JPH0788220B2 - Manufacturing method of easily sinterable ceramic powder for high-density dielectric ceramics - Google Patents
Manufacturing method of easily sinterable ceramic powder for high-density dielectric ceramicsInfo
- Publication number
- JPH0788220B2 JPH0788220B2 JP15563386A JP15563386A JPH0788220B2 JP H0788220 B2 JPH0788220 B2 JP H0788220B2 JP 15563386 A JP15563386 A JP 15563386A JP 15563386 A JP15563386 A JP 15563386A JP H0788220 B2 JPH0788220 B2 JP H0788220B2
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- Prior art keywords
- precipitate
- calcination
- mixed
- ceramic powder
- raw material
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Links
- 239000000843 powder Substances 0.000 title claims description 25
- 239000000919 ceramic Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- -1 oxynitrate Chemical compound 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、低温焼結性で高性能のPZT系圧電セラミック
ス原料粉末の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a PZT-based piezoelectric ceramic raw material powder having a low temperature sinterability and high performance.
PZT系セラミックスは、高周波フィルター、超音波振動
子、共振子エレメント（ピックアップエレメント、着火
素子メカニカルフィルタ、遅延線用変換素子、バイモル
フ素子等）として広範囲に利用されている。PZT ceramics are widely used as high frequency filters, ultrasonic vibrators, and resonator elements (pickup elements, ignition element mechanical filters, delay line conversion elements, bimorph elements, etc.).
従来のPZT系セラミックスの原料粉末の製造方法として
は、乾式法と湿式共沈法が知られている。The dry method and the wet coprecipitation method are known as conventional methods for producing a raw material powder of PZT ceramics.
乾式法は、構成成分の酸化物又は炭酸塩等の粉末を混合
し、これを仮焼する方法である。湿式共沈法は、PZTの
構成成分の全ての混合液を作り、これにアルカリ等の沈
殿形成液を添加して共沈させ、乾燥、仮焼する方法であ
る。The dry method is a method in which powders such as oxides or carbonates of the constituents are mixed and calcined. The wet coprecipitation method is a method in which a mixed solution of all the constituents of PZT is prepared, and a precipitation-forming solution such as an alkali is added to this to coprecipitate, followed by drying and calcination.
従来から知られている乾式法では、均一な組成の原料粉
末が得難く、またPZTの生成反応を完遂させるために仮
焼温度を高くすることが必要であるので、粒子が粗大化
して易焼結性になり難い欠点があった。In the conventionally known dry method, it is difficult to obtain a raw material powder having a uniform composition, and it is necessary to raise the calcination temperature in order to complete the PZT formation reaction. There was a drawback that it was difficult to become connected.
また、湿式共沈法では、沈殿形成液の添加時の濃度が一
定であるため、各成分の沈殿形成能が異なる場合には、
ある成分は100％沈殿を生成するが、他の成分は100％沈
殿を生成し得ないことがあり、所望組成のものを得難い
欠点がある。更に、PZTは鉛とチタンとを含有している
ので、これを共沈法で製造する場合、チタン原料として
安価な四塩化チタンを使用すると、四塩化チタンの塩素
イオンが鉛イオンと反応して白色沈殿を生成するため、
四塩化チタンは使用できない。この場合、オキシ硝酸チ
タンを使用すればこの沈殿の生成を防ぐことができる
が、高価であるため実用的でない。Further, in the wet coprecipitation method, since the concentration at the time of adding the precipitate forming liquid is constant, when the precipitation forming ability of each component is different,
Some components may produce 100% precipitates, while other components may not be able to produce 100% precipitates, making it difficult to obtain the desired composition. Furthermore, since PZT contains lead and titanium, when it is produced by the coprecipitation method, if inexpensive titanium tetrachloride is used as the titanium raw material, the chlorine ion of titanium tetrachloride reacts with the lead ion. To produce a white precipitate,
Titanium tetrachloride cannot be used. In this case, the use of titanium oxynitrate can prevent the formation of this precipitate, but it is not practical because it is expensive.
また、湿式法として、有機金属化合物を用いる方法もあ
り、この場合、有害な陰イオンの生成はないが、原料が
高価であり工業的生産には適していない。There is also a method using an organometallic compound as a wet method. In this case, no harmful anion is generated, but the raw material is expensive and it is not suitable for industrial production.
更に、Mg,Ni,Zn,Mnは、共通の沈殿形成液を用い、同一p
H領域内で沈殿を形成させることが困難であり、Nb,Ta
は、水系溶媒に溶解する塩が少なく、そのため、これら
の金属を含有するPZT系セラミックス粉末を、水系溶液
から沈殿形成させる方法で、正しい化学量論比を持つペ
ロブスカイト系酸化物として得ることは困難であった。Furthermore, for Mg, Ni, Zn, and Mn, a common precipitate-forming solution was used and the same p
It is difficult to form a precipitate in the H region, and Nb, Ta
Since there are few salts that dissolve in aqueous solvents, it is difficult to obtain PZT ceramic powders containing these metals as perovskite oxides with the correct stoichiometric ratio by the method of precipitation formation from an aqueous solution. Met.
本発明の目的は、Mg,Ni,Zn,Mn,Nb,Ta等の金属を含有す
るPZT系圧電セラミックスの原料粉末の製法における従
来法の欠点を解消し、チタン原料として安価な四塩化チ
タンも使用でき、高密度で電気特性の優れたPZT系圧電
セラミックスの製造に適した、低温焼結性の粉末を製造
する方法を提供するにある。The object of the present invention is to eliminate the drawbacks of the conventional method in the method of producing the raw material powder of PZT-based piezoelectric ceramics containing a metal such as Mg, Ni, Zn, Mn, Nb, and Ta, and inexpensive titanium tetrachloride as a titanium raw material. Another object of the present invention is to provide a method for producing a low-temperature sinterable powder suitable for producing a PZT-based piezoelectric ceramic that can be used and has a high density and excellent electrical characteristics.
本発明は、一般式Pb（Zrt Ti1-t）O3（但し、ｔ＝0.1〜
0.9）で表される酸化物と一般式 PbA1/3Ｂ2/3O3（但し、ＡはMg,Ni,Zn及びMnからなる群
から選ばれた１種又は２種以上を、ＢはNb及び又はTaを
表す）で表される酸化物とからなるペロブスカイト系構
造を持つPZT系圧電セラミックス粉末の製造において、
ジルコニウム及びチタニウム化合物の溶液、並びに予め
仮焼して得られたAO・B2O5で表される複合酸化物を沈殿
形成液と混合し、得られた沈殿を仮焼した後、鉛酸化物
と混合し、仮焼することからなる鉛含有ペロブスカイト
複合酸化物の製造法である。The present invention has the general formula Pb (Zr t Ti 1-t ) O 3 (where t = 0.1 to
0.9) and an oxide represented by the general formula PbA 1/3 B 2/3 O 3 (where A is one or more selected from the group consisting of Mg, Ni, Zn and Mn, and B is In the production of PZT-based piezoelectric ceramic powder having a perovskite structure consisting of an oxide represented by Nb and / or Ta),
A solution of zirconium and titanium compounds, and a composite oxide represented by AO.B 2 O 5 obtained by preliminary calcination were mixed with a precipitation forming liquid, and the obtained precipitate was calcined, and then lead oxide was obtained. It is a method for producing a lead-containing perovskite composite oxide, which comprises mixing with and calcining.
本発明において、PZT系圧電セラミックスとは、前記一
般式のPbの原子比を1.0より高くあるいは低くずらした
もの、また微量の他金属元素を添加した系をも含むもの
である。In the present invention, PZT-based piezoelectric ceramics include those in which the atomic ratio of Pb in the above general formula is shifted higher or lower than 1.0, and also include systems in which trace amounts of other metal elements are added.
本発明方法においては、Zr及びTi成分はそれらの原料化
合物の溶液を沈殿形成液と混合し、共沈法により沈殿形
成させる。In the method of the present invention, the Zr and Ti components are formed by a coprecipitation method by mixing a solution of these raw material compounds with a precipitation forming liquid.
原料化合物として使用するZr,Ti化合物としては、水酸
化物、オキシ塩化物、炭酸塩、オキシ硝酸塩、硫酸塩、
硝酸塩、酢酸塩、ギ酸塩、酸塩、塩化物、酸化物等が
挙げられる。これらが水に可溶でない場合は、鉱酸等を
添加して可溶とするができるが、最も安価で、本発明方
法に適したものは、オキシ塩化ジルコニウム又はオキシ
硝酸ジルコニウム、及び四塩化チタンである。As the Zr, Ti compound used as the raw material compound, hydroxide, oxychloride, carbonate, oxynitrate, sulfate,
Examples thereof include nitrates, acetates, formates, acid salts, chlorides and oxides. When these are not soluble in water, mineral acids and the like can be added to make them soluble, but the cheapest one suitable for the method of the present invention is zirconium oxychloride or zirconium oxynitrate, and titanium tetrachloride. Is.
Ａ及びＢ成分は、予め、両成分原料化合物を混合した
後、400〜1000℃、好ましくは700〜1000℃で仮焼して得
られた、不溶性複合酸化物AO・B2O5を粉砕し、通常、縣
濁液として添加する。As for the components A and B, the insoluble complex oxide AO.B 2 O 5 obtained by previously mixing the raw material compounds of both components and calcination at 400 to 1000 ° C., preferably 700 to 1000 ° C. is pulverized. , Usually added as a suspension.
AO・B2O5粉末は、原料、仮焼温度、粉砕工程等を制御す
ることにより、粒径分布が均一で粒径が小さいものとす
る必要がある。粒径は1.0μｍ以下とすることが好まし
い。The AO / B 2 O 5 powder needs to have a uniform particle size distribution and a small particle size by controlling the raw material, the calcination temperature, the pulverization process, and the like. The particle size is preferably 1.0 μm or less.
AO・B2O5の添加は、Zr−Ti成分の沈殿形成前にAO・B2O5
を沈殿形成液に分散させておく方法、Zr−Ti成分の沈殿
形成後、該沈殿の分散した沈殿形成液にAO・B2O5を加え
分散させる方法を採用することが出来る。Addition of AO · B 2 O 5 is, Zr-Ti AO · before precipitation of the components B 2 O 5
It is possible to employ a method in which the above is dispersed in a precipitate forming liquid, or a method in which after forming a precipitate of the Zr—Ti component, AO.B 2 O 5 is added to and dispersed in the precipitate forming liquid in which the precipitate is dispersed.
Ａ及びＢ成分の原料化合物としては、水酸化物、オキシ
塩化物、炭酸塩、オキシ硝酸塩、硝酸塩、酢酸塩、ギ酸
塩、硝酸塩、酸化物等が挙げられる。Examples of the raw material compounds of the components A and B include hydroxide, oxychloride, carbonate, oxynitrate, nitrate, acetate, formate, nitrate and oxide.
沈殿形成液としては、例えば、アンモニア、苛性アルカ
リ、炭酸ソーダ、酸アンモニウム，アミン等の溶液が
挙げられるが、微量の混入が電気特性に影響するナトリ
ウム、カリウムを含まず、仮焼段階で容易に分解し、か
つ安価なアンモニア水が好ましい。Examples of the precipitation-forming liquid include solutions of ammonia, caustic alkali, sodium carbonate, ammonium acid, amines, etc. Ammonia water that decomposes and is inexpensive is preferable.
Zr−Tiの混合水酸化物沈殿の形成にあたっては、沈殿形
成後、洗浄により陰イオンの除去を十分に行う必要があ
る。洗浄は、通常、水又はアンモニア水を使用し、リパ
ルプ水洗を繰り返すことが好ましい。該洗浄が十分でな
いと、塩化鉛等を生成し焼結時に重量減少し、焼結性及
び電気特性が低下する。In forming a mixed hydroxide precipitate of Zr-Ti, it is necessary to sufficiently remove anions by washing after the precipitate is formed. For washing, it is usually preferable to use water or ammonia water and repeat washing with repulp. If the cleaning is not sufficient, lead chloride or the like is produced, and the weight is reduced during sintering, so that the sinterability and the electrical characteristics are deteriorated.
また、より性能の優れた粉末を得るためには、沈殿生成
後、熟成を行うことが好ましい。熟成は、低温の場合は
長時間、高温の場合は短時間であり、通常、10〜80℃で
30分以上、好ましくは１〜24時間である。Further, in order to obtain a powder having more excellent performance, it is preferable to perform aging after the formation of the precipitate. Aging is long at low temperature and short at high temperature, usually at 10-80 ° C.
It is 30 minutes or more, preferably 1 to 24 hours.
本発明における沈殿形成は、水系溶媒、例えば、水又は
水−アルコール中で行われる。The precipitate formation in the present invention is carried out in an aqueous solvent such as water or water-alcohol.
上記の方法により得られたZr−Ti−Ａ−Ｂの水酸化物と
酸化物との混合沈殿を仮焼した後、鉛酸化物を混合し、
更に仮焼することにより、本発明の複合酸化物粉末を得
ることが出来る。After calcining the mixed precipitate of the hydroxide and oxide of Zr-Ti-AB obtained by the above method, lead oxide is mixed,
Further calcination makes it possible to obtain the composite oxide powder of the present invention.
鉛酸化物としてはPbO又はPb3O4が使用できる。PbO or Pb 3 O 4 can be used as the lead oxide.
Zr−Ti−Ａ−Ｂの混合沈殿の仮焼は、400〜1000℃、好
ましくは600〜900℃で行う。また、最終仮焼は400〜100
0℃、好ましくは700〜1000℃で行う。The calcination of the mixed precipitate of Zr-Ti-AB is performed at 400 to 1000 ° C, preferably 600 to 900 ° C. Also, the final calcination is 400-100
It is carried out at 0 ° C, preferably 700 to 1000 ° C.
本発明において、PZT系セラミックスの焼結性や特性を
制御するために、微量成分、例えば、Ba,Ca,Sr.Sn,Mn,A
l,La,Nb,Cs,Ge,V,Y,Bi,Fe,Cr,Ni,Ir,Rh,Na,Sc,In,K,Ga,
Tl,W,Th等の元素の化合物を添加してもよい。In the present invention, in order to control the sinterability and properties of PZT ceramics, trace components, for example, Ba, Ca, Sr.Sn, Mn, A
l, La, Nb, Cs, Ge, V, Y, Bi, Fe, Cr, Ni, Ir, Rh, Na, Sc, In, K, Ga,
You may add the compound of elements, such as Tl, W, and Th.
本発明により得られるPZT系圧電セラミックス原料粉末
は低温焼結性の粉末であり、800〜1220℃で焼結するこ
とにより、高密度で電気特性の優れたPZT系圧電セラミ
ックス焼結体を得ることが出来る。The PZT-based piezoelectric ceramic raw material powder obtained by the present invention is a low-temperature sinterable powder, and by sintering at 800 to 1220 ° C., a PZT-based piezoelectric ceramics sintered body having high density and excellent electrical characteristics can be obtained. Can be done.
以下、実施例を挙げ本発明を更に詳細に説明するが、本
発明はこれら実施例によりなんら限定されるものではな
い。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例1. MgO0.0167モルとNb2O50.0167モルとをボールミルで混合
し、850℃で２時間仮焼した。この仮焼粉末を１のア
ンモニア水中に分散した分散液に、オキシ塩化ジルコニ
ウム0.0135モルと四塩化チタン0.0365モルとを水500ml
中に溶解した混合水溶液を徐々に滴下し、濾過後、濾過
ケーキを再び希アンモニア水に分散させて濾過する方法
（リパルプ洗浄）を数回繰り返し、塩素イオンを十分除
去した。尚、リパルプ洗浄時の濾紙への付着による各成
分の量論比が変わることを防ぐため、常に同じ濾紙上で
濾過を行った。Example 1. 0.0167 mol of MgO and 0.0167 mol of Nb 2 O 5 were mixed in a ball mill and calcined at 850 ° C. for 2 hours. This calcined powder was dispersed in 1 of ammonia water, and 0.0135 mol of zirconium oxychloride and 0.0365 mol of titanium tetrachloride were added to 500 ml of water.
A mixed aqueous solution dissolved therein was gradually added dropwise, and after filtration, a method of dispersing the filter cake in diluted ammonia water again and filtering (repulp washing) was repeated several times to sufficiently remove chlorine ions. In addition, in order to prevent the stoichiometric ratio of each component from changing due to adhesion to the filter paper during repulp washing, filtration was always performed on the same filter paper.
次いで、この混合沈殿を乾燥した後、900℃で２時間仮
焼し、仮焼粉末とPb3O4とを混合し、800℃で２時間仮焼
し、再びボールミルで粉砕し、Pb（Mg1/3Nb2/3）0.500Z
r0.135Ti0.365O3組成のセラミックス粉末を得た。Next, after drying this mixed precipitate, it is calcined at 900 ° C. for 2 hours, the calcined powder and Pb 3 O 4 are mixed, calcined at 800 ° C. for 2 hours, and then pulverized again with a ball mill to obtain Pb (Mg 1/3 Nb 2/3 ) 0.500 Z
A ceramic powder of r 0.135 Ti 0.365 O 3 composition was obtained.
比較例 市販のPbO、TiO2、ZrO2、MgO、Nb2O5の粉末をPb（Mg1/3
Nb2/3）0.500Zr0.135Ti0.365O3の組成になるように配合
し、ボールミルで混合した後、800℃で約２時間仮称
し、再びボールミルで粉砕した後乾燥し、Pb（Mg1/3Nb
2/3）0.500Zr0.135Ti0.365O3組成のセラミックス粉末を
得た。Comparative Example Commercially available powders of PbO, TiO 2 , ZrO 2 , MgO, and Nb 2 O 5 were mixed with Pb (Mg 1/3
Nb 2/3 ) 0.500 Zr 0.135 Ti 0.365 O 3 was mixed and mixed in a ball mill, then tentatively named at 800 ° C. for about 2 hours, pulverized again in a ball mill, and then dried to obtain Pb (Mg 1 / 3 Nb
2/3 ) 0.500 Zr 0.135 Ti 0.365 O 3 A ceramic powder having a composition was obtained.
（評価試験） （Ａ） 原料粉末の特性 粒度分布は遠心沈降式粒度分布測定機（島津製作所・SA
−CP型）を用いて測定した。(Evaluation test) (A) Characteristics of raw material powder The particle size distribution is a centrifugal sedimentation type particle size distribution measuring device (Shimadzu SA
-CP type).
（Ａ−１） 平均粒径D50:累積重量百分率が50％を示す
粒径 （Ａ−２） 粒度分布D90/D10:累積重量百分率が90％を
示す粒径D90を累積重量百分率が10％を示す粒径D10で除
した値 （Ａ−３） 比表面積：比表面積自動測定装置（島津マ
イクロメリティクス2200型）を用いて測定下。(A-1) Average particle size D 50 : Particle size showing cumulative weight percentage of 50% (A-2) Particle size distribution D 90 / D 10 : Particle size D 90 showing cumulative weight percentage of 90% Cumulative weight percentage There divided by the particle size D 10 showing a 10% (a-3) the specific surface area: measured under using a specific surface area automatic measurement apparatus (Shimadzu Micromeritics 2200 type).
（Ｂ） 誘電体磁器の特性 実施例及び比較例で得られた粉末を使用して圧電体磁器
を製造した。(B) Characteristics of Dielectric Porcelain A piezoelectric ceramic was manufactured using the powders obtained in Examples and Comparative Examples.
原料粉末1gを直径20mmの金型に入れ、2ton/cm2の圧力で
加圧成形し成形体を得た。この成形体をマグネシアルツ
ボに入れ蓋をし、焼成炉で焼結し圧電体磁器を得た。1 g of the raw material powder was placed in a mold having a diameter of 20 mm and pressure-molded at a pressure of 2 ton / cm 2 to obtain a molded body. This molded body was put in a magnificial crucible, covered with a lid, and sintered in a firing furnace to obtain a piezoelectric ceramic.
（Ｂ−１） 焼結密度：水中置換法により測定した。(B-1) Sintering density: Measured by an underwater substitution method.
（Ｂ−２） 誘電特性ε及びtanδ:LCZメーター（横河
ヒューレットパッカード製4276A）を使用し、20℃、1KH
zの条件で比誘電率ε及び誘電正接tanδを測定した。(B-2) Dielectric properties ε and tan δ: Using LCZ meter (Yokogawa Hewlett Packard 4276A), 20 ℃, 1KH
The relative permittivity ε and the dielectric loss tangent tan δ were measured under the condition of z.
結果を第１表に記載した。The results are shown in Table 1.
〔発明の効果〕 本発明方法は、工業的方法としても優れたものであり、
本発明の方法で製造された原料粉末は、低温焼結性であ
り、該粉末の焼結により得られるPZT系圧電セラミック
ス焼結体は、高密度で電気特性に優れている。 [Effect of the invention] The method of the present invention is excellent as an industrial method,
The raw material powder produced by the method of the present invention has low-temperature sinterability, and the PZT-based piezoelectric ceramics sintered body obtained by sintering the powder has high density and excellent electrical characteristics.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 3/00 Ｈ 3/12 ３０１ Ｈ０１Ｌ 41/24 Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location H01B 3/00 H 3/12 301 H01L 41/24
Claims (3)
〜0.9）で表される酸化物と一般式 PbA1/3Ｂ2/3O3（但し、ＡはMg,Ni,Zn及びMnからなる群
から選ばれた１種又は２種以上を、ＢはNb及び又はTaを
表す）で表される酸化物とからなるペロブスカイト系圧
電セラミックス粉末の製造において、ジルコニウム及び
チタニウム化合物の溶液、並びに予め仮焼して得られた
AO・B2O5で表される複合酸化物を沈殿形成液と混合し、
得られた沈殿を仮焼した後、鉛酸化物と混合し、仮焼す
ることを特徴とする鉛含有ペロブスカイト系酸化物の製
造法。1. A general formula Pb (Zr t Ti 1-t ) O 3 (where t = 0.1
To 0.9) and a general formula PbA 1/3 B 2/3 O 3 (where A is one or more selected from the group consisting of Mg, Ni, Zn and Mn, Is a solution of zirconium and titanium compounds, and obtained by pre-calcination in the production of a perovskite-based piezoelectric ceramic powder consisting of an oxide represented by Nb and / or Ta).
The composite oxide represented by AO / B 2 O 5 is mixed with the precipitation forming liquid,
A method for producing a lead-containing perovskite oxide, which comprises calcination of the obtained precipitate, mixing with lead oxide, and calcination.
ニウム及びチタニウム化合物の溶液を加え沈殿形成させ
る特許請求の範囲第（１）項記載の方法。2. The method according to claim 1, wherein a solution of zirconium and a titanium compound is added to a precipitate forming solution in which AO.B 2 O 5 is dispersed to form a precipitate.
の分散した沈殿形成液にAO・B2O5を加える特許請求の範
囲第（１）項記載の方法。3. The method according to claim 1, wherein AO.B 2 O 5 is added to a precipitate forming liquid in which zirconium and titanium mixed hydroxide are dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15563386A JPH0788220B2 (en) | 1986-07-02 | 1986-07-02 | Manufacturing method of easily sinterable ceramic powder for high-density dielectric ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15563386A JPH0788220B2 (en) | 1986-07-02 | 1986-07-02 | Manufacturing method of easily sinterable ceramic powder for high-density dielectric ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6311521A JPS6311521A (en) | 1988-01-19 |
| JPH0788220B2 true JPH0788220B2 (en) | 1995-09-27 |
Family
ID=15610247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15563386A Expired - Lifetime JPH0788220B2 (en) | 1986-07-02 | 1986-07-02 | Manufacturing method of easily sinterable ceramic powder for high-density dielectric ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788220B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117164357B (en) * | 2023-01-03 | 2024-07-19 | 广东捷成科创电子股份有限公司 | Five-element high-power piezoelectric ceramic material and preparation method thereof |
-
1986
- 1986-07-02 JP JP15563386A patent/JPH0788220B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6311521A (en) | 1988-01-19 |
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