CN101921112A - Sol-gel method for preparing potassium-sodium niobate nano-powder - Google Patents
Sol-gel method for preparing potassium-sodium niobate nano-powder Download PDFInfo
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- CN101921112A CN101921112A CN 201010228873 CN201010228873A CN101921112A CN 101921112 A CN101921112 A CN 101921112A CN 201010228873 CN201010228873 CN 201010228873 CN 201010228873 A CN201010228873 A CN 201010228873A CN 101921112 A CN101921112 A CN 101921112A
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- oxalic acid
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Abstract
The invention discloses a process for preparing potassium-sodium niobate lead-free piezoelectric ceramic nano-powder by using a sol-gel method. The newly prepared niobium hydroxide (Nb(OH)5), sodium carbonate (Na2CO3) and potassium carbonate (K2CO3) are used as raw materials, glycol (C2H6O2) is used as an esterifying agent and oxalic acid is used as a metal coordination agent. The preparation process comprises the following steps: dripping the oxalic acid solution into a solution containing sodium carbonate and potassium carbonate; standing for 1 h at a temperature between 75 and 90 DEG C; adding the newly prepared niobium hydroxide into the system; after the niobium hydroxide is dissolved and a clear solution is formed, adding the glycol to obtain light yellow sol; performing constant-temperature drying in a 90 DEG C air dry oven so that gelation and drying of the gel are finished at a time; and sintering the dry gel powder in a corundum crucible at a temperature of 750 DEG C and a temperature of 800 DEG C to obtain the light yellow potassium-sodium niobate lead-free piezoelectric ceramic nano-powder. The invention has the advantages of simple and convenient process, relatively low cost and stable product quality.
Description
Technical field
A kind of sol-gel process for preparing potassium-sodium niobate nano-powder.
Background technology
Potassium-sodium niobate leadless piezoelectric ceramics (K, Na) NbO
3, abbreviate the KNN material as, be ABO with uhligite phase structure
3The type piezoceramic material is especially formed near the potassium-sodium niobate (K accurate homotype phase boundary point
0.5Na
0.5NbO
3) pottery, because of it has good piezoelectricity, pyroelectricity, dielectricity, photo, ferroelectricity, easy doping vario-property, plurality of advantages such as good stability, its Application Areas is constantly excavated and is developed.
The KNN preparation methods is existing multiple, and that domestic present discussion is maximum is oxide compound solid phase method, hydrothermal method and citric acid method, wherein K
0.5Na
0.5NbO
3The preparation of nano-powder material mainly is hydrothermal method and citric acid method.In people's such as Zhang Mei the patent of invention (application number is CN200710178705.2), be raw material with potassium hydroxide, sodium hydroxide, Niobium Pentxoxide and tantalum pentoxide wherein, hydro-thermal is synthesized the adulterated K of tantalum
0.5Na
0.5NbO
3Powder.People such as Hao Jigong are at " citric acid method preparation (K
1/2Na
1/2) NbO
3Leadless piezoelectric ceramics and performance study thereof " in the literary composition (" functional materials " supplementary issue 38 volumes in 2007,722-723 page or leaf), combine citric acid method and solid-phase synthesis are effective, with analytically pure Na
2CO
3, K
2CO
3, Nb
2O
5With citric acid be raw material, first preparation Na
2CO
3The aqueous solution, K
2CO
3The aqueous solution after two solution mixing and stirring, adds an amount of aqueous citric acid solution, regulates pH to 7～8 with ammoniacal liquor, adds load weighted Nb again
2O
5, the back oven dry stirs; The powder of oven dry is incubated the synthetic K of 2h down at 800-900 ℃
0.5Na
0.5NbO
3Powder.This method is Nb when actually operating
2O
5Solvability bad, the sintering temperature height.
Summary of the invention
It is a kind of simple to operate that goal of the invention of the present invention is to provide, and institute's consumption material cost is lower, and the good Sol-gel legal system of quality product is equipped with the processing method of potassium-sodium niobate nano-powder.
The present invention has designed following technical scheme for achieving the above object:
The raw material that is adopted is niobium hydroxide (Nb (OH)
5), yellow soda ash (Na
2CO
3), salt of wormwood (K
2CO
3), ethylene glycol, oxalic acid, wherein mol ratio is Na: K: Nb=1: 1: 2.
Its concrete preparation technology is as follows:
1, under 75 ℃～90 ℃ condition, by measuring ratio respectively with yellow soda ash (Na
2CO
3), salt of wormwood (K
2CO
3) soluble in water, oxalic acid is soluble in water.
2, oxalic acid aqueous solution slowly is added drop-wise to yellow soda ash (Na
2CO
3), salt of wormwood (K
2CO
3) in the aqueous solution, at 75 ℃～90 ℃ static 1h.In system, add niobium hydroxide, white casse solution occurs, 75 ℃～90 ℃ static 2 hours transparent to mixed solution.
3, ethylene glycol solution is joined in the settled solution in 2, obtain faint yellow colloidal sol.
4, the colloidal sol freeze-day with constant temperature in 90 ℃ of air dry ovens that obtains was obtained xerogel in 24 hours.
5,, be placed on that the heat-up rate with 3～5 ℃/min is warming up to 200 ℃, constant temperature 1 hour in the corundum crucible with the xerogel grinding powder; Be warming up to 750 ℃ with 3～5 ℃ of heat-up rates again, constant temperature is furnace cooling after 5 hours, gets faint yellow nanometer potassium-sodium niobate (K
0.5Na
0.5NbO
3) nano-powder.
At present the domestic solid phase method that mostly adopts prepares KNN, and its shortcoming is the synthesis temperature height, thereby is operational path with the sol-gel method in the technical solution of the present invention.Preparation niobate compound niobium source commonly used mainly contains niobium oxides, niobium oxalate, ethanol niobium and niobium chloride etc. at present.The oxalate that produces after niobium oxalate is water-soluble can produce precipitation with a lot of ions, has influenced chemical constitution.Niobium oxides is a kind of common niobium source.But Nb
2O
5Chemical property very stable, with the ability of other substance reactions a little less than.The price of ethanol niobium is very expensive, very easily hydrolysis and need in dry and rare gas element, keeping, can only be in test among a small circle trial, can not in industry, promote.NbCl
5In use can introduce chloride impurity, influence the electrical property of material.And freshly prepd niobium hydroxide compares Nb
2O
5Active strong, can be dissolved in carboxylic acids such as oxalic acid, citric acid and tartrate.In view of the shortcoming in above niobium commonly used source, this paper utilizes Nb
2O
5Convert fresh sedimentary niobium hydroxide to, and produce potassium-sodium niobate nano-powder by sol-gel method.
In addition, the preparation manipulation temperature of colloidal sol is very big to the stability influence of product colloidal sol.Analyzed comparison by the collosol stability that condition of different temperatures is made, the service temperature that the present invention suits is 75～90 ℃.The collosol stability that obtains under this temperature is good especially.
The invention has the beneficial effects as follows:, adopt to yellow soda ash (Na owing to use niobium hydroxide that cost is reduced greatly
2CO
3), salt of wormwood (K
2CO
3) processing method that drips oxalic acid solution in the aqueous solution make colloidal sol preparation technology more rationally, be convenient to operation, colloidal sol is more stable, Drying of gels is finished easily, has made things convenient for operation, sintering process is simple, the time is short.
Embodiment
Embodiment 1
To prepare 11.00 gram K
0.5Na
0.5NbO
3Nano-powder is an example, and required raw material is oxalic acid 24 grams, niobium hydroxide 11.5 grams, yellow soda ash 6.88 grams, salt of wormwood 5.28 grams, ethylene glycol 15ml.Concrete operations are as follows:
1, under 80 ℃ of conditions, yellow soda ash 6.88 grams, salt of wormwood 5.28 grams are dissolved in the 100ml water, oxalic acid 24 grams are dissolved in the 300ml water.
2, the 300ml oxalic acid solution slowly is added drop-wise in yellow soda ash and the salt of wormwood blended solution, at 80 ℃ of static 1h, after treating fully to react.In system, add 11.5 gram niobium hydroxides, white casse solution occurs, 80 ℃ static 2 hours transparent to mixed solution.
3, the 15ml ethylene glycol solution is joined in the mixing solutions in 2, obtain faint yellow colloidal sol.
4, with the colloidal sol that obtains freeze-day with constant temperature 24 hours in 90 ℃ of air dry ovens, obtain white xerogel.
5,, be placed on that the heat-up rate with 3～5 ℃/min is warming up to 200 ℃, constant temperature 0.5 hour in the crucible with the xerogel grinding powder; Be warming up to 750 ℃ with 3～5 ℃ of heat-up rates again, constant temperature is furnace cooling after 5 hours, gets 11.00 gram nano level K
0.5Na
0.5NbO
3Powder.
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, yellow soda ash 3.44 grams, salt of wormwood 2.64 grams, ethylene glycol 8ml.Concrete operations are as follows:
1, under 90 ℃ of conditions, yellow soda ash 3.44 grams, salt of wormwood 2.64 grams are dissolved in the 100ml water, oxalic acid 12 grams are dissolved in the 400ml water.
2, the 400ml oxalic acid solution slowly is added drop-wise in yellow soda ash and the salt of wormwood blended solution, at 90 ℃ of static 1h, after treating fully to react.In system, add 5.8 gram niobium hydroxides, white casse solution occurs, 90 ℃ static 2 hours transparent to mixed solution, regulating the pH value with ammoniacal liquor then is 2.
3, the 8ml ethylene glycol solution is joined in the mixing solutions in 2, obtain faint yellow colloidal sol.
4, with the colloidal sol that obtains freeze-day with constant temperature 24 hours in 90 ℃ of air dry ovens, obtain white dry gel powder.
5, xerogel is ground, be placed on that the heat-up rate with 3～5 ℃/min is warming up to 180 ℃, constant temperature 0.5 hour in the crucible; Be warming up to 750 ℃ with 3～5 ℃ of heat-up rates again, constant temperature is furnace cooling after 5 hours, gets 5.50 gram nano level K
0.5Na
0.5NbO
3Powder.
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, yellow soda ash 1.73 grams, salt of wormwood 1.33 grams, ethylene glycol 10ml.Concrete operations are as follows:
1, under 75 ℃ of conditions, yellow soda ash 1.73 grams, salt of wormwood 1.33 grams are dissolved in the 100ml water, oxalic acid 8 grams are dissolved in the 400ml water.
2, the 400ml oxalic acid solution slowly is added drop-wise in yellow soda ash and the salt of wormwood blended solution, at 75 ℃ of static 1h, after treating fully to react.In system, add 2.9 gram niobium hydroxides, white casse solution occurs, 75 ℃ static 2 hours transparent to mixed solution.
3, the 10ml ethylene glycol solution is joined in the mixing solutions in 2, obtain faint yellow colloidal sol.
4, with the colloidal sol that obtains freeze-day with constant temperature 24 hours in 90 ℃ of air dry ovens, obtain transparent sticky xerogel.
5, xerogel is placed on the heat-up rate with 3～5 ℃/min is warming up to 120 ℃, constant temperature 0.5 hour in the crucible; Be warming up to 200 ℃ with 3～5 ℃ of heat-up rates again, constant temperature 0.5 hour; Be warming up to 750 ℃ with 3～5 ℃ of heat-up rates again, constant temperature is furnace cooling after 5 hours, gets 2.8 gram nano level K
0.5Na
0.5NbO
3Powder.
Claims (1)
1. a method for preparing potassium-sodium niobate nano-powder is based on sol-gel method, with niobium hydroxide (Nb (OH)
5), yellow soda ash (Na
2CO
3), salt of wormwood (K
2CO
3) be raw material, with ethylene glycol (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
0.5Na
0.5NbO
3It is characterized in that: the solvent of obtain solution for water preparation technology is:
1) under 75 ℃～90 ℃ conditions, by measuring than Na: K=1: 1, respectively with yellow soda ash (Na
2CO
3), salt of wormwood (K
2CO
3) be dissolved in the 100ml water, oxalic acid is dissolved in the 300ml water;
2) oxalic acid aqueous solution slowly is added drop-wise in the aqueous solution of Na, K, static 30 minutes at 75～90 ℃.In system, add niobium hydroxide, white casse solution occurs, 75～90 ℃ static 2 hours transparent to mixed solution;
3) ethylene glycol is added in the solution in above-mentioned 2, obtain faint yellow colloidal sol.
4) the colloidal sol freeze-day with constant temperature in 90 ℃ of air dry ovens that obtains was obtained xerogel in 24 hours;
5), be placed on that the heat-up rate with 3～5 ℃/min is warming up to 200 ℃, constant temperature 0.5 hour in the crucible with the xerogel grinding powder; Be warming up to 750 ℃ with 3～5 ℃ of heat-up rates again, constant temperature is furnace cooling after 5 hours, gets faint yellow nanometer potassium-sodium niobate K
0.5Na
0.5NbO
3Powder.
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|---|---|---|---|
| CN 201010228873 CN101921112A (en) | 2010-07-06 | 2010-07-06 | Sol-gel method for preparing potassium-sodium niobate nano-powder |
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| CN 201010228873 CN101921112A (en) | 2010-07-06 | 2010-07-06 | Sol-gel method for preparing potassium-sodium niobate nano-powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102583538A (en) * | 2012-02-28 | 2012-07-18 | 齐齐哈尔大学 | Sol-gel method for preparation of nanometer potassium sodium niobate rod |
| 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 |
| CN108558401A (en) * | 2018-05-17 | 2018-09-21 | 韶关学院 | A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330697A (en) * | 1963-08-26 | 1967-07-11 | Sprague Electric Co | Method of preparing lead and alkaline earth titanates and niobates and coating method using the same to form a capacitor |
| CN101538067A (en) * | 2009-04-27 | 2009-09-23 | 桂林工学院 | Method for chemically synthesizing potassium sodium niobate nano-powder |
-
2010
- 2010-07-06 CN CN 201010228873 patent/CN101921112A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330697A (en) * | 1963-08-26 | 1967-07-11 | Sprague Electric Co | Method of preparing lead and alkaline earth titanates and niobates and coating method using the same to form a capacitor |
| CN101538067A (en) * | 2009-04-27 | 2009-09-23 | 桂林工学院 | Method for chemically synthesizing potassium sodium niobate nano-powder |
Non-Patent Citations (1)
| Title |
|---|
| 《陶瓷》 20081231 杨海波等 聚合物前驱体法低温制备铌酸钾钠超细粉体 第22-23页及第28页 1 , 第5期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102030531B (en) * | 2010-12-31 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Method for preparing potassium sodium niobate nano powder |
| CN102583538A (en) * | 2012-02-28 | 2012-07-18 | 齐齐哈尔大学 | Sol-gel method for preparation of nanometer potassium sodium niobate rod |
| CN102583538B (en) * | 2012-02-28 | 2016-07-20 | 齐齐哈尔大学 | A kind of sol-gel process preparing potassium-sodium niobate nanometer rods |
| 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 |
| CN104876269B (en) * | 2015-05-18 | 2016-08-24 | 哈尔滨工业大学 | There is the synthetic method of the potassium-sodium niobate nanostructures of monocline thing phase |
| CN108558401A (en) * | 2018-05-17 | 2018-09-21 | 韶关学院 | A kind of sol-gal process preparation Bi2/3Cu2Ta2Ti2O12The method of ceramic powder |
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Application publication date: 20101222 |