JP3710100B2 - Manufacturing method of oxide piezoelectric material - Google Patents
Manufacturing method of oxide piezoelectric material Download PDFInfo
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- JP3710100B2 JP3710100B2 JP16692695A JP16692695A JP3710100B2 JP 3710100 B2 JP3710100 B2 JP 3710100B2 JP 16692695 A JP16692695 A JP 16692695A JP 16692695 A JP16692695 A JP 16692695A JP 3710100 B2 JP3710100 B2 JP 3710100B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000000463 material Substances 0.000 title claims description 24
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 42
- 150000001413 amino acids Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052745 lead Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 8
- 238000011899 heat drying method Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、酸化物圧電材料の製造方法に関し、特に、圧電磁器製品に使用されるＰＺＴ系材料の製造方法に関する。
【０００２】
【従来の技術】
現在、ＰＺＴは、圧電材料として幅広い電子部品に使用されているが、その部品の高性能化、小型化、低コスト化が進むにつれて、従来のＰＺＴ合成法では、限界に近付いているといわれている。
【０００３】
一般に、ＰＺＴの製造方法としては、鉛、ジルコニウム、チタンの各酸化物粉末をボールミル等で混合した後、予焼し、微粉砕工程を経て得られるＰＺＴ粉を造粒し、プレスして圧粉体を作製し、これを焼成することによって、目的のＰＺＴ焼成体を得ている。
【０００４】
【発明が解決しようとする課題】
通常、焼結温度は、１２００〜１３００℃であるが、例えば、積層型アクチュエータの場合、予焼粉にバインダー等を混合してシート化し、内部電極を印刷した後に積層して焼成するため、使用する内部電極は、焼結温度よりも融点の高いものを選択する必要がでてくる。
【０００５】
このようなＰＺＴと電極を同時に焼結する場合、一般に、Ａｇ−Ｐｄが電極として用いられている。Ｐｄは、融点が１５５２℃と高いため、Ａｇの比率の多い電極材を用いることが、コスト的に有利である。
【０００６】
しかし、Ａｇの融点は９６１℃なので、Ａｇの比率を多くするのには限界がある。従って、ＰＺＴの焼結温度を低くすることができれば、Ａｇの比率の多い安価な電極材を使用することが可能になる。
【０００７】
ところで、セラミックの焼成において、原料となる粉体の粒径が細かくなるほど、焼結温度が低下することが知られている。
【０００８】
通常、ＰＺＴの焼結温度は、１２００〜１３００℃であるが、従来のＰＺＴの製造方法では、焼結温度を低下させるには、先に述べたとおり、ＰＺＴ成分の各酸化物原材料を混合、予焼し、更に、微粉砕することで、微細な粉末を得なければならない。
【０００９】
しかしながら、この方法で得られる予焼粉の粒径は、数μｍとかなり大きいため、長時間の微粉砕を要して微細の粉末を得て焼結しなくてはならない。
【００１０】
又、圧電的な諸特性の焼結体粒径依存性について、常温での誘電率εｒ、電気機械結合係数ｋは、ほぼ一定であるが、焼結体粒径が小さくなるにつれて、機械的品質係数Ｑｍは増大する傾向にあることが知られている。
【００１１】
圧電材は、その製造過程で分極処理を行うが、粒径が大きければ粒子が動くことによって生じる応力が大きくなる。
【００１２】
機械的品質係数には、内部応力が大きく関わっており、分極後の圧電体中において、粒径が小さいほど内部応力が小さくなり、ひいては、高いＱｍ値を得ることが可能となる。
【００１３】
これには、やはり微細粉を用いて低温焼結することが必要条件であると考えられるが、先に述べたとおり、従来の方法では限界がある。
【００１４】
又、従来の製法において、原材料の各酸化物の混合、予焼は、ＰＺＴ材を得るのに不可欠な工程であった。なぜなら、各酸化物の固相反応でＰＺＴを作製するため、原材料の混合、予焼なしでは、均一なＰＺＴ材は得られないからである。
【００１５】
【発明が解決しようとする課題】
従って、まず、原材料を長時間混合した上に、８００℃前後の温度で予焼をし、酸化物を完全にＰＺＴとした後で焼成するというような、２段階の高温処理の工程を経なければならないという欠点があった。
【００１６】
しかも、このような製造プロセスを経ても、完全に均一な組成の材料を製造することは不可能であり、常に組成変動を含んでいるため、試料特性のばらつきを生じる要因となってしまう欠点があった。
【００１７】
このような従来の方法では、長時間の粉砕を要するため、コスト高になるという点、更に、粉砕媒体からの異物混入が増大し、組成比がずれるという欠点があった。
【００１８】
従って、本発明の目的は、組成比がずれず、焼結温度が低く、かつ特性ばらつきのない酸化物圧電材料を、少ない工程で簡便に、安価に製造する酸化物圧電材料の製造方法を提供することにある。
【００１９】
【課題を解決するための手段】
前記の問題を解決するため、種々の検討を行った結果、本発明者は、Ｐｂ，Ｚｒ，Ｔｉを含むアミノ酸錯体の溶液を加熱して得られる粉末を原料とすることで、従来の製法に比べて、非常に低い温度で焼結できることを見い出したものである。
【００２０】
即ち、本発明は、Ｐｂ，Ｔｉ，Ｚｒの元素を含む金属塩とアミノ酸との錯体の溶液を加熱して得られるジルコン酸チタン酸鉛（ＰＺＴ）粉末を原料とし、混合、造粒、成形、焼結して焼結体を得ることを特徴とする酸化物圧電材料の製造方法である。
【００２１】
又、本発明は、Ｐｂ，Ｔｉ，Ｚｒの元素を含む金属塩とアミノ酸との錯体の溶液を加熱して得られるジルコン酸チタン酸鉛（ＰＺＴ）粉末を原料とし、混合、造粒、成形、焼結して焼結体を得る酸化物圧電材料の製造方法において、前記金属塩がＰｂ（ＮＯ3）2，ＺｒＯ（ＮＯ3）2，Ｔｉ［ＯＣＨ（ＣＨ3）2］4であることを特徴とする酸化物圧電材料の製造方法である。
【００２２】
又、本発明は、Ｐｂ，Ｔｉ，Ｚｒの元素を含む金属塩とアミノ酸との錯体の溶液を加熱して得られるジルコン酸チタン酸鉛（ＰＺＴ）粉末を原料とし、混合、造粒、成形、焼結して焼結体を得る酸化物圧電材料の製造方法において、金属塩の総ｍｏｌ数とアミノ酸の総ｍｏｌ数の比が１：（０.５〜２）であることを特徴とする酸化物圧電材料の製造方法である。
【００２３】
又、本発明は、Ｐｂ，Ｔｉ，Ｚｒの元素を含む金属塩とアミノ酸との錯体の溶液を加熱して得られるジルコン酸チタン酸鉛（ＰＺＴ）粉末を原料とし、混合、造粒、成形、焼結して焼結体を得る酸化物圧電材料の製造方法において、前記ＰＺＴ粉末を得る方法が噴霧熱乾燥法であることを特徴とする酸化物圧電材料の製造方法である。
【００２４】
【作用】
Ｐｂ，Ｚｒ，Ｔｉの各アミノ酸錯体の混合溶液を加熱乾燥し、溶媒を除去すると、残留物が自己燃焼を起こす。この燃焼は、極めて短時間で終了するため、粉体粒径が非常に微細な粉末を得ることが可能となる。
【００２５】
この方法により製造したＰＺＴ粉を用いると、低温での焼結が可能となるため、焼結体粒径が小さくなり、高Ｑｍ化が図れる。
【００２６】
更に、この粉末製造法は、溶液状態から出発しているため、混合が容易であるばかりでなく、従来の固相反応による製造法では困難であった原子レベルの均一な組成が可能となる。
【００２７】
又、本発明は、ＰＺＴ粉を得るのに適したアミノ酸の混合量を見い出したものである。本製造方法において、金属塩の総ｍｏｌ数とアミノ酸の総ｍｏｌ数の比が、１：（０.５〜２）とした理由は、種々の検討の結果、この混合量のみで、微細で均一なＰＺＴ粉末を得ることができるからである。
【００２８】
即ち、金属塩の総ｍｏｌ数を１ｍｏｌとした時、アミノ酸が０.５ｍｏｌ未満の場合、溶液の溶媒を除いても自己燃焼を起こさず、又、２ｍｏｌを越えて反応を行った場合には得られたＰＺＴ粉末の粒径が大きくなってしまうからである。
【００２９】
又、本発明によれば、自己燃焼を引き起こす際には、溶媒を除去できる程度の温度であれば良いので、比較的低温の炉内に噴霧することで、製造が可能である。
【００３０】
更に、各金属塩とアミノ酸を含む溶媒には、工業的に水が安価であり、コスト的にも望ましい。
【００３１】
【実施例】
以下に、本発明の実施例について、図面を用いて説明する。
【００３２】
（実施例１）
高純度のＰｂ（ＮＯ3）2，ＺｒＯ（ＮＯ3）2，Ｔｉ［ＯＣＨ（ＣＨ3）2］4をｍｏｌ比で１：０.５２：０.４８となるように秤量し、更に、グリシンをＰｂ（ＮＯ3）2，ＺｒＯ（ＮＯ3）2，Ｔｉ［ＯＣＨ（ＣＨ3）2］4の総ｍｏｌ数に対して同ｍｏｌ数（比率１：１）秤量して、純水中に溶解し、よく混合した。
【００３３】
次に、この溶液を３００℃に保持した炉内に噴霧した。その後、炉内で反応し得られた生成物を見たところ、粉末状となっていた。
【００３４】
この粉末のＢ.Ｅ.Ｔ.径を測定したところ、０.１μｍであった。又、この粉末をＸ線回折により調査したところ、単一相のＰＺＴペロブスカイト構造となっていた。
【００３５】
続いて、バインダー混合の後、成形し、焼結温度８００〜１３００℃の範囲で変化させて、それぞれ２時間焼結した。
【００３６】
（実施例２）
高純度のＰｂ（ＮＯ3）2，ＺｒＯ（ＮＯ3）2，Ｔｉ［ＯＣＨ（ＣＨ3）2］4をｍｏｌ比で１：０.５２：０.４８となるように秤量し、更に、アラニンをＰｂ（ＮＯ3）2，ＺｒＯ（ＮＯ3）2，Ｔｉ［ＯＣＨ（ＣＨ3）2］4の総ｍｏｌ数に対して同ｍｏｌ数（比率１：１）秤量して、実施例１と同様にして反応させたところ、得られた生成物は粉末状となっており、この粉末のＢ.Ｅ.Ｔ.径は０.１μｍであった。又、Ｘ線回折をしたところ、ＰＺＴペロブスカイト単相であった。
【００３７】
この粉末を用いて実施例１と同様に成形し、９００℃で２時間焼結した。
【００３８】
（比較例１）
高純度の酸化鉛、酸化ジルコニウム、酸化チタンを用いて実施例と同組成になるよう秤量し、ボールミルで４５時間混合し、８００℃で予焼した。続いて、予焼粉を、更にボールミルにて２０時間及び１００時間粉砕して、Ｂ.Ｅ.Ｔ.径を測定したところ、それぞれ１.０μｍと０.５μｍであった。
【００３９】
各粉末を用いて、前記実施例と同様にして成形し、焼結温度８００℃〜１３００℃の範囲で変化させて２時間焼結した。
【００４０】
（比較例２）
従来の製造方法によって、酸化鉛、酸化ジルコニウム、酸化チタンを用いて比較例１と同組成になるよう秤量し、ボールミルで４５時間混合し、８００℃で予焼した。続いて、予焼粉を、更にボールミルにて５時間粉砕して、Ｂ.Ｅ.Ｔ.径を測定したところ、それぞれ５〜６μｍであった。
【００４１】
各粉末を用いて、前記比較例１と同様に成形し、焼結温度８００℃〜１３００℃の範囲で変化させて、２時間焼結した。
【００４２】
実施例１、比較例１、比較例２の各々の焼結体の焼結温度と焼結体密度との関係を、図１に各々Ａ，Ｂ，Ｃの曲線としてグラフに示した。
【００４３】
比較例１、比較例２の曲線Ｂ，Ｃと比べた時、実施例１のＡの曲線より、本発明のＰＺＴ粉末を原料とした場合、９００℃と、かなり低温でも、焼結性がよいことがわかる。
【００４４】
比較例１の微細粉を用いた場合、１１００℃でも焼結性がよく、予焼粉を２０時間、粉砕した場合の１２００℃焼結時と同等の焼結密度となるが、焼結温度としては、やはり高いと言わねばならない。
【００４５】
比較例２では、やはり焼結温度としては、１２００℃〜１３００℃と高い。
【００４６】
実施例１、実施例２、比較例１、比較例２の各々の焼結体の粒径、比誘電率εｒ、電気機械結合係数Ｋ31、機械的品質係数Ｑｍを表１に示す。
【００４７】
表１より、実施例１、実施例２では、機械的品質係数が比較例１、比較例２の従来のものより高い値が得られているのがわかる。
【００４９】
【発明の効果】
以上の実施例で述べた通り、ＰＺＴ材を製造する方法において、Ｐｂ，Ｚｒ，Ｔｉの各金属塩の総ｍｏｌ数に対し、適した量のアミノ酸を混合することで、組成比がずれず、均一な組成、かつ微細なＰＺＴ粉末を得ることができる。この粉末を原料とすることにより、従来と比べて、極めて低温で焼結が可能となり、特性のばらつきが少ない圧電材料を、少ない工程で簡便に安価に製造する酸化物圧電材料の製造方法を提供できた。
【図面の簡単な説明】
【図１】本実施例及び比較例により作製した焼結体の焼結温度と焼結体密度の関係を示す図。
【符号の説明】
Ａ 実施例１
Ｂ 比較例１
Ｃ 比較例２[0001]
[Industrial application fields]
The present invention relates to a method for manufacturing an oxide piezoelectric material, and more particularly to a method for manufacturing a PZT-based material used for a piezoelectric ceramic product.
[0002]
[Prior art]
Currently, PZT is used as a piezoelectric material in a wide range of electronic parts, but it is said that the conventional PZT synthesis method is approaching the limit as the performance of the parts, miniaturization, and cost reduction progress. Yes.
[0003]
In general, PZT is produced by mixing lead, zirconium, and titanium oxide powders with a ball mill, etc., pre-baking, granulating PZT powder obtained through a fine pulverization process, pressing and compacting the powder. A target PZT fired body is obtained by producing a body and firing the body.
[0004]
[Problems to be solved by the invention]
Usually, the sintering temperature is 1200 to 1300 ° C. For example, in the case of a laminated actuator, a binder is mixed with pre-baked powder to form a sheet, and the internal electrode is printed and then laminated and fired. It is necessary to select an internal electrode having a melting point higher than the sintering temperature.
[0005]
When such PZT and an electrode are sintered simultaneously, generally Ag-Pd is used as an electrode. Since Pd has a high melting point of 1552 ° C., it is advantageous in terms of cost to use an electrode material having a high Ag ratio.
[0006]
However, since the melting point of Ag is 961 ° C., there is a limit to increasing the Ag ratio. Therefore, if the sintering temperature of PZT can be lowered, it becomes possible to use an inexpensive electrode material having a large Ag ratio.
[0007]
By the way, in ceramic firing, it is known that the sintering temperature decreases as the particle size of the raw material powder becomes finer.
[0008]
Usually, the sintering temperature of PZT is 1200 to 1300 ° C. However, in the conventional method of producing PZT, in order to reduce the sintering temperature, as described above, each oxide raw material of the PZT component is mixed, A fine powder must be obtained by pre-baking and further pulverizing.
[0009]
However, since the particle size of the pre-baked powder obtained by this method is as large as several μm, fine powder must be obtained by sintering for a long time and sintered.
[0010]
In addition, regarding the dependence of piezoelectric characteristics on the sintered body particle size, the dielectric constant εr and electromechanical coupling coefficient k at room temperature are almost constant, but the mechanical quality decreases as the sintered body particle size decreases. It is known that the coefficient Qm tends to increase.
[0011]
Piezoelectric materials are polarized during the manufacturing process, but if the particle size is large, the stress caused by the movement of the particles increases.
[0012]
Internal stress is greatly related to the mechanical quality factor, and in the piezoelectric body after polarization, the smaller the particle diameter, the smaller the internal stress, and thus, a higher Qm value can be obtained.
[0013]
This is considered to be a necessary condition for low-temperature sintering using fine powder, but as described above, the conventional method has its limitations.
[0014]
Moreover, in the conventional manufacturing method, mixing and pre-calcination of each raw material oxide were indispensable steps for obtaining a PZT material. This is because PZT is produced by a solid-state reaction of each oxide, and a uniform PZT material cannot be obtained without mixing and pre-firing raw materials.
[0015]
[Problems to be solved by the invention]
Therefore, first of all, the raw materials must be mixed for a long time, followed by pre-baking at a temperature of around 800 ° C., and after the oxide is completely converted to PZT, the two-step high-temperature treatment process must be performed. There was a drawback of having to.
[0016]
In addition, it is impossible to manufacture a material with a completely uniform composition even through such a manufacturing process, and since it always includes a composition variation, there is a drawback that it causes a variation in sample characteristics. there were.
[0017]
Such a conventional method requires a long time of pulverization, which increases the cost, and further has a disadvantage that the mixing of foreign substances from the pulverization medium increases and the composition ratio is shifted.
[0018]
Accordingly, an object of the present invention is to provide a method for producing an oxide piezoelectric material, which can easily and inexpensively produce an oxide piezoelectric material having a composition ratio, a low sintering temperature, and no characteristic variation, with few steps. There is to do.
[0019]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventor made a conventional manufacturing method by using, as a raw material, powder obtained by heating a solution of an amino acid complex containing Pb, Zr, Ti. In comparison, it has been found that sintering can be performed at a very low temperature.
[0020]
That is, the present invention uses lead zirconate titanate (PZT) powder obtained by heating a solution of a complex of a metal salt containing an element of Pb, Ti, Zr and an amino acid as a raw material, mixed, granulated, molded, A method for producing an oxide piezoelectric material, comprising obtaining a sintered body by sintering.
[0021]
Further, the present invention uses lead zirconate titanate (PZT) powder obtained by heating a solution of a complex of a metal salt containing an element of Pb, Ti, and Zr and an amino acid as a raw material, and is mixed, granulated, molded, In the method of manufacturing an oxide piezoelectric material obtained by sintering to obtain a sintered body, the metal salt is Pb (NO 3 ) 2 , ZrO (NO 3 ) 2 , Ti [OCH (CH 3 ) 2 ] 4 It is the manufacturing method of the characteristic oxide piezoelectric material.
[0022]
Further, the present invention uses lead zirconate titanate (PZT) powder obtained by heating a solution of a complex of a metal salt containing an element of Pb, Ti, and Zr and an amino acid as a raw material, and is mixed, granulated, molded, In the method for producing an oxide piezoelectric material obtained by sintering to obtain a sintered body, the ratio of the total number of moles of metal salt to the total number of moles of amino acids is 1: (0.5 to 2). This is a method for manufacturing a piezoelectric material.
[0023]
Further, the present invention uses lead zirconate titanate (PZT) powder obtained by heating a solution of a complex of a metal salt containing an element of Pb, Ti, and Zr and an amino acid as a raw material, and is mixed, granulated, molded, In the method of manufacturing an oxide piezoelectric material obtained by sintering to obtain a sintered body, the method of obtaining the PZT powder is a spray heat drying method.
[0024]
[Action]
When the mixed solution of amino acid complexes of Pb, Zr, and Ti is dried by heating and the solvent is removed, the residue causes self-combustion. Since this combustion is completed in an extremely short time, it is possible to obtain a powder with a very fine powder particle size.
[0025]
When the PZT powder produced by this method is used, sintering at a low temperature is possible, so that the sintered body particle size is reduced and high Qm can be achieved.
[0026]
Furthermore, since this powder manufacturing method starts from a solution state, not only is mixing easy, but also a uniform composition at the atomic level, which has been difficult with a conventional manufacturing method using a solid phase reaction, is possible.
[0027]
In addition, the present invention has found out an amino acid mixture amount suitable for obtaining PZT powder. In this production method, the ratio of the total number of moles of metal salt to the total number of moles of amino acids was 1: (0.5 to 2). This is because a simple PZT powder can be obtained.
[0028]
That is, when the total number of moles of the metal salt is 1 mol, if the amino acid is less than 0.5 mol, self-combustion will not occur even if the solvent of the solution is removed, and if the reaction exceeds 2 mol, it will be obtained. This is because the particle size of the obtained PZT powder becomes large.
[0029]
In addition, according to the present invention, when self-combustion is caused, the temperature may be a temperature at which the solvent can be removed. Therefore, it can be manufactured by spraying in a relatively low temperature furnace.
[0030]
Furthermore, water is industrially inexpensive for the solvent containing each metal salt and amino acid, which is desirable in terms of cost.
[0031]
【Example】
Embodiments of the present invention will be described below with reference to the drawings.
[0032]
(Example 1)
High-purity Pb (NO 3 ) 2 , ZrO (NO 3 ) 2 , and Ti [OCH (CH 3 ) 2 ] 4 were weighed so that the molar ratio was 1: 0.52: 0.48. Is weighed in the same number of moles (ratio 1: 1) with respect to the total number of moles of Pb (NO 3 ) 2 , ZrO (NO 3 ) 2 , Ti [OCH (CH 3 ) 2 ] 4 and dissolved in pure water. And mixed well.
[0033]
Next, this solution was sprayed into a furnace maintained at 300 ° C. Then, when the product obtained by reacting in the furnace was observed, it was in a powder form.
[0034]
The BET diameter of this powder was measured and found to be 0.1 μm. When this powder was examined by X-ray diffraction, it had a single-phase PZT perovskite structure.
[0035]
Then, after binder mixing, it shape | molded, it changed in the range of 800-1300 degreeC sintering temperature, and sintered for 2 hours, respectively.
[0036]
(Example 2)
High-purity Pb (NO 3 ) 2 , ZrO (NO 3 ) 2 , and Ti [OCH (CH 3 ) 2 ] 4 were weighed so that the molar ratio was 1: 0.52: 0.48. Was weighed in the same number of moles (ratio 1: 1) with respect to the total number of moles of Pb (NO 3 ) 2 , ZrO (NO 3 ) 2 , and Ti [OCH (CH 3 ) 2 ] 4. The product thus obtained was in the form of powder, and the BET diameter of this powder was 0.1 μm. Further, X-ray diffraction revealed a single phase of PZT perovskite.
[0037]
Using this powder, it was molded in the same manner as in Example 1, and sintered at 900 ° C. for 2 hours.
[0038]
(Comparative Example 1)
Using high-purity lead oxide, zirconium oxide, and titanium oxide, they were weighed to have the same composition as in the examples, mixed in a ball mill for 45 hours, and pre-fired at 800 ° C. Subsequently, the prefired powder was further pulverized with a ball mill for 20 hours and 100 hours, and the BET diameter was measured to be 1.0 μm and 0.5 μm, respectively.
[0039]
Each powder was molded in the same manner as in the above example, and sintered for 2 hours while changing the sintering temperature in the range of 800 ° C to 1300 ° C.
[0040]
(Comparative Example 2)
Using a conventional manufacturing method, lead oxide, zirconium oxide, and titanium oxide were weighed so as to have the same composition as in Comparative Example 1, mixed in a ball mill for 45 hours, and pre-fired at 800 ° C. Subsequently, the pre-baked powder was further pulverized with a ball mill for 5 hours, and the BET diameter was measured to be 5 to 6 μm, respectively.
[0041]
Each powder was molded in the same manner as in Comparative Example 1, and the sintering temperature was changed in the range of 800 ° C. to 1300 ° C. and sintered for 2 hours.
[0042]
The relationship between the sintering temperature and the sintered body density of each of the sintered bodies of Example 1, Comparative Example 1, and Comparative Example 2 is shown in a graph as curves A, B, and C in FIG.
[0043]
When compared with the curves B and C of Comparative Example 1 and Comparative Example 2, when the PZT powder of the present invention is used as a raw material from the curve of A of Example 1, the sinterability is good even at a considerably low temperature of 900 ° C. I understand that.
[0044]
When the fine powder of Comparative Example 1 is used, the sinterability is good even at 1100 ° C., and the sintering density is equivalent to that at 1200 ° C. sintering when the pre-baked powder is pulverized for 20 hours. Must be said that it is still expensive.
[0045]
In Comparative Example 2, the sintering temperature is still as high as 1200 ° C to 1300 ° C.
[0046]
Table 1 shows the grain size, relative dielectric constant εr, electromechanical coupling coefficient K 31 , and mechanical quality factor Qm of each of the sintered bodies of Example 1, Example 2, Comparative Example 1, and Comparative Example 2.
[0047]
From Table 1, it can be seen that in Example 1 and Example 2, the mechanical quality factor is higher than that of Comparative Example 1 and Comparative Example 2 in the related art.
[0049]
【The invention's effect】
As described in the above examples, in the method for producing a PZT material, by mixing an appropriate amount of amino acid with respect to the total number of moles of each metal salt of Pb, Zr, Ti, the composition ratio does not shift, A uniform composition and fine PZT powder can be obtained. By using this powder as a raw material, we provide a method for manufacturing an oxide piezoelectric material that can be sintered at an extremely low temperature compared to conventional methods and that can easily and inexpensively produce a piezoelectric material with little variation in properties. did it.
[Brief description of the drawings]
FIG. 1 is a view showing a relationship between a sintering temperature and a sintered body density of sintered bodies produced by Examples and Comparative Examples.
[Explanation of symbols]
A Example 1
B Comparative Example 1
C Comparative Example 2
Claims (4)
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| JP16692695A JP3710100B2 (en) | 1995-06-07 | 1995-06-07 | Manufacturing method of oxide piezoelectric material |
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| JP16692695A JP3710100B2 (en) | 1995-06-07 | 1995-06-07 | Manufacturing method of oxide piezoelectric material |
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| JP2006282434A (en) * | 2005-03-31 | 2006-10-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for producing perovskite complex oxide |
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