JP3345974B2 - Piezoelectric ceramic composition - Google Patents
Piezoelectric ceramic compositionInfo
- Publication number
- JP3345974B2 JP3345974B2 JP20901793A JP20901793A JP3345974B2 JP 3345974 B2 JP3345974 B2 JP 3345974B2 JP 20901793 A JP20901793 A JP 20901793A JP 20901793 A JP20901793 A JP 20901793A JP 3345974 B2 JP3345974 B2 JP 3345974B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- piezoelectric ceramic
- temperature
- ceramic composition
- sintering
- 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 - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 40
- 239000000919 ceramic Substances 0.000 title claims description 25
- 238000010304 firing Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000010955 niobium Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000009766 low-temperature sintering Methods 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、圧電体セラミックス
に関し、詳しくは、圧電アクチュエータやブザーなどの
材料として用いるのに適した圧電ｄ定数の大きな圧電磁
器組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic, and more particularly to a piezoelectric ceramic composition having a large piezoelectric d constant suitable for use as a material for a piezoelectric actuator or a buzzer.
【０００２】[0002]
【従来の技術】圧電ｄ定数の大きな圧電体セラミックス
として知られる、Ｐｂ（Ｎｉ1/3Ｎｂ2／3）Ｏ3−ＰｂＺ
ｒＯ3−ＰｂＴｉＯ3を基本組成とする圧電体材料は、通
常、酸化鉛（ＰｂＯ）、酸化ジルコニウム（Ｚｒ
Ｏ2）、酸化チタン（ＴｉＯ2）、酸化ニッケル（Ｎｉ
Ｏ）、五酸化ニオブ（Ｎｂ2Ｏ5）などの酸化物原料を所
定の化学量論組成となるように調合し、ボールミルなど
を用いて混合分散させた後、所定の温度で仮焼し、さら
に、粉砕及びバインダー混合を行った後、所定の形状に
成形し、これを１２００℃以上の高温で焼成して焼結反
応を行わせることにより製造されている。Known as large piezoelectric ceramics of the Related Art piezoelectric d constant, Pb (Ni 1/3 Nb 2/ 3) O 3 -PbZ
Piezoelectric materials having a basic composition of rO 3 —PbTiO 3 are generally lead oxide (PbO), zirconium oxide (Zr
O 2 ), titanium oxide (TiO 2 ), nickel oxide (Ni
O), an oxide material such as niobium pentoxide (Nb 2 O 5 ) is prepared to have a predetermined stoichiometric composition, mixed and dispersed using a ball mill or the like, and then calcined at a predetermined temperature. Furthermore, after pulverizing and mixing a binder, the mixture is formed into a predetermined shape, which is fired at a high temperature of 1200 ° C. or more to perform a sintering reaction.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記従来の製
造方法では、仮焼後の圧電磁器組成物（セラミックス）
の焼成温度が１２００℃以上と高温であるため、セラミ
ックスからのＰｂの蒸発が激しく、セラミックス内部に
圧電性のばらつきを生じさせるという問題点がある。However, in the above-mentioned conventional manufacturing method, the calcined piezoelectric ceramic composition (ceramics) is used.
Since the baking temperature is as high as 1200 ° C. or more, Pb evaporates vigorously from the ceramics, causing a problem that the piezoelectricity varies within the ceramics.
【０００４】また、Ｐｂの蒸発を抑制しようとすると、
焼成時に密閉度の高いさや鉢を用いたり、さや鉢の内部
にＰｂＯなどを入れて過剰のＰｂ雰囲気を作るというよ
うな雰囲気制御技術を用いたりすることが必要になる。
そして、その結果として、製造工程が複雑になったり、
品質にばらつきが生じたりするという問題点がある。ま
た、さや鉢は、高温で繰り返して使用されることからそ
の寿命が短く、製造コストが増大するという問題点があ
る。In order to suppress the evaporation of Pb,
It is necessary to use a pod having a high degree of sealing at the time of firing, or to use an atmosphere control technique such as creating an excessive Pb atmosphere by putting PbO or the like inside the pod.
And as a result, the manufacturing process becomes complicated,
There is a problem that the quality varies. In addition, since pods are repeatedly used at a high temperature, there is a problem that the life is short and the manufacturing cost is increased.
【０００５】さらに、圧電アクチュエータなどの一体焼
成型のセラミックスを製造するにあたっては、焼成温度
が高いため、内部電極材料として、Ｐｔなどの高融点の
貴金属を用いることが必要になり、これがセラミックス
素子のコストを上昇させる原因になるという問題点があ
る。[0005] Further, in manufacturing an integrally fired ceramic such as a piezoelectric actuator, a high firing temperature necessitates the use of a high melting point noble metal such as Pt as an internal electrode material. There is a problem that the cost is increased.
【０００６】この発明は、上記問題点を解決するもので
あり、低い温度で焼成することが可能で、Ｐｂの蒸発が
少なく、焼成時に特殊なさや鉢を用いたり、Ｐｂの雰囲
気制御を行ったりする必要がなく、また、圧電アクチュ
エータのような一体焼成型のセラミックス素子を製造す
る場合に、内部電極として高価なＰｔなどの材料を使用
する必要のない圧電磁器組成物を提供することを目的と
する。The present invention solves the above-mentioned problems, and can be fired at a low temperature, has low evaporation of Pb, uses a special pod during firing, or controls the atmosphere of Pb. It is another object of the present invention to provide a piezoelectric ceramic composition that does not require the use of expensive materials such as Pt as internal electrodes when manufacturing an integrally fired ceramic element such as a piezoelectric actuator. I do.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、この発明の圧電磁器組成物は、ＸＰｂβ（Ｎｉα /3
Ｎｂ2/3）Ｏ3−ＹＰｂＺｒＯ3−ＺＰｂＴｉＯ3を基本組
成とし、一般記号ＡＢＯ3で表されるペロブスカイト型
の圧電磁器組成物であって、Ｘ，Ｙ，Ｚがそれぞれ、 ０．２０≦Ｘ≦０．６０ ０．１５≦Ｙ≦０．６０ ０．３０≦Ｚ≦０．６０ の範囲にあり、かつ、ＢサイトのＮｉ比率（α）が、 １＜α＜２ の範囲にあって、化学量論組成よりも過剰であるととも
に、ＡサイトのＰｂ比率（β）が、 １＜β≦１．０６ の範囲にあって、化学量論組成よりも過剰であることを
特徴とする。[MEANS FOR SOLVING THE PROBLEMS] To achieve the above object
In addition, the piezoelectric ceramic composition of the present invention comprises XPbβ (Niα /Three
Nb2/3) OThree-YPbZrOThree-ZPbTiOThreeThe basic group
And the general symbol ABOThreePerovskite type represented by
Wherein X, Y, and Z are respectively in the range of 0.20 ≦ X ≦ 0.60 0.15 ≦ Y ≦ 0.60 0.30 ≦ Z ≦ 0.60, and , The B site has an Ni ratio (α) in the range of 1 <α <2, which is more than the stoichiometric composition.
In addition, the fact that the Pb ratio (β) of the A site is in the range of 1 <β ≦ 1.06 and is more than the stoichiometric composition.
Features.
【０００８】また、焼成前の圧電磁器材料粉末の比表面
積（ＳＳ）が、１０ｍ2／ｇ以上（ＳＳ≧１０ｍ2／ｇ）
であることを特徴とするFurther, the specific surface area (SS) of the piezoelectric ceramic material powder before firing is 10 m 2 / g or more (SS ≧ 10 m 2 / g)
Is characterized by
【０００９】[0009]
【作用】化学量論組成を越えて存在するＢサイトのＮｉ
及びＡサイトのＰｂが低温焼結を可能にする詳細なメカ
ニズムは必ずしも明らかではないが、現時点ではおよそ
次のように考えられる。[Action] Ni of the B site existing beyond the stoichiometric composition
Although the detailed mechanism by which Pb at site A and Pb enables low-temperature sintering is not necessarily clear, at this time, it is considered as follows.
【００１０】Ｎｂを多く含むチタン酸ジルコン酸鉛（Ｐ
ＺＴ）系材料では、焼成途中に中間生成物としてパイロ
クロア相（ＰｂとＮｂの酸化物）が生成しやすいことは
よく知られている。したがって、上記組成を有するこの
発明の圧電磁器組成物においては、焼成段階においてパ
イロクロア相からＰｂ（Ｎｉ，Ｎｂ）Ｏ3が生成する過
程を経ることになる。[0010] Lead zirconate titanate containing a large amount of Nb (P
It is well known that a pyrochlore phase (an oxide of Pb and Nb) is easily generated as an intermediate product in the course of sintering in a ZT) -based material. Therefore, the piezoelectric ceramic composition of the present invention having the above composition undergoes a process of producing Pb (Ni, Nb) O 3 from the pyrochlore phase in the firing step.
【００１１】ところで、原料中のＮｉ（ＮｉＯ）はその
分散性が悪いため、焼成前のセラミックス中には、Ｎｉ
が過剰の部分とＮｉが不足している部分が生じる。By the way, Ni (NiO) in the raw material has a poor dispersibility, so that the ceramic before firing contains Ni (NiO).
There is an excess portion and a portion lacking Ni.
【００１２】そして、Ｎｉが不足している系（部分）で
は、焼成中にパイロクロア相からＰｂ（Ｎｉ，Ｎｂ）Ｏ
3への反応が完全には進まず、一部がＰｂとのＮｂで構
成されるパイロクロア構造の中間生成物（Ｐｂ2Ｎｂ2Ｏ
7）として残存しやすくなる。このパイロクロア相の焼
結性はチタン酸ジルコン酸鉛（Ｐｂ（Ｚｒ，Ｔｉ）Ｏ
3）の焼結性と同等であり、この相が残っていると低温
での焼結は望めない。Then, in a system (part) in which Ni is insufficient,
Means that Pb (Ni, Nb) O is converted from pyrochlore phase during firing.
ThreeReaction does not proceed completely, and part of the reaction consists of Nb with Pb.
The formed intermediate product of pyrochlore structure (PbTwoNbTwoO
7). Grilling this pyrochlore phase
The binding properties are lead zirconate titanate (Pb (Zr, Ti) O
3) Equivalent to sinterability, and if this phase remains, low temperature
Sintering cannot be expected.
【００１３】一方、Ｎｉが過剰に存在する系（部分）で
は、パイロクロア相からＰｂ（Ｎｉ，Ｎｂ）Ｏ3への反
応が完全に進行し、Ｐｂ2Ｎｂ2Ｏ7（パイロクロア構造
の中間生成物）として残存しにくくなり、また、パイロ
クロア相のうち、Ｐｂ3Ｎｂ2Ｏ 8はＰｂ（Ｎｉ，Ｎｂ）
Ｏ3と反応する化合物であって、融点が９２５℃と低い
ために、液相となってＰＺＴセラミックスの低温焼結に
寄与するものと考えられる。On the other hand, in a system (part) in which Ni is excessively present,
Means Pb (Ni, Nb) O from pyrochlore phaseThreeAnti against
Response progressed completely and PbTwoNbTwoO7(Pyrochlore structure
Is difficult to remain as an intermediate product of
Of the chlor phase, PbThreeNbTwoO 8 is Pb (Ni, Nb)
OThreeWith a low melting point of 925 ° C
Liquid phase for low-temperature sintering of PZT ceramics
It is considered to contribute.
【００１４】加えて、ＡサイトのＰｂ比率を過剰にする
ことにより、この液相の生成がさらに加速され、焼結温
度の低温化が促進されるものと考えられる。In addition, it is considered that by making the Pb ratio of the A site excessive, the generation of the liquid phase is further accelerated and the lowering of the sintering temperature is promoted.
【００１５】したがって、この発明の圧電磁器組成物の
ようにＢサイトのＮｉ及びＡサイトのＰｂを化学量論組
成以上に含有させて、組成物の多くの部分でＮｉ及びＰ
ｂが過剰に存在する状態を生じさせることにより、低温
で焼結することが可能になる。Therefore, as in the piezoelectric ceramic composition of the present invention, Ni of the B site and Pb of the A site are contained in a stoichiometric composition or more, and Ni and P are contained in many parts of the composition.
By generating a state in which b is excessively present, sintering can be performed at a low temperature.
【００１６】なお、この発明の圧電磁器組成物におい
て、Ｘ（すなわちＰｂのモル比）を０．２０〜０．６０
としたのは、Ｘが０．２０未満では、中間生成物の生成
量が少なくなるため、焼結性への寄与が少なくなり、ま
た、Ｘの量が０．６０を越えるとキュリー点（Ｔｃ）が
１００℃以下となり、室温付近での共振周波数や変位特
性の温度安定性が悪くなることによる。In the piezoelectric ceramic composition of the present invention, X (that is, the molar ratio of Pb) is set to 0.20 to 0.60.
The reason is that when X is less than 0.20, the amount of the intermediate product produced is small, so that the contribution to sinterability is reduced. When the amount of X exceeds 0.60, the Curie point (Tc ) Is 100 ° C. or less, and the temperature stability of the resonance frequency and the displacement characteristic near room temperature deteriorates.
【００１７】また、Ｙ（すなわちＰｂＺｒＯ3のモル
比）を０．１５〜０．６０としたのは、ＹがＭＰＢから
離れる０．１５未満や、０．６０を越える範囲では圧電
性が小さく、高い電気機械結合係数（Ｋｐ）や比誘電率
（ε33／ε0）を必要とする圧電アクチュエータやブザ
ーなどの用途には適用できなくなることによる。Further, the reason why Y (that is, the molar ratio of PbZrO 3 ) is set to 0.15 to 0.60 is that the piezoelectricity is small when Y is less than 0.15 away from MPB or exceeds 0.60, This is because it cannot be applied to applications such as piezoelectric actuators and buzzers that require a high electromechanical coupling coefficient (Kp) and a relative dielectric constant (ε 33 / ε 0 ).
【００１８】なお、Ｚは、１＝Ｘ＋Ｙ＋Ｚを満たすため
に、０．３０〜０．６０の範囲に限定される。Note that Z is limited to a range of 0.30 to 0.60 in order to satisfy 1 = X + Y + Z.
【００１９】また、αの値を１＜α＜２の範囲に限定し
たのは、αの値が１以下ではパイロクロア相の生成を促
進することになり、低温焼結性を得ることができず、ま
た、αの値が２以上になると焼成中にＮｉが粒内に固溶
して電気特性を大きく変化させてしまい、必要な特性を
得ることができなくなることによる。The reason why the value of α is limited to the range of 1 <α <2 is that if the value of α is 1 or less, the formation of a pyrochlore phase is promoted, and low-temperature sinterability cannot be obtained. Also, when the value of α is 2 or more, Ni solid-dissolves in the grains during sintering, causing significant changes in the electrical characteristics, making it impossible to obtain the required characteristics.
【００２０】また、βの値を１＜β≦１．０６の範囲に
限定したのは、βの値が１以下の場合、低温焼結性を向
上させる効果が必ずしも十分ではなく、また、βの値が
１．０６を越えると過剰のＰｂがガラス相となって焼結
体中に残り、圧電性の低下を招き、好ましくないことに
よる。The reason that the value of β is limited to the range of 1 <β ≦ 1.06 is that when the value of β is 1 or less, the effect of improving the low-temperature sinterability is not always sufficient. Exceeds 1.06, excess Pb becomes a glass phase and remains in the sintered body, causing a decrease in piezoelectricity, which is not preferable.
【００２１】なお、βの値に関しては、上記αとの関係
を問題にすることなく、βを単独で過剰にしても低温焼
結の効果を得ることは可能であるが、圧電性が大きく低
下するため、βのみを単独で過剰にすることは好ましく
ない。Regarding the value of β, it is possible to obtain the effect of low-temperature sintering even if β alone is excessive, without making the relationship with α a problem, but the piezoelectricity is greatly reduced. Therefore, it is not preferable to increase β alone alone.
【００２２】さらに、焼成前の圧電磁器材料粉末の比表
面積（ＳＳ）を、１０ｍ2／ｇ以上（ＳＳ≧１０ｍ2／
ｇ）とすることにより、低温焼結性をさらに向上させ、
９００℃を下回るような温度で焼結させることが可能に
なる。これは、圧電磁器材料粉末の粒子が微細化するこ
とにより、Ｎｉ及びＰｂの分散性が向上するためである
と考えられる。Furthermore, the specific surface area of the piezoelectric ceramic material powder before firing (SS), 10m 2 / g or more (SS ≧ 10m 2 /
g) further improves low-temperature sinterability,
It becomes possible to perform sintering at a temperature below 900 ° C. It is considered that this is because the dispersibility of Ni and Pb is improved by making the particles of the piezoelectric ceramic material finer.
【００２３】[0023]
【実施例】以下に、この発明の実施例を示して、その特
徴とするところをさらに具体的に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, and the features thereof will be described more specifically.
【００２４】まず、出発原料として、Ｐｂ3Ｏ4，ＴｉＯ
2，ＺｒＯ2，ＮｉＯ，Ｎｂ2Ｏ5を用意し、これらの出発
原料を表１，表２に示すような組成となるように秤取
し、ボールミルを用いて湿式混合した後、７００〜９０
０℃で２時間仮焼し、粉砕（微粉砕）して仮焼粉末を得
た。それから、この仮焼粉末に酢酸ビニル系のバインダ
ーを加えてさらに湿式混合を行い、乾燥、造粒後に１０
００〜２０００kg／cm2の圧力で円板状に成形し、これ
を８５０〜１２００℃で焼成し、直径１０mm、厚さ１mm
の磁器円板を得た。First, as starting materials, Pb 3 O 4 and TiO
2 , ZrO 2 , NiO, and Nb 2 O 5 are prepared, these starting materials are weighed to have the composition shown in Tables 1 and 2, and wet-mixed using a ball mill.
The mixture was calcined at 0 ° C. for 2 hours and pulverized (finely pulverized) to obtain a calcined powder. Then, a vinyl acetate-based binder was added to the calcined powder, and wet mixing was further performed.
It is shaped into a disc at a pressure of 00 to 2000 kg / cm 2 and fired at 850 to 1200 ° C. to have a diameter of 10 mm and a thickness of 1 mm.
Was obtained.
【００２５】そして、この磁器円板の表面（両主面）
に、銀ペーストを塗布し、８００℃で２時間焼き付けて
銀電極を形成した後、８０℃のシリコンオイル中で３ｋ
Ｖ／mmの直流電圧を印加して分極処理を施し、圧電磁器
円板（試料）を得た。The surface (both main surfaces) of this porcelain disk
Is coated with a silver paste and baked at 800 ° C. for 2 hours to form a silver electrode.
Polarization treatment was performed by applying a DC voltage of V / mm to obtain a piezoelectric ceramic disk (sample).
【００２６】そして、これらの試料について、比誘電率
（ε33／ε0）、電気機械結合係数（Ｋｐ）、及び機械
的品質係数（Ｑｍ）を測定した。その結果を表１，表２
に示す。なお、表１，表２において、試料No.に*印を付
したものは、この発明の範囲外の組成を有する試料であ
る。The relative permittivity (ε 33 / ε 0 ), the electromechanical coupling coefficient (Kp), and the mechanical quality coefficient (Qm) of these samples were measured. Table 1 and Table 2 show the results.
Shown in In Tables 1 and 2, samples marked with an asterisk (*) are samples having compositions outside the scope of the present invention.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】表１，表２に示すように、この発明の実施
例にかかる各試料については、比誘電率（ε33／
ε0）、電気機械結合係数（Ｋｐ）、及び機械的品質係
数（Ｑｍ）に関し、ほぼ良好な結果が得られていること
がわかる。As shown in Tables 1 and 2, the relative dielectric constant (ε 33 /
It can be seen that almost satisfactory results were obtained with respect to ε 0 ), the electromechanical coupling coefficient (Kp), and the mechanical quality coefficient (Qm).
【００３０】なお、αについては、表２の試料No.１６
（α＝１．０）と試料No.１７（α＝１．５）の比較に
みられるように、αの値が１以下の場合には、パイロク
ロア相の生成を促進する結果となり、十分な低温焼結性
を得ることができないことがわかる。また、試料No.２
１（α＝２．５）にみられるように、αの値が２以上に
なると焼成中にＮｉが粒内に固溶して電気特性が大きく
変化する（すなわち、Ｋｐが小さくなり、Ｑｍが大きく
なる）ため好ましくないことがわかる。As for α, sample No. 16 in Table 2 was used.
(Α = 1.0) and Sample No. 17 (α = 1.5), when the value of α is 1 or less, the result is that the formation of the pyrochlore phase is promoted, and It turns out that low temperature sinterability cannot be obtained. Sample No. 2
As can be seen from 1 (α = 2.5), when the value of α is 2 or more, Ni solid-dissolves in the grains during sintering and the electrical characteristics change greatly (that is, Kp decreases and Qm decreases). It is found that this is not preferable.
【００３１】また、βについては、表１の試料No.１２
（β＝１．０２）と試料No.１３（β＝０．９８）の比
較にみられるように、βが１以下になると、βを１より
大きくすることにより得られる効果が失われ、また、表
２の試料No.１８と２０の比較にみられるように、βの
値が１．０６を越えると過剰のＰｂがガラス相となって
焼結体中に残り、圧電性の低下を招くことがわかる。As for β, sample No. 12 in Table 1 was used.
As can be seen from the comparison between (β = 1.02) and Sample No. 13 (β = 0.98), when β becomes 1 or less, the effect obtained by making β larger than 1 is lost. As can be seen from the comparison between Samples Nos. 18 and 20 in Table 2, when the value of β exceeds 1.06, excess Pb becomes a glass phase and remains in the sintered body, causing a decrease in piezoelectricity. You can see that.
【００３２】なお、βの値に関しては、αとの関係を問
題にすることなく、βを単独で過剰にしても低温焼結の
効果を得ることは可能であるが、表２の試料No.１６
（α＝１．０，β＝１．０２でβのみ過剰）と試料No.
１７（α＝１．５，β＝１．０２でαとβの両方が過
剰）の比較にみられるように、βのみを単独で過剰にし
た場合には、圧電性が大きく低下するため好ましくな
い。Regarding the value of β, it is possible to obtain the effect of low-temperature sintering even if β alone is excessive without making the relationship with α a problem. 16
(Α = 1.0, β = 1.02 and β only excess) and sample No.
As shown in the comparison of 17 (α = 1.5, β = 1.02 and both α and β are excessive), when only β alone is excessive, the piezoelectricity is greatly reduced, which is preferable. Absent.
【００３３】また、図１に、Ｘ＝０．４０，Ｙ＝０．２
３，Ｚ＝０．３８の組成において、α＝１．０及びα＝
１．５（ともにβ＝１．００）とした場合の焼結性、す
なわち、焼成温度と焼結密度（焼結体の密度）との関係
を示すとともに、図２に、Ｘ＝０．４０，Ｙ＝０．２
３，Ｚ＝０．３８の組成において、α＝１．０，β＝
１．００とした場合及びα＝１．５，β＝１．０２とし
た場合の焼結性を示す。FIG. 1 shows that X = 0.40 and Y = 0.2
3, in the composition of Z = 0.38, α = 1.0 and α =
The sinterability when 1.5 (both β = 1.00), that is, the relationship between the sintering temperature and the sintering density (density of the sintered body) is shown, and FIG. , Y = 0.2
In the composition of 3, Z = 0.38, α = 1.0, β =
The sinterability when 1.00 and α = 1.5 and β = 1.02 are shown.
【００３４】図１，図２より、ＮｉとＰｂの両方を過剰
にした原料（α＝１．５，β＝１．０２）を用いた場合
には、Ｎｉのみを過剰にした原料（α＝１．５，β＝
１．００）を用いた場合よりも低温焼結性が向上してい
ることがわかる。From FIG. 1 and FIG. 2, when the raw material in which both Ni and Pb are excessive (α = 1.5, β = 1.02) is used, the raw material in which only Ni is excessive (α = 1.5, β =
1.00), the low-temperature sinterability is improved.
【００３５】さらに、仮焼後に原料粉末（圧電磁器材料
粉末）を微粉砕することにより、さらに、低温焼結性を
高めることが可能であり、試料No.１７（特に微粉砕し
ない原料粉末を使用）と試料No.１８（微粉砕した原料
粉末を使用）との比較にみられるように、Ｎｉ及びＰｂ
が過剰で、かつ、仮焼後に微粉砕した原料粉末を用いる
ことにより、９００℃を下回るような低い焼成温度（試
料No.１８では８５０℃）で焼成しても十分な圧電性が
得られることがわかる。なお、この発明では、粉砕粒度
の指標として比表面積（ＳＳ）の値を用いたが、このＳ
Ｓ値が１０ｍ2／ｇより小さくなると９００℃を下回る
ような低温で焼成できるような低温焼結性を得ることは
困難になる。したがって、９００℃を下回るような温度
で焼成することが可能な低温焼結性と圧電性とを両立さ
せるためには、比表面積を１０ｍ 2／ｇ以上にすること
が必要になる。Further, after calcining, the raw material powder (piezoelectric ceramic material)
Powder) to further improve low-temperature sinterability.
Sample No. 17 (especially finely pulverized
No raw material powder) and Sample No. 18 (finely ground raw material)
Powders), Ni and Pb
Is excessive and uses raw material powder finely pulverized after calcination
As a result, a low firing temperature (below 900 ° C)
Sufficient piezoelectricity even when fired at 850 ° C for material No. 18)
It can be seen that it can be obtained. In the present invention, the pulverized particle size
The value of the specific surface area (SS) was used as an index of
S value is 10mTwo/ G is less than 900 ° C
To obtain low-temperature sinterability that can be fired at such low temperatures
It becomes difficult. Therefore, a temperature below 900 ° C
Low temperature sinterability and piezoelectricity that can be fired by
In order to make the specific surface area 10m 2 / g or more
Is required.
【００３６】なお、この発明の圧電磁器組成物は、上記
実施例に限定されるものではなく、発明の要旨の範囲内
において、その組成や製造方法を変化させるなどの応
用、変形を加えることが可能である。It should be noted that the piezoelectric ceramic composition of the present invention is not limited to the above-described embodiment, but may be applied or modified by changing its composition or manufacturing method within the scope of the invention. It is possible.
【００３７】[0037]
【発明の効果】上述のように、この発明の圧電磁器組成
物は、ＸＰｂβ（Ｎｉα/3Ｎｂ2/3）Ｏ3−ＹＰｂＺｒＯ
3−ＺＰｂＴｉＯ3を基本組成とし、一般記号ＡＢＯ3で
表されるペロブスカイト型の圧電磁器組成物の、Ｘ，
Ｙ，Ｚを上記所定の範囲とし、かつ、ＢサイトのＮｉ比
率（α）を１＜α＜２と化学量論組成よりも過剰にする
とともに、ＡサイトのＰｂ比率（β）を１＜β≦１．０
６と化学量論組成よりも過剰にしているので、特に、共
沈法や、ゾル−ゲル法などの化学的合成方法を用いるこ
となく、従来の酸化物を混合して合成する方法をとりな
がら、必要な圧電性を確保しつつ焼成温度を従来よりも
相当に低下させることが可能になる。As described above, the piezoelectric ceramic composition of the present invention has a composition of XPbβ (Niα / 3Nb 2/3 ) O 3 -YPbZrO.
A perovskite-type piezoelectric ceramic composition having a basic composition of 3- ZPbTiO 3 and represented by the general symbol ABO 3 , X,
Y and Z are set in the above-mentioned predetermined ranges, and the Ni ratio (α) of the B site is set to 1 <α <2, which is more than the stoichiometric composition, and the Pb ratio (β) of the A site is set to 1 <β. ≦ 1.0
6, which is an excess of the stoichiometric composition, so that a conventional method of mixing and synthesizing an oxide without using a chemical synthesis method such as a coprecipitation method or a sol-gel method is used. In addition, the firing temperature can be considerably reduced as compared with the related art while securing necessary piezoelectricity.
【００３８】さらに、焼成前の原料粉末を微粉砕してそ
の比表面積（ＳＳ）を１０ｍ2／ｇ以上（ＳＳ≧１０ｍ2
／ｇ）とすることにより、さらに低温で焼結させること
が可能になる。Further, the raw material powder before firing is finely pulverized to have a specific surface area (SS) of at least 10 m 2 / g (SS ≧ 10 m 2
/ G), it is possible to perform sintering at a lower temperature.
【００３９】したがって、この発明の圧電磁器組成物に
よれば、従来の圧電磁器組成物を製造する場合のよう
に、焼成時に密閉度の高い特殊なさや鉢を用いたり、Ｐ
ｂの雰囲気制御を行ったりする必要がなくなるととも
に、焼成温度が低くなることから、さや鉢の寿命を大幅
に向上させることが可能になる。さらに、一体焼成の圧
電アクチュエータを製造する場合においても、内部電極
として、Ｐｔなどの高融点の貴金属を用いる必要がな
く、比較的安価なＡｇ−Ｐｄ合金などを使用することが
可能になるため、製造コストを大幅に削減することがで
きる。Therefore, according to the piezoelectric ceramic composition of the present invention, as in the case of producing a conventional piezoelectric ceramic composition, a special sheath having a high degree of sealing can be used at the time of sintering.
It is not necessary to control the atmosphere of b, and the firing temperature is lowered, so that the life of the pod can be greatly improved. Further, even in the case of manufacturing an integrally fired piezoelectric actuator, it is not necessary to use a high melting point noble metal such as Pt as an internal electrode, and it becomes possible to use a relatively inexpensive Ag-Pd alloy or the like. Manufacturing costs can be significantly reduced.
【図１】Ｘ＝０．４０，Ｙ＝０．２３，＝０．３８の組
成において、α＝１．０及びα＝１．５（ともにβ＝
１．００）とした場合の焼結性を示す線図である。FIG. 1 shows a composition of X = 0.40, Y = 0.23, 0.38, α = 1.0 and α = 1.5 (both β =
1.00) is a diagram showing the sinterability in the case of (1.00).
【図２】Ｘ＝０．４０，Ｙ＝０．２３，＝０．３８の組
成において、α＝１．０，β＝１．００とした場合と、
α＝１．５，β＝１．０２とした場合の焼結性を示す線
図である。FIG. 2 shows a case where α = 1.0 and β = 1.00 in a composition where X = 0.40, Y = 0.23, and 0.38,
FIG. 3 is a diagram illustrating sinterability when α = 1.5 and β = 1.02.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 41/187 ──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) H01L 41/187
Claims (2)
ｂＺｒＯ3−ＺＰｂＴｉＯ3を基本組成とし、一般記号Ａ
ＢＯ3で表されるペロブスカイト型の圧電磁器組成物で
あって、Ｘ，Ｙ，Ｚがそれぞれ、 ０．２０≦Ｘ≦０．６０ ０．１５≦Ｙ≦０．６０ ０．３０≦Ｚ≦０．６０ の範囲にあり、かつ、ＢサイトのＮｉ比率（α）が、 １＜α＜２ の範囲にあって、化学量論組成よりも過剰であるととも
に、ＡサイトのＰｂ比率（β）が、 １＜β≦１．０６ の範囲にあって、化学量論組成よりも過剰であることを
特徴とする圧電磁器組成物。1. XPbβ (Niα / 3Nb 2/3 ) O 3 -YP
bZrO 3 —ZPbTiO 3 as a basic composition and a general symbol A
A perovskite-type piezoelectric ceramic composition represented by BO 3 , wherein X, Y, and Z are each 0.20 ≦ X ≦ 0.60 0.15 ≦ Y ≦ 0.60 0.30 ≦ Z ≦ 0 .60, and the Ni ratio (α) of the B site is in the range of 1 <α <2, which is more than the stoichiometric composition, and the Pb ratio (β) of the A site is 1 <β ≦ 1.06, wherein the composition is in excess of the stoichiometric composition.
（ＳＳ）が、１０ｍ2／ｇ以上（ＳＳ≧１０ｍ2／ｇ）で
あることを特徴とする請求項１記載の圧電磁器組成物。2. The piezoelectric ceramic composition according to claim 1, wherein the specific surface area (SS) of the piezoelectric ceramic material powder before firing is 10 m 2 / g or more (SS ≧ 10 m 2 / g).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20901793A JP3345974B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20901793A JP3345974B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0745883A JPH0745883A (en) | 1995-02-14 |
| JP3345974B2 true JP3345974B2 (en) | 2002-11-18 |
Family
ID=16565894
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20901793A Expired - Fee Related JP3345974B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition |
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| JP3119101B2 (en) * | 1994-11-28 | 2000-12-18 | 株式会社村田製作所 | Piezoelectric ceramic composition |
| JP4506187B2 (en) * | 2004-02-09 | 2010-07-21 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric element |
| WO2006038389A1 (en) | 2004-10-01 | 2006-04-13 | Murata Manufacturing Co., Ltd | Piezoelectric porcelain composition and piezoelectric ceramic electronic component |
| WO2006046597A1 (en) * | 2004-10-26 | 2006-05-04 | Murata Manufacturing Co., Ltd | Conductive paste and stacked type piezoelectric ceramic component |
| JP4755919B2 (en) * | 2006-02-23 | 2011-08-24 | 富士フイルム株式会社 | Lead zirconate titanate composition, method for producing the same, piezoelectric body, and piezoelectric element |
| US8470211B2 (en) * | 2006-04-13 | 2013-06-25 | Agency For Science, Technology And Research | Ferroelectric ceramic material with a low sintering temperature |
| US9887344B2 (en) * | 2014-07-01 | 2018-02-06 | Seiko Epson Corporation | Piezoelectric element, piezoelectric actuator device, liquid ejecting head, liquid ejecting apparatus, and ultrasonic measuring apparatus |
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