JPH0246531B2 - - Google Patents
Info
- Publication number
- JPH0246531B2 JPH0246531B2 JP60215627A JP21562785A JPH0246531B2 JP H0246531 B2 JPH0246531 B2 JP H0246531B2 JP 60215627 A JP60215627 A JP 60215627A JP 21562785 A JP21562785 A JP 21562785A JP H0246531 B2 JPH0246531 B2 JP H0246531B2
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- barium
- reaction
- strontium
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910002367 SrTiO Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- -1 nitrate compound Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
本発明は、微細で均一な粒径を有するチタン酸
バリウムまたはチタン酸ストロンチウム粉末の合
成法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing barium titanate or strontium titanate powder having a fine and uniform particle size.
近年、電子製品の小形化、高性能化に伴い、セ
ラミツクコンデンサーも小形化高容量化が望まれ
ており、その一つとして積層コンデンサーが注目
を集めている。この多層セラミツクのコンデンサ
ーには、強誘導体として、主としてチタン酸バリ
ウム(BaTiO3)およびチタン酸ストロンチウム
(SrTiO3)が用いられ、厚みを薄く、均一にする
ためにこれらの材料粉末の微細化が要望されてい
る。 In recent years, as electronic products have become smaller and have higher performance, ceramic capacitors are also desired to be smaller and have higher capacity, and multilayer capacitors are one of them that is attracting attention. Barium titanate (BaTiO 3 ) and strontium titanate (SrTiO 3 ) are mainly used as ferroconductors in this multilayer ceramic capacitor, and there is a demand for finer powders of these materials in order to make the thickness thinner and more uniform. has been done.
現在、積層コンデンサーの電極間距離は、最小
で20μm程度であり、今後、さらに小さくするこ
とを検討されている。したがつて、焼結体の粒径
は10μm以下であることが必要であり、そのため
には原料粉末の粒径は1μm以下であることが好
ましい。 Currently, the minimum distance between the electrodes of multilayer capacitors is about 20 μm, and further reductions are being considered in the future. Therefore, it is necessary that the particle size of the sintered body is 10 μm or less, and for this purpose, the particle size of the raw material powder is preferably 1 μm or less.
粒径が1μm以下のBaTiO3またはSrTiO3の製造
方法として、炭酸バリウム、または炭酸ストロン
チウムと、二酸化チタンを1000℃以上の高温で反
応させてBaTiO3またはSrTiO3を含成し、機械的
に粉砕、分級する方法がある。しかしこの方法で
は、反応時に焼結が進み、粗大化した粒子を多量
に含むので、微細で均一な粒度を有する粉末を得
ることは、本質的に困難であるという欠点を有し
ている。 As a method for producing BaTiO 3 or SrTiO 3 with a particle size of 1 μm or less, barium carbonate or strontium carbonate is reacted with titanium dioxide at a high temperature of 1000°C or higher to contain BaTiO 3 or SrTiO 3 , and then mechanically pulverized. , there is a method of classification. However, this method has the disadvantage that it is essentially difficult to obtain powder with fine and uniform particle size because sintering progresses during the reaction and contains a large amount of coarse particles.
また最近、金属アルコキシドを使用する合成法
が試みられているが、原料が高価で工業化には問
題がある。またシユウ酸法は、シユウ酸塩を600
℃以上で焼成して、チタン酸塩を合成する方法で
あるが、本質的には炭酸バリウムまたは炭酸スト
ロンチウムと酸化チタンとの反応であり、固相反
応に近いものになり、均一な粒度を有する粒末を
得ることは困難である。 Recently, synthetic methods using metal alkoxides have been attempted, but the raw materials are expensive and there are problems with industrialization. In addition, the oxalic acid method uses oxalate at 600%
This method synthesizes titanate by firing at temperatures above ℃, but it is essentially a reaction between barium carbonate or strontium carbonate and titanium oxide, which is close to a solid phase reaction and has a uniform particle size. It is difficult to obtain granules.
一方、水酸化物法は原料も比較的安価であり、
得られる粉末も焼結性が高いという点で注目され
ている。たとえば特開昭60−90825号公報におい
て、チタン酸と水酸化バリウムを多量の杉の存在
下で、沸点以下の温度で加熱する方法が提案され
ているが、該発明の場合、チタン酸をあらかじ
め、調整する工程が必要である。 On the other hand, the raw materials for the hydroxide method are relatively cheap;
The resulting powder is also attracting attention because of its high sinterability. For example, in JP-A-60-90825, a method is proposed in which titanic acid and barium hydroxide are heated at a temperature below the boiling point in the presence of a large amount of cedar. , an adjustment process is required.
チタン酸を、チタン化合物の水溶液の中和によ
つて、沈澱させた場合には、コロイドであるた
め、洗浄および過が工業的に困難であると云う
問題がある。また、特開昭50−86024号公報にお
いて、硫酸法二酸化チタン製造工程で生成するチ
タン酸を精製して、用いる方法が提案されている
が、チタン酸に含まれているニオブ、および硫酸
根を、十分に取り除くことは困難である。 When titanic acid is precipitated by neutralizing an aqueous solution of a titanium compound, there is a problem in that it is industrially difficult to wash and filter because it is a colloid. In addition, JP-A-50-86024 proposes a method of purifying and using titanic acid produced in the sulfuric acid method titanium dioxide production process, but the niobium and sulfate groups contained in titanic acid are , it is difficult to remove it sufficiently.
チタン酸を、あらかじめ調整せずに、チタン酸
バリウムを合成する方法が特開昭59−9726号公報
で提案されている。該発明の方法は、チタン塩の
水溶液に塩化バリウム、硝酸バリウムを溶解し、
アルカリを加えてPHを13以上に調整して、沸点以
下で加熱する方法である。しかしながら該発明を
詳細に検討した結果、反応生成物のTiO2とBaO
のモル比を所定のモル比に調整することが困難で
あること、および、粉末の粒径が200〜300Åと微
細であるため、成形加工した場合の密度が低く、
焼結時の収縮が大きいと云う問題があり、用途に
よつては好ましくない場合がある。 JP-A-59-9726 proposes a method for synthesizing barium titanate without preparing titanic acid in advance. The method of the invention includes dissolving barium chloride and barium nitrate in an aqueous solution of titanium salt,
This method involves adding alkali to adjust the pH to 13 or higher, and then heating below the boiling point. However, as a result of a detailed study of the invention, the reaction products TiO 2 and BaO
It is difficult to adjust the molar ratio of
There is a problem of large shrinkage during sintering, which may be undesirable depending on the application.
ところが、本発明者らは、水酸物法について鋭
意研究を進めた結果、四塩化チタンの水溶液に、
バリウムまたはストロンチウムの炭酸塩、塩化
物、硝酸塩のうち、いずれか1種類の化合物を溶
解し、水酸化ナトリウム、または、水酸化カリウ
ムを加えて、オートクレーブ中で加熱することに
より、平均粒径が0.05〜0.5μmで均一な粒度を有
するBaTiO3またはSrTiO3が得られることを見い
出し、この知見にもとづいて本発明をなすに至つ
た。 However, as a result of intensive research into the hydroxide method, the present inventors found that an aqueous solution of titanium tetrachloride,
By dissolving any one type of barium or strontium carbonate, chloride, or nitrate compound, adding sodium hydroxide or potassium hydroxide, and heating in an autoclave, the average particle size is 0.05. It has been discovered that BaTiO 3 or SrTiO 3 having a uniform particle size of ~0.5 μm can be obtained, and the present invention has been completed based on this finding.
本発明に方法において、オートクレーブで加熱
せずに、大気下、沸点で加熱する場合、たとえ
ば、仕込みのBaO/TiO2のモル比が1.0であつて
も反応率は70%程度と低く、従つて生成物の
BaO/TiO2のモル比が0.7のように低いものしか
得られない。反応時の仕込みのモル比を2.0と高
くすれば、生成物のモル比は1.0に近くなるが、
経済的に好ましくない。また粉末の1次粒子径は
100Å以下で微細であるが、0.02〜0.3μmの不均
一な粒径の凝集粒子を形成しており、粒子密度も
小さく好ましくない。しかるに、オートクレーブ
を用いて、水熱反応させた場合、反応率は97%以
上になり、かつ非常に均一な粒度の分散性の良い
粒末が得られることを見い出した。 In the method of the present invention, when heating at the boiling point in the atmosphere without heating in an autoclave, for example, even if the molar ratio of BaO/TiO 2 charged is 1.0, the reaction rate is as low as about 70%. of the product
Only BaO/TiO 2 molar ratios as low as 0.7 can be obtained. If the molar ratio of the feed during the reaction is increased to 2.0, the molar ratio of the product will be close to 1.0, but
Economically unfavorable. Also, the primary particle size of the powder is
Although it is fine with a size of 100 Å or less, it forms agglomerated particles with a non-uniform particle size of 0.02 to 0.3 μm, and the particle density is also small, which is not preferable. However, it has been found that when a hydrothermal reaction is carried out using an autoclave, the reaction rate is 97% or more, and particles with very uniform particle size and good dispersibility can be obtained.
また、本発明においては、合成反応を多量の塩
化ナトリウム、塩化カリウム等の塩類の存在下で
行うが、反応生成物を十分に洗浄すれば、アルカ
リ金属の含有量を0.01重量%程度にすることが可
能である。山村らは日本化学会誌1974年No.7にお
いて、Naイオンの存在下でチタン酸と水酸化バ
リウムを反応させて得られたBaTiO3には0.14重
量%のNaを含むことを報告しており、これらの
知見からは本発明の効果は予想されなかつたこと
である。 Furthermore, in the present invention, the synthesis reaction is carried out in the presence of large amounts of salts such as sodium chloride and potassium chloride, but if the reaction product is thoroughly washed, the alkali metal content can be reduced to about 0.01% by weight. is possible. Yamamura et al. reported in the Journal of the Chemical Society of Japan, No. 7, 1974, that BaTiO 3 obtained by reacting titanic acid and barium hydroxide in the presence of Na ions contains 0.14% by weight of Na. The effects of the present invention were unexpected from these findings.
以下、本発明を詳細に説明する。まず、四塩化
チタンを水に徐々に溶解して、チタン塩化物の溶
液を調整する。この溶液に溶解するバリウム塩ま
たはストロンチウム塩としては、水溶性の塩化
物、硝酸塩のほかに炭酸塩を用いうる。チタンの
塩化物の溶液には多量の塩酸が存在するので、炭
酸塩も容易に溶解することができる。 The present invention will be explained in detail below. First, a titanium chloride solution is prepared by gradually dissolving titanium tetrachloride in water. As the barium salt or strontium salt dissolved in this solution, carbonate can be used in addition to water-soluble chloride and nitrate. Since a large amount of hydrochloric acid is present in the solution of titanium chloride, carbonate can also be easily dissolved.
次に、この溶液に水酸化ナトリウムまたは水酸
化カリウムを加えて、アルカリ性にする。加える
アルカリの量は、チタンとバリウムまたはストロ
ンチウムの溶液中に存在する塩素イオンおよび/
または硝酸イオン等の酸根に対して当量か、わず
かに過剰とする。 Next, sodium hydroxide or potassium hydroxide is added to this solution to make it alkaline. The amount of alkali added depends on the chloride ions and/or ions present in the titanium and barium or strontium solution.
Or in an equivalent amount or slightly in excess of the acid radical such as nitrate ion.
本発明の方法において、水熱反応を行う前に、
バリウムまたはストロンチウムが炭酸塩の形で存
在する場合、チタンと反応せずに、そのまま反応
生成物に混入して組成が不均質になるので、炭酸
塩の混入および生成は極力避けねばならない。 In the method of the present invention, before carrying out the hydrothermal reaction,
If barium or strontium is present in the form of carbonate, it will not react with titanium and will be mixed into the reaction product as it is, resulting in a heterogeneous composition, so the mixing and formation of carbonate must be avoided as much as possible.
BaTiO3またはSrTiO3の合成は、撹拌機を装着
したオートクレーブを用いて行うが、加熱温度は
120〜200℃程度で良い。温度が高くなるに従い、
生成物粒子の密度は大きくなるが、200℃以上に
加熱しても、顕著な効果はなく、コスト的に好ま
しくない。120〜200℃程度の温度であれば、装置
材質も特別なものを使用する必要はなく、コスト
面での負担は、それほど大きくない。反応終了後
は通常の方法により、生成物を別、洗浄、乾燥
して製品とする。 The synthesis of BaTiO 3 or SrTiO 3 is performed using an autoclave equipped with a stirrer, but the heating temperature is
A temperature of about 120 to 200℃ is sufficient. As the temperature increases,
Although the density of the product particles increases, heating above 200°C has no significant effect and is not desirable from a cost perspective. If the temperature is around 120 to 200°C, there is no need to use special equipment materials, and the cost burden is not so large. After the reaction is completed, the product is separated, washed, and dried using a conventional method.
本発明の方法により得られたBaTiO3および
SrTiO3粉末は、粒径が小さく、粒度が均一であ
るため、各種のドーピング剤との反応性が高く、
積層コンデンサー用原料のみでなく、各種コンデ
ンサー、PTC半導体等に使用する原料として好
適である。また、粒度が小さいため、焼結温度が
低くなり、積層コンデンサーの場合の電極コスト
を大幅に低くすることが可能になる。 BaTiO3 obtained by the method of the present invention and
SrTiO3 powder has small particle size and uniform particle size, so it has high reactivity with various doping agents.
It is suitable not only as a raw material for multilayer capacitors, but also for various types of capacitors, PTC semiconductors, etc. In addition, the small particle size allows for lower sintering temperatures, making it possible to significantly reduce electrode costs in multilayer capacitors.
本発明の方法において、ペロブスカイト型複合
化合物が形成される範囲内で、チタン塩化物の一
部をジルコニウム、ニオブ、錫等の金属塩で置き
換えて実施することができ、またバリウムまたは
ストロンチウムの一部をストロンチウム、バリウ
ム、カルシウム、マグネシウム、鉛、セリウム、
ランタン等の金属塩で置き換けて実施することが
できる。 In the method of the present invention, part of the titanium chloride can be replaced with a metal salt such as zirconium, niobium, tin, etc., and part of the barium or strontium can be replaced within the range where a perovskite-type composite compound is formed. Strontium, barium, calcium, magnesium, lead, cerium,
It can be carried out by replacing it with a metal salt such as lanthanum.
つぎに実施例によつて本発明をさらに詳細に説
明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 1
TiCl4を氷水中に撹拌しながら加えて、TiO2と
して100g/を含む溶液を調整した。この溶液
300mlにTiと当量のBaCO3を溶解し、窒素がスを
吹き込み、空気を遮断しながら、溶液中の塩素イ
オンと当量のNaOHを加え、ステンレス製のオ
ートクレーブに入れて、130〜140℃で6時間、撹
拌加熱した。この反応による生成物を過し、水
で洗浄した後、再び希釈、過、洗浄し、105℃
で10時間乾燥して白色粉末を得た。この粉末の化
学分析の結果は、BaO/TiO2のモル比は0.99で
あり、Na2Oの含有量は、0.008重量%であつた。
またX線回析解析の結果、結晶性の良い立方晶チ
タン酸バリウムであり、電子顕微鏡で観察する
と、非常に分散性の良い0.1〜0.2μmの粒子で粒
度は均一なものであつた。Example 1 TiCl 4 was added to ice water with stirring to prepare a solution containing 100 g/TiO 2 . this solution
Dissolve BaCO3 in an amount equivalent to Ti in 300 ml, add NaOH in an amount equivalent to the chlorine ion in the solution while blowing nitrogen gas and shutting off air, place in a stainless steel autoclave, and incubate at 130-140℃ for 6 hours. Stir and heat for an hour. The product from this reaction was filtered and washed with water, then diluted again, filtered and washed at 105°C.
After drying for 10 hours, a white powder was obtained. As a result of chemical analysis of this powder, the molar ratio of BaO/TiO 2 was 0.99 and the content of Na 2 O was 0.008% by weight.
Further, as a result of X-ray diffraction analysis, it was found to be cubic barium titanate with good crystallinity, and when observed under an electron microscope, it was found to be particles of 0.1 to 0.2 μm with very good dispersibility and uniform particle size.
実施例 2
実施例1と同様にして、調整した塩化チタン水
溶液300mlにチタンに対して0.99当量のBaCl2・
2H2Oを溶解し、空気を遮断しながら、溶液中の
塩化イオンと当量のKOHを加え、オートクレー
ブに入れて、170〜180℃で3時間、撹拌加熱し
た。この反応による生成物を実施例1と同様に
過、洗浄、乾燥して白色粒末を得た。粉末の
BaO/TiO2モル比は0.99であり、K2Oの含有量
は0.012%であつた。結晶性の良い立方晶チタン
酸バリウムであり、粒径は0.2〜0.3μmで均一で、
分散性の良いものであつた。Example 2 In the same manner as in Example 1, 0.99 equivalent of BaCl 2 .
2H 2 O was dissolved, and KOH in an amount equivalent to the chloride ion in the solution was added while blocking air, and the mixture was placed in an autoclave and stirred and heated at 170 to 180° C. for 3 hours. The product resulting from this reaction was filtered, washed and dried in the same manner as in Example 1 to obtain white powder. powder
The BaO/TiO 2 molar ratio was 0.99 and the K 2 O content was 0.012%. It is cubic barium titanate with good crystallinity, and the particle size is uniform at 0.2 to 0.3 μm.
It had good dispersibility.
比較例
実施例2において、1.5当量のBaCl2・2H2Oを
加え、これに応じて加えるKOHの量を増加し、
常圧下で100℃で7時間、撹拌加熱した以外は、
実施例2と同様に行い、白色粉末を得た。粉末の
BaO/TiO2モル比は0.77で、反応率が低いこと
を示しており、K2O含有量は0.77%であつた。ま
た粒子径が0.01μm程度の微粒子と0.3μm程度の
粒子が混在しており、好ましいものではない。Comparative Example In Example 2, 1.5 equivalents of BaCl 2 2H 2 O were added and the amount of KOH added was increased accordingly,
Except for stirring and heating at 100℃ for 7 hours under normal pressure.
A white powder was obtained in the same manner as in Example 2. powder
The BaO/TiO 2 molar ratio was 0.77, indicating a low reaction rate, and the K 2 O content was 0.77%. Further, fine particles with a particle size of about 0.01 μm and particles with a particle size of about 0.3 μm are mixed, which is not preferable.
実施例 3
実施例1において、BaCO3の替りにSrCO3を
用いた以外は、実施例と同様に行い、白色粒末を
得た。X線回折解析の結果、立方晶チタン酸スト
ロンチウムであり、電子顕微鏡で観察すると、粒
径は0.05〜0.1μmであり、粒度は均一で、分散性
の良いものであつた。Example 3 A white powder was obtained in the same manner as in Example 1 except that SrCO 3 was used instead of BaCO 3 . As a result of X-ray diffraction analysis, it was found to be cubic strontium titanate, and when observed with an electron microscope, the particle size was 0.05 to 0.1 μm, and the particle size was uniform and had good dispersibility.
Claims (1)
トロンチウムの炭酸塩、塩化物、硝酸塩のうち1
種を溶解し、水酸化ナトリウムまたは水酸化カリ
ウムを加えて、撹拌下で水熱反応させることを特
徴とするチタン酸バリウムまたはチタン酸ストロ
ンチウムの製造法。1 Add one of barium or strontium carbonate, chloride, or nitrate to an aqueous solution of titanium tetrachloride.
A method for producing barium titanate or strontium titanate, which comprises dissolving seeds, adding sodium hydroxide or potassium hydroxide, and carrying out a hydrothermal reaction under stirring.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21562785A JPS6272525A (en) | 1985-09-27 | 1985-09-27 | Production of barium titanate or strontium titanate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21562785A JPS6272525A (en) | 1985-09-27 | 1985-09-27 | Production of barium titanate or strontium titanate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6272525A JPS6272525A (en) | 1987-04-03 |
JPH0246531B2 true JPH0246531B2 (en) | 1990-10-16 |
Family
ID=16675531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21562785A Granted JPS6272525A (en) | 1985-09-27 | 1985-09-27 | Production of barium titanate or strontium titanate |
Country Status (1)
Country | Link |
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JP (1) | JPS6272525A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0747487B2 (en) * | 1990-07-30 | 1995-05-24 | 電気化学工業株式会社 | Method for producing powder for easily sinterable microwave dielectric |
WO2001010781A1 (en) * | 1999-08-05 | 2001-02-15 | Korea Institute Of Science And Technology | METHOD FOR MANUFACTURING BaTiO3 BASED POWDERS |
KR100395218B1 (en) * | 2001-03-24 | 2003-08-21 | 한국과학기술연구원 | METHOD FOR MANUFACTURING BaTiO3 BASED POWDERS |
KR100489403B1 (en) * | 2002-05-30 | 2005-05-12 | 주식회사 나노 | METHOD OF PREPARING BaTiO3 POWDER |
KR100503857B1 (en) * | 2002-11-01 | 2005-07-25 | (주)아해 | Preparation of Nano-sized Crystalline Titanic Acid Barium Powder from Aqueous Titanium Tetrachloride and Barium Chloride Solutions Prepared by Use of Inorganic Acids |
KR100503858B1 (en) * | 2002-11-01 | 2005-07-26 | (주)아해 | Preparation of Nano-sized Crystalline Titanic Acid Strontium Powder from Aqueous Titanium Tetrachloride and Strontium Carbonate Solutions Prepared by Use of Inorganic Acids |
JP6065286B2 (en) * | 2014-02-14 | 2017-01-25 | 富士フイルム株式会社 | Method for producing strontium titanate fine particles |
CN105036184A (en) * | 2015-07-27 | 2015-11-11 | 上海海事大学 | Method for preparing nanometer strontium titanate powder |
CN118005072B (en) * | 2024-04-10 | 2024-06-18 | 杭州兴容科技有限公司 | Hydrothermal synthesis method of barium titanate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61146712A (en) * | 1984-12-21 | 1986-07-04 | Asahi Chem Ind Co Ltd | Production of barium-strontium titanate solid solution or barium titanate |
-
1985
- 1985-09-27 JP JP21562785A patent/JPS6272525A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61146712A (en) * | 1984-12-21 | 1986-07-04 | Asahi Chem Ind Co Ltd | Production of barium-strontium titanate solid solution or barium titanate |
Also Published As
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