JPH07115873B2 - Method for producing piezoelectric oxide fine powder - Google Patents
Method for producing piezoelectric oxide fine powderInfo
- Publication number
- JPH07115873B2 JPH07115873B2 JP61279785A JP27978586A JPH07115873B2 JP H07115873 B2 JPH07115873 B2 JP H07115873B2 JP 61279785 A JP61279785 A JP 61279785A JP 27978586 A JP27978586 A JP 27978586A JP H07115873 B2 JPH07115873 B2 JP H07115873B2
- Authority
- JP
- Japan
- Prior art keywords
- fine powder
- piezoelectric oxide
- precipitate
- oxide fine
- methanol
- 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
- 239000000843 powder Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 229910052745 lead Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000010936 titanium Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910020684 PbZr Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ANBZWDBEKOZNHY-UHFFFAOYSA-N ethanol;oxalic acid Chemical compound CCO.OC(=O)C(O)=O ANBZWDBEKOZNHY-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CETRJNFIKWWGQO-UHFFFAOYSA-N methanol;oxalic acid Chemical compound OC.OC(=O)C(O)=O CETRJNFIKWWGQO-UHFFFAOYSA-N 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はしゅう酸−メタノール溶液を用いて金属しゅう
酸塩を沈澱させてつくる圧電性酸化物微粉末の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a piezoelectric oxide fine powder prepared by precipitating a metal oxalate using an oxalic acid-methanol solution.
圧電性酸化物粉末、特にPbZrxTi1-xO3粉末は強誘電体材
料、圧電体材料として広く実用に供されている。Piezoelectric oxide powder, especially PbZr x Ti 1-x O 3 powder, has been widely put to practical use as a ferroelectric material and a piezoelectric material.
その圧電性酸化物の製法は乾式法、湿式法あるいは両者
の組み合わせ法など多くの方法が開発されている。最近
では圧電性酸化物粉末の純度が高く、かつ一定の組成比
を有する圧電性酸化物（例えばPbZr0.52Ti0.48O3）粉末
をつくる方法としてしゅう酸エタノール法が提案され
た。Many methods have been developed for producing the piezoelectric oxide, such as a dry method, a wet method, or a combination of both methods. Recently, the ethanol oxalate method has been proposed as a method for producing a piezoelectric oxide powder (for example, PbZr 0.52 Ti 0.48 O 3 ) powder having a high purity and a constant composition ratio of the piezoelectric oxide powder.
この方法はしゅう酸がエタノールに可溶であること、お
よびPb、Zr、Tiの各しゅう酸塩がエタノールに難溶であ
ることに着目して開発されたものである。具体的にはエ
タノールにしゅう酸を溶かした溶液に、別に準備してお
いたPb、Zr、Tiを含む水溶液を滴下して混液中に金属し
ゅう酸塩の沈澱物を生成させ、得られた沈澱物をエタノ
ールで洗浄後、乾燥し、空気中で仮焼してつくる圧電性
酸化物粉末の改良湿式製造法である（窯協誌94〔５〕、
1986 pp18〜23）。This method was developed paying attention to the fact that oxalic acid is soluble in ethanol, and that the oxalates of Pb, Zr, and Ti are hardly soluble in ethanol. Specifically, a separately prepared aqueous solution containing Pb, Zr, and Ti is added dropwise to a solution of ethanol and oxalic acid to form a metal oxalate precipitate in the mixed solution. This is an improved wet manufacturing method of piezoelectric oxide powder, which is produced by washing the product with ethanol, drying it, and then calcining it in the air (Kyokyo Journal 94 [5],
1986 pp18-23).
前記従来法はエタノールを大量に使用する。その理由
は、沈澱したPb、Zr、Tiの各しゅう酸塩の中で、しゅう
酸チタンが混液中の水に対する溶解度が他の金属しゅう
酸塩より大きいので、沈澱物中のPb、Zr、Tiの比率のバ
ランスがくずれ、所望の圧電性酸化物が得られない。そ
れを防ぐため、混液中の水の影響を極力小さくするべ
く、水に比し大量のエタノールを使用したものである。
その結果、圧電性酸化物1Kgを製造するのに約39もの
エタノールを使用しなければならなかった。The conventional method uses a large amount of ethanol. The reason is that among the precipitated Pb, Zr, and Ti oxalates, the solubility of titanium oxalate in water in the mixed solution is higher than that of other metal oxalates. The balance of the ratio is broken, and the desired piezoelectric oxide cannot be obtained. In order to prevent this, a large amount of ethanol is used compared to water in order to minimize the influence of water in the mixed liquid.
As a result, about 39 ethanol had to be used to produce 1 kg of piezoelectric oxide.
そのため、該エタノールが製造工程から副産物として大
量に発生するが、環境衛生上廃棄もできず、また、回収
してもエタノール中に硝酸イオンなどが残存しているた
め再生使用も困難であり、その処理に難儀をきわめてい
た。Therefore, although a large amount of the ethanol is generated as a by-product from the manufacturing process, it cannot be discarded in terms of environmental hygiene, and it is difficult to recycle it because nitrate ions and the like remain in ethanol even after collection. It was extremely difficult to process.
そこで、本発明者らは水の影響を排除でき、かつ入手容
易な溶媒について研究した結果、エタノールより極性の
強いメタノールを用いれば、メタノール−水の混液中の
水に対するしゅう酸チタンの溶解度が激減し、少量のメ
タノールの使用で所望のPb、Zr、Tiの原子比を有する沈
澱物が得られることを見い出し、これに基づいて以下に
述べる発明を完成した。Therefore, as a result of research on a solvent that can eliminate the influence of water and is easily available, the present inventors drastically reduced the solubility of titanium oxalate in water in a methanol-water mixture by using methanol having a stronger polarity than ethanol. Then, it was found that a precipitate having a desired atomic ratio of Pb, Zr, and Ti was obtained by using a small amount of methanol, and based on this, the invention described below was completed.
すなわち、本発明はしゅう酸をメタノールに溶解させた
溶液とPb、ZrおよびTiの各イオンを含む水溶液を混合し
て沈澱物をつくり、該沈澱物を乾燥し、仮焼してつくる
圧電性酸化物微粉末の製造方法を要旨とする。That is, according to the present invention, a solution of oxalic acid dissolved in methanol and an aqueous solution containing Pb, Zr and Ti ions are mixed to form a precipitate, and the precipitate is dried and calcined to produce a piezoelectric oxide. The gist is a method for producing fine powder.
本発明で使用するしゅう酸とメタノールは市販されてい
るものが用いられる。Commercially available oxalic acid and methanol are used in the present invention.
しゅう酸をメタノールに溶解させた溶液のつくり方は慣
用の方法にしたがう。しゅう酸の濃度は特に限定しない
が、飽和状態で用いるのが後述の沈澱物を大量に生成で
きるので好ましい。The method for preparing a solution of oxalic acid in methanol follows a conventional method. The concentration of oxalic acid is not particularly limited, but it is preferable to use it in a saturated state since a large amount of the precipitate described below can be produced.
Pb、ZrおよびTiの各イオンを含む水溶液は、水中でPb、
ZrおよびTiの各金属原子を解離し、イオンとなる化合物
を水に溶解させることにより得られる。そのさい使用す
る水は多少多めでも沈澱の生成にはさしつかえないが、
できるだけ少い水量で溶解させる方が、副産物の発生が
少ないので好ましい。化合物としては金属原子を含む硝
酸塩、オキシ硝酸塩のほか、有機化合物たとえば金属ア
ルコキシドが示される。それら化合物に金属原子が２種
以上含まれていてもさしつかえない。Aqueous solution containing Pb, Zr and Ti ions, Pb in water,
It is obtained by dissociating each metal atom of Zr and Ti and dissolving a compound that becomes an ion in water. In that case, even if a little more water is used, it may be possible to form a precipitate,
It is preferable to dissolve in as little water as possible, because the generation of by-products is less. Examples of the compound include nitrates and oxynitrates containing a metal atom, as well as organic compounds such as metal alkoxides. It does not matter if those compounds contain two or more metal atoms.
化合物の配合割合は、Pb、ZrおよびTiの比が仮焼したさ
いに所望の圧電性酸化物になるような割合にすればよ
く、本発明ではその比を特に限定しない。The compounding ratio may be such that the ratio of Pb, Zr and Ti becomes a desired piezoelectric oxide upon calcination, and the ratio is not particularly limited in the present invention.
次に、沈澱物のつくり方を説明する。Next, how to make a precipitate will be described.
しゅう酸をメタノールに溶解させた溶液とPb、Zrおよび
Tiの各イオンを含む水溶液とを混合すると、しゅう酸と
Pb、ZrおよびTiの各イオンとが反応して原子レベルで均
一に分散した複合金属しゅう酸塩の沈澱物が得られる。
生成した金属しゅう酸塩は、溶媒である水−メタノール
混液に難溶であるため、水に溶解することなく、ほぼ配
合設計どおりのPb、ZrおよびTiの各金属元素比で構成さ
れた沈澱物となる。A solution of oxalic acid in methanol and Pb, Zr and
When mixed with an aqueous solution containing each ion of Ti, oxalic acid and
By reacting with Pb, Zr and Ti ions, a precipitate of a composite metal oxalate uniformly dispersed at the atomic level is obtained.
The produced metal oxalate is hardly soluble in the solvent water-methanol mixture, so it does not dissolve in water and is a precipitate composed of Pb, Zr, and Ti metal element ratios almost as designed. Becomes
その沈澱物を過したのち、乾燥し、500〜900℃空気中
で仮焼すれば粒径がサブミクロンの圧電性酸化物微粉末
が得られる。After the precipitate is passed, it is dried and calcined in air at 500 to 900 ° C. to obtain a piezoelectric oxide fine powder having a particle size of submicron.
以下に、本発明を実施例によって説明する。The present invention will be described below with reference to examples.
オキシ硝酸ジルコニウム水溶液52.5ml（Zr3.0mol/）
に濃硝酸30mlを加えたのち、チタンイソプロポキシド液
44.4ml（Ti 3.32mol/）を滴下し、撹拌して透明な溶
液をつくった。この溶液を加熱して40℃に保持しながら
無水硝酸鉛101.6gを加え、溶解させてPb、ZrおよびTiの
比が100:52:48の水溶液を調製した。Zirconium oxynitrate aqueous solution 52.5ml (Zr3.0mol /)
After adding 30 ml of concentrated nitric acid to the solution, titanium isopropoxide solution
44.4 ml (Ti 3.32 mol /) was added dropwise and stirred to make a clear solution. To this solution, 101.6 g of anhydrous lead nitrate was added while heating at 40 ° C. and dissolved to prepare an aqueous solution having a Pb, Zr and Ti ratio of 100: 52: 48.
一方無水しゅう酸85gをメタノール200mlに溶解させて溶
液をつくった。On the other hand, a solution was prepared by dissolving 85 g of oxalic anhydride in 200 ml of methanol.
この溶液に前記Pb、ZrおよびTiの各イオンを含む水溶液
を滴下し沈澱させた。An aqueous solution containing each of the Pb, Zr and Ti ions was added dropwise to this solution for precipitation.
その沈澱物を70℃、24hr乾燥したのち、600℃、1hr電気
炉で仮焼して酸化物微粉末100.0gを得た。The precipitate was dried at 70 ° C. for 24 hours and then calcined in an electric furnace at 600 ° C. for 1 hour to obtain 100.0 g of oxide fine powder.
この微粉末を自然沈降式粒度測定機およびＸ線回折計で
細かさおよび生成鉱物について調べたところ、平均粒径
0.15μｍのPb.（Zr0.52Ti0.48）O3からなる単一鉱物の
圧電性酸化物微粉末であった。This fine powder was examined for fineness and produced minerals by a natural sedimentation type particle sizer and an X-ray diffractometer, and found that the average particle size was
It was a single mineral piezoelectric oxide fine powder composed of 0.15 μm Pb. (Zr 0.52 Ti 0.48 ) O 3 .
この圧電性酸化物微粉末1Kgあたりの製造に要したメタ
ノールの使用量は僅か２であった。The amount of methanol required for the production per 1 kg of this piezoelectric oxide fine powder was only 2.
本発明は、金属しゅう酸塩の沈澱物をつくるにあたり、
極性の強いメタノールを採用することによって共存する
水による金属しゅう酸塩の溶解を防いだ圧電性酸化物微
粉末の製造方法であり、従来のしゅう酸エタノール法で
できなかった該酸化物単位量当りのアルコール使用量を
大幅に減らすことができた。In the present invention, in forming a metal oxalate precipitate,
A method for producing a fine powder of a piezoelectric oxide in which dissolution of a metal oxalate by coexisting water is prevented by adopting strongly polar methanol, and a unit amount of the oxide which cannot be obtained by a conventional ethanol oxalate method. I was able to drastically reduce the amount of alcohol used.
Claims (1)
Pb、ZrおよびTiの各イオンを含む水溶液を混合して沈澱
物をつくり、該沈澱物を乾燥し、仮焼することを特徴と
する圧電性酸化物微粉末の製造方法。1. A solution of oxalic acid dissolved in methanol
A method for producing a piezoelectric oxide fine powder, which comprises mixing an aqueous solution containing each of Pb, Zr and Ti ions to form a precipitate, drying the precipitate and calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61279785A JPH07115873B2 (en) | 1986-11-26 | 1986-11-26 | Method for producing piezoelectric oxide fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61279785A JPH07115873B2 (en) | 1986-11-26 | 1986-11-26 | Method for producing piezoelectric oxide fine powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63134518A JPS63134518A (en) | 1988-06-07 |
| JPH07115873B2 true JPH07115873B2 (en) | 1995-12-13 |
Family
ID=17615881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61279785A Expired - Lifetime JPH07115873B2 (en) | 1986-11-26 | 1986-11-26 | Method for producing piezoelectric oxide fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07115873B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9714150D0 (en) * | 1997-07-05 | 1997-09-10 | Secr Defence | Process for the preparation of lead zirconate titanate compounds |
-
1986
- 1986-11-26 JP JP61279785A patent/JPH07115873B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63134518A (en) | 1988-06-07 |
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