CN1255465A - Process for preparing nm-class barium titanate material - Google Patents
Process for preparing nm-class barium titanate material Download PDFInfo
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- CN1255465A CN1255465A CN 98113027 CN98113027A CN1255465A CN 1255465 A CN1255465 A CN 1255465A CN 98113027 CN98113027 CN 98113027 CN 98113027 A CN98113027 A CN 98113027A CN 1255465 A CN1255465 A CN 1255465A
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- barium titanate
- barium
- preparing
- salt
- solution
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 38
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 29
- 239000002086 nanomaterial Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 10
- 159000000009 barium salts Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- -1 sodium alkylsulfonate Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- PILOURHZNVHRME-UHFFFAOYSA-N [Na].[Ba] Chemical compound [Na].[Ba] PILOURHZNVHRME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A quick deposition method for preparing nm-class barium titanate material includes preparing 0.2M of soluble Ba ion salt solution, mixing the metatitanic acid that is equal mole ratio to the Ba ions salt with strong oxidant in mole ratio of 1 : (5-30), regulating pH value to 10-14, reaction with the prepared Ba ion salt solution and post processing. Its advantages are very low cost and high productivity.
Description
The invention relates to a preparation method of a barium titanate nano material.
The barium titanate material is an important ferroelectric, has very high dielectric constant and changes along with the change of an external electric field, and the barium titanate ceramic prepared by taking the barium titanate material as a main raw material has wide application in industry and can be used for manufacturing ferroelectric dielectric ceramics, ceramic capacitors on a surface layer or a boundary layer and the like. The particle size of the barium titanate material has a significant influence on the properties of the sintered barium titanate ceramic and the barium titanate ceramic itself, such as: when the particle size of the barium titanate material is 20 micrometers (mum) to 50 micrometers (mum), the sintering temperature is about 1350 ℃, and when the particle size is 20 nanometers (nm), the sintering temperature of the barium titanate ceramic can be reduced by about 100 ℃; the sintering density of the barium titanate ceramic prepared from the barium titanate material containing 1 percent of ultrafine powder (nano material) is greatly improved; when the particle size of the barium titanate material is 1nm, the room temperature dielectric constant of the barium titanate ceramic is increased to 6000 from 1500-2000 with the particle size of 20-50 mu m; but also has great influence on characteristics such as Curie temperature, crystal structure, humidity sensitivity and the like. In conclusion, the sodium barium titanate nano material plays a crucial role in the properties of barium titanate ceramics. The conventional barium titanate nano material is prepared by four common preparation methods, wherein one of the common main raw materials of a sol-gel method, a sol-precipitation method and a stearate method is butyl titanate which reacts with a substance containing barium ions to prepare barium titanate, and the fourth method is a coprecipitation method which takes titanium tetrachloride and barium chloride as raw materials and then dissolves in oxalic acid solution to react to prepare barium titanate. And after the reaction is finished, calcining the generated sol or precipitate to obtain the barium titanate material. The four preparation methods have the common defects of high raw material cost, slow reaction speed, long production period, uncontrollable products and more impurities.
The invention aims to provide a preparation method of a barium titanate nano material with low cost, short production period, high product yield and less impurities by changing raw materials and an original process method.
In order to achieve the purpose of the invention, the technical scheme is as follows, which is characterized in that the production is carried out in a reaction kettle by adopting a rapid precipitation method, and the method sequentially comprises the following steps: adding deionized water into a container, adding soluble barium ion salt into the container, and stirring to prepare a solution with the concentration of 0.2M for later use; secondly, adding metatitanic acid with the same mole as barium ion salt into the reaction kettle; thirdly, slowly adding a strong oxidant into the reaction kettle while stirring, wherein the adding amount is metatitanic acid: the molar ratio of the strong oxidant is 1: 5-30; fourthly, adding an alkaline solution, and adjusting the pH value to be 10-14; fifthly, adding the barium salt solution for later use into the reaction kettle; and sixthly, performing post-treatment, after the precipitate is generated, filtering to obtain a precipitate barium titanate, washing with deionized water until the pH value of a washing solution is 7-9, soaking with a surfactant until the washing solution is completely wet, drying with a dryer, and calcining at 300-900 ℃ for 1 hour (h) to obtain a finished product.
In the above method, the molar ratio of the added metatitanic acid to the added strong oxidant is 1: 16-24, preferably in this range.
In the above method, the calcination temperature is preferably 380 to 650 ℃.
In the above method, the barium salt solution is prepared，Ba2+The amount may be in excess, which is not more than 5% of the equimolar amount of the barium salt, to suppress Ba2Ti4O4、BaTi5O11、Ba2Ti9O20And the like.
In the above method, when preparing the barium salt solution, an equimolar or excessive amount of Ba may be added2+Adding soluble salt such as Pb in an amount not more than 2% by mole of the barium salt2+、La3+、Sr2+、Li+Isosoluble salts to inhibit Ba2Ti4O4、BaTi5O11、Ba2Ti9O20And the like.
In the above process, Ba2+The salt can be Ba (NO)3)2Or BaCI2。
In the above method, the strong oxidant is selected from H2O2、KMnO4、KCrO4Etc. to select H2O2Preferably, the purity of the product is high.
In the above method, the alkaline solution can be NaOH or NH4OH, etc. to select NH4Better OH, high product purity and the like.
In the above method, the surfactant can be selected from anhydrous alcohol, alkyl sodium sulfonate, etc.
Compared with the prior art, the invention has the following advantages:
1. the cost is low. The metatitanic acid is a chemical raw material with lower price, and the price of the raw material selected by the method is reduced by 5-10 times compared with that of the raw material used in the prior art, so that the method is suitable for the requirement of industrial mass production.
2. The reaction speed is high and the production period is short. For general reactions, the reaction speed of the reactions in which organic matters participate is relatively slow, and in the prior art, organic matters participate, for example, a coprecipitation method in the prior art, a reaction period of which takes about three days. Meanwhile, in the post-treatment step, the dispersibility of the barium titanate is improved by washing with a surfactant, so that the calcined barium titanate precipitate is not easy to agglomerate and can directly generate a nano material, obviously, the production efficiency is greatly improved.
3. The yield is high. In the prior art, three methods taking butyl titanate as a main raw material are taken as examples, ester can be hydrolyzed when meeting water, and the reaction is reversible reaction, so that the ester is difficult to completely react in one direction, and is difficult to fully utilize when reacting with other substances, so that the yield is low.
4. The impurities are less. In the above preparation method, an excess of soluble Ba is added2+Salt, or adding sufficiently soluble Ba2+Adding a proper amount of Pb on the basis of the salt2+、La3+、Sr2+、Li+And soluble salts of the same kind, one or two kinds being added according to circumstances, the additive being effective in suppressing Ba2Ti4O4、BaTi5O11、Ba2Ti9O20And the like.
5. And the material performance is improved. When adding Pb2+、Sr2+When the soluble salt is of equivalent value, PbTiO will be present in the resultant product3、SrTiO3Etc., wherein PbTiO is present3Can improve the high-temperature sintering performance of barium titanate ceramics, and the existence of Li+、La3+The barium titanate material of the precipitate of isovalent ions can realize semiconducting.
Example 1:
weighing 4.72kg of 20mol Ba (NO)3)2Putting into a container, adding deionized water into the container, and uniformly preparing into 0.2M Ba with a magnetic stirrer2+Salt solution is reserved;
secondly, adding 1.56kg of 20mol H into the reaction kettle2TiO2；
Thirdly, adding 30 percent of H into the reaction kettle2O2Solution 57L with stirring, H2TiO2And H2O2The molar ratio of the added amount is equal to 1: 25, ；
fourthly, adding NH with the concentration of 25 percent into the reaction kettle4OH, adjusting the pH value to be about 12;
fifthly, mixing Ba2+Adding the salt solution into the reaction kettle, stirring uniformly, standing for 1h to allow BaTiO to react3Completely precipitating;
sixthly, post-treatment: filtering to obtain precipitate, washing the precipitate with deionized water until the pH value of the washing solution is about 8, soaking twice with anhydrous ethanol until the precipitate is completely wet, drying in a dryer, and calcining at 600 deg.C for 55min to obtain barium titanate nano material with particle size of about 30 nm.
Examples 2 to 5: in contrast to example 1, as shown in the following table,
(unit: mol)
Claims (8)
1. The preparation method of the barium titanate nano material is characterized by comprising the following steps: the method adopts a rapid precipitation method to produce in a reaction kettle, and sequentially comprises the following steps: adding deionized water into a container, adding soluble barium ion salt into the container, and stirring to prepare a solution with the concentration of 0.2M for later use; secondly, adding metatitanic acid with the same mole as barium ion salt into the reaction kettle; thirdly, slowly adding a strong oxidant into the reaction kettle while stirring, wherein the adding amount is metatitanic acid: the molar ratio of the strong oxidant is 1: 5-30; fourthly, adding an alkaline solution, and adjusting the pH value to be 10-14; fifthly, adding the barium salt solution for later use into the reaction kettle; and sixthly, performing post-treatment, after the precipitate is generated, filtering to obtain a precipitate barium titanate, washing with deionized water until the pH value of a washing solution is 7-9, soaking with a surfactant until the washing solution is completely wet, drying with a dryer, and calcining at 300-900 ℃ for 1 hour to obtain a finished product.
2. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: the molar ratio of the added metatitanic acid to the strong oxidant is 1: 16-24.
3. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: the calcining temperature is 380-650 ℃.
4. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: ba in the barium salt solution2+The amount of addition is equal to or in excess of metatitanic acid, and the excess is not more than 5% of the equimolar amount of barium salt.
5. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: preparing barium salt solution by adding equimolar or overweight Ba2+When the salt is prepared, soluble salt with the molar weight not more than 2% of the barium salt is added. Such as Pb2+、La3+、Sr2+、Li+A soluble salt of (a).
6. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: the strong oxidant is H2O2、KMnO4Or KCrO4。
7. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: the alkaline solution is NH4OH、NaOH。
8. The method for preparing a barium titanate nanomaterial according to claim 1, characterized in that: the surfactant is selected from anhydrous alcohol and sodium alkylsulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113027A CN1098826C (en) | 1998-11-26 | 1998-11-26 | Process for preparing nm-class barium titanate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113027A CN1098826C (en) | 1998-11-26 | 1998-11-26 | Process for preparing nm-class barium titanate material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1255465A true CN1255465A (en) | 2000-06-07 |
| CN1098826C CN1098826C (en) | 2003-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113027A Expired - Fee Related CN1098826C (en) | 1998-11-26 | 1998-11-26 | Process for preparing nm-class barium titanate material |
Country Status (1)
| Country | Link |
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| CN (1) | CN1098826C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362147C (en) * | 2006-04-28 | 2008-01-16 | 河北大学 | Method for preparing nano-barium titanate and doped solid solution by low-temperature solid-state reaction |
| CN100386265C (en) * | 2004-11-11 | 2008-05-07 | 中国科学院成都有机化学有限公司 | Using metatitanic acid as a raw material, the method for synthesizing nano barium titanate powder by atmospheric pressure alcohol thermal method |
| CN100450934C (en) * | 2005-06-14 | 2009-01-14 | 清华大学 | Barium titanate low-dimensional nano powder material and its preparation method |
| CN101792311A (en) * | 2010-03-09 | 2010-08-04 | 武汉理工大学 | Preparation method of barium dititanate target |
| CN101805179A (en) * | 2010-03-04 | 2010-08-18 | 西北工业大学 | Preparation method for barium strontium titanate (BST) thick film material |
| CN109928423A (en) * | 2018-12-28 | 2019-06-25 | 南通奥新电子科技有限公司 | A kind of preparation method of the nano barium phthalate for lithium battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0297823B1 (en) * | 1987-07-02 | 1992-03-18 | Mitsui Petrochemical Industries, Ltd. | Process for producing barium titanates |
| CN1061764A (en) * | 1990-11-23 | 1992-06-10 | 南开大学 | The preparation of ultra-micropowder of high purity barium titanate |
-
1998
- 1998-11-26 CN CN98113027A patent/CN1098826C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386265C (en) * | 2004-11-11 | 2008-05-07 | 中国科学院成都有机化学有限公司 | Using metatitanic acid as a raw material, the method for synthesizing nano barium titanate powder by atmospheric pressure alcohol thermal method |
| CN100450934C (en) * | 2005-06-14 | 2009-01-14 | 清华大学 | Barium titanate low-dimensional nano powder material and its preparation method |
| CN100362147C (en) * | 2006-04-28 | 2008-01-16 | 河北大学 | Method for preparing nano-barium titanate and doped solid solution by low-temperature solid-state reaction |
| CN101805179A (en) * | 2010-03-04 | 2010-08-18 | 西北工业大学 | Preparation method for barium strontium titanate (BST) thick film material |
| CN101805179B (en) * | 2010-03-04 | 2012-11-21 | 西北工业大学 | Preparation method for barium strontium titanate (BST) thick film material |
| CN101792311A (en) * | 2010-03-09 | 2010-08-04 | 武汉理工大学 | Preparation method of barium dititanate target |
| CN101792311B (en) * | 2010-03-09 | 2012-11-07 | 武汉理工大学 | Preparation method of barium dititanate target |
| CN109928423A (en) * | 2018-12-28 | 2019-06-25 | 南通奥新电子科技有限公司 | A kind of preparation method of the nano barium phthalate for lithium battery |
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| Publication number | Publication date |
|---|---|
| CN1098826C (en) | 2003-01-15 |
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