃/min of temperature rise rate, to obtain the potassium-sodium niobate nanometer rod at 750 ℃ of following sintering 3h.
CN201210047754.3A 2012-02-28 2012-02-28 A kind of sol-gel process preparing potassium-sodium niobate nanometer rods Expired - Fee Related CN102583538B (en)

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CN104876269A (en) * 2015-05-18 2015-09-02 哈尔滨工业大学 Synthetic method of sodium potassium columbate ferroelectric nano structure with monoclinic phase
CN105461311A (en) * 2016-01-15 2016-04-06 北京工业大学 Method for making NaNbO3 powder through sol-gel method and obtaining monocrystals through sintering

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Cited By (3)

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CN104876269A (en) * 2015-05-18 2015-09-02 哈尔滨工业大学 Synthetic method of sodium potassium columbate ferroelectric nano structure with monoclinic phase
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CN105461311A (en) * 2016-01-15 2016-04-06 北京工业大学 Method for making NaNbO3 powder through sol-gel method and obtaining monocrystals through sintering

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