JP5550401B2 - Piezoelectric ceramic and piezoelectric element using the same - Google Patents
Piezoelectric ceramic and piezoelectric element using the same Download PDFInfo
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Description
本発明は、圧電磁器に関し、例えば、位置決め、光学装置の光路長制御、流量制御用バルブ、ポンプ、超音波モータ、エンジンの燃料噴射装置、自動車等のブレーキ装置、インクジェットプリンターのインク吐出ヘッド等に使用されるアクチュエータなどに好適に用いられる圧電磁器および圧電素子に関するものである。 The present invention relates to a piezoelectric ceramic, for example, positioning, optical path length control of an optical device, flow control valve, pump, ultrasonic motor, engine fuel injection device, automobile brake device, inkjet printer ink discharge head, etc. The present invention relates to a piezoelectric ceramic and a piezoelectric element which are preferably used for an actuator used.
圧電磁器を利用した製品としては、例えば、フィルタ、位置決め、光学装置の光路長制御、流量制御用バルブ、超音波モータあるいは自動車のブレーキ装置等に使用されるアクチュエータなどがある。 Examples of products using piezoelectric ceramics include filters, positioning, optical path length control of optical devices, flow rate control valves, ultrasonic motors, actuators used in automobile brake devices, and the like.
従来、アクチュエータとしては、圧電性の高い、ＰＺＴ（チタン酸ジルコン酸鉛）系材料やＰＴ（チタン酸鉛）系材料が使用されていた。しかしながら、ＰＺＴ系材料やＰＴ系材料は、鉛を約６０質量％の割合で含有しているため、酸性雨により鉛の溶出が起こり、環境汚染を招く危険性が指摘されている。そこで、鉛を主成分としない圧電材料へ高い期待が寄せられている。 Conventionally, PZT (lead zirconate titanate) -based materials and PT (lead titanate) -based materials having high piezoelectricity have been used as actuators. However, since PZT-based materials and PT-based materials contain lead in a proportion of about 60% by mass, the elution of lead due to acid rain has been pointed out as a risk of environmental pollution. Therefore, high expectations are placed on piezoelectric materials that do not contain lead as a main component.
鉛を含有しない圧電磁器としてはニオブ酸アルカリ系ペロブスカイトが知られている。｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３、ただし、０≦ｘ≦０．２、０≦ｙ≦１、０≦ｚ≦０．４、０≦ｗ≦０．２、ｘ＋ｚ＋ｗ＞０、で表される一般式１ｍｏｌに対して周期律表における２〜１５族に属する金属元素、半金属元素、遷移金属元素、貴金属元素、及びアルカリ土類金属元素から選ばれるいずれか一種以上の添加元素を０．０００１〜０．１５ｍｏｌ含有する多結晶体のセラミックスであって、該多結晶体を構成する各結晶粒の特定の結晶面が配向していることを特徴とする結晶配向セラミックスが提案されている（例えば、特許文献１を参照。）。この結晶配向セラミックスでは、板状や柱状などの異方形状粒子を配向させて成形した後、焼成することにより結晶が配向させられている。 As a piezoelectric ceramic not containing lead, an alkali niobate perovskite is known. {Lix (K1-yNay) 1-x} (Nb1-z-wTazSbw) O3, where 0≤x≤0.2, 0≤y≤1, 0≤z≤0.4, 0≤w≤0. 2, any of metal elements belonging to group 2 to 15 in the periodic table, metalloid elements, transition metal elements, noble metal elements, and alkaline earth metal elements with respect to 1 mol of the general formula represented by x + z + w> 0 A polycrystalline ceramic containing 0.0001 to 0.15 mol of one or more additive elements, characterized in that specific crystal planes of crystal grains constituting the polycrystalline body are oriented. Crystal-oriented ceramics have been proposed (see, for example, Patent Document 1). In this crystal-oriented ceramic, crystals are oriented by orienting anisotropically shaped particles such as plates and columns and then firing them.
しかしながら、ニオブ酸アルカリ系ペロブスカイトだけのでは圧電定数が低いという問題があり、特許文献１に記載の圧電磁器は、圧電定数を向上させるため前述のような複雑な作製プロセスを用いなければならず、安定して製造できないという問題があった。
However, there is a problem that only the alkali niobate-based perovskite has a low piezoelectric constant, and the piezoelectric ceramic described in
本発明は、かかる事情に鑑みて、圧電定数の大きな圧電磁器およびそれを用いた圧電素子を提供することを目的とする。 In view of such circumstances, an object of the present invention is to provide a piezoelectric ceramic having a large piezoelectric constant and a piezoelectric element using the piezoelectric ceramic.
本発明の圧電磁器は、組成式を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分と、該成分１００質量部に対して、ＭｎＯ２換算で０．０１〜０．５質量部のＭｎ成分とを合量で９９質量％以上含有することを特徴とする。
The piezoelectric ceramic of the present invention has a composition formula of (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2/3 ) O 3 , 0.46 ≦ x ≦ 0.56, 0.045 ≦ y ≦ 0.060, and α and β were expressed as (α, β). When α and β are point A (0.0005, 0), point B (0.005, 0), point C (0.005, 0.005), point D (0, 0.0125) and point and component is in the range connecting the E (0,0.001), relative to said components 100 parts by weight of 99 weight in total and the Mn component of 0.01 to 0.5 parts by M nO 2 terms % Or more .
また、α＝０、０．００７５≦β≦０．０１２５であることが好ましい。 Moreover, it is preferable that α = 0 and 0.0075 ≦ β ≦ 0.0125.
また、本発明の圧電素子は、前記圧電磁器が対向面を有し、該対向面に、互いを対向させて配置した一対の電極を備えることを特徴とする。 In the piezoelectric element of the present invention, the piezoelectric ceramic has a facing surface, and the facing surface includes a pair of electrodes arranged to face each other.
本発明の圧電磁器によれば、組成式を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分と、該成分１００質量部に対して、ＭｎＯ２換算で０．０１〜０．５質量部のＭｎ成分とを合量で９９質量％以上含有することにより、圧電定数を高くできる。
According to the piezoelectric ceramic of the present invention, the composition formula is (1−α−β) {(K 1−x Na x ) 1−y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa When expressed as (Mg 1/3 Nb 2/3 ) O 3 , 0.46 ≦ x ≦ 0.56, 0.045 ≦ y ≦ 0.060, and α and β are (α, β) and When α and β are expressed, point A (0.0005, 0), point B (0.005, 0), point C (0.005, 0.005), point D (0, 0.0125) a component and in the range connecting the point E (0,0.001), relative to said components 100 parts by weight in total and the Mn component of 0.01 to 0.5 parts by M nO 2 terms By containing 99% by mass or more , the piezoelectric constant can be increased.
また、α＝０、０．００７５≦β≦０．０１２５である場合、１０００℃以下の低い焼成温度でも焼成可能となる。 In addition, when α = 0 and 0.0075 ≦ β ≦ 0.0125, firing is possible even at a low firing temperature of 1000 ° C. or less.
また、本発明の圧電素子は、前記圧電磁器が対向面を有し、該対向面に、互いを対向させて配置した一対の電極を備えることにより、高性能なアクチュエータやセンサが得られる。 In the piezoelectric element of the present invention, the piezoelectric ceramic has a facing surface, and a pair of electrodes disposed on the facing surface so as to face each other provides a high-performance actuator or sensor.
組成式を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分１００質量部に対して、ＭｎをＭｎＯ２換算で０．０１〜０．５質量部含有している。 The composition formula is (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2/3 ) When expressed as O 3 , 0.46 ≦ x ≦ 0.56 and 0.045 ≦ y ≦ 0.060, and when α and β are expressed as (α, β), α and β are Point A (0.0005, 0), Point B (0.005, 0), Point C (0.005, 0.005), Point D (0, 0.0125) and Point E (0, 0.001) Mn is contained in an amount of 0.01 to 0.5 parts by mass in terms of MnO 2 with respect to 100 parts by mass of the component that is within the range of).
本発明の圧電磁器は、このような組成であることにより、比較的低い温度での焼成でも安定して焼成可能な大きな結晶粒子を含む圧電磁器が得られ、安定して安定して製造することができる。 The piezoelectric ceramic according to the present invention has such a composition, so that a piezoelectric ceramic containing large crystal particles that can be stably fired even when fired at a relatively low temperature can be obtained and stably produced. Can do.
圧電磁器の主な成分である｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３は、ペロブスカイト構造をもつものである。また、その組成で作製した圧電磁器は、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０の範囲で圧電定数の高くなり、この比率はいわゆるＭＰＢ（Morphotoropic Phase Boundary）領域となる比率である。ただし、まだ正方晶が主体の結晶相であり、この系にＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３あるいはＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３を導入することに結晶相は立方晶に近づいていく。その間の導入量では、混合相の結晶相を示し、ＭＰＢを形成している。 {(K 1-x Na x ) 1-y Li y } NbO 3 which is a main component of the piezoelectric ceramic has a perovskite structure. In addition, a piezoelectric ceramic manufactured with the composition has a high piezoelectric constant in the range of 0.46 ≦ x ≦ 0.56 and 0.045 ≦ y ≦ 0.060, and this ratio is a so-called MPB (Morphotoropic Phase Boundary) region. This is the ratio. However, it is still a crystal phase mainly composed of tetragonal crystals, and the crystal phase is obtained by introducing Bi (Mg 2/3 Nb 1/3 ) O 3 or Ba (Mg 1/3 Nb 2/3 ) O 3 into this system. Approaches a cubic crystal. The amount introduced during that time indicates a mixed crystal phase and forms MPB.
また、上述の組成式でｙが０．０４５以上であることにより、圧電磁器の焼結性が高くなり、圧電定数を高くすることができる。また、ｙが０．０６０以下であることにより圧電定数を高くすることができる。 Moreover, when y is 0.045 or more in the above composition formula, the sinterability of the piezoelectric ceramic is increased, and the piezoelectric constant can be increased. Further, when y is 0.060 or less, the piezoelectric constant can be increased.
そして、さらに、ニオブ酸アルカリ系ペロブスカイトにＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３あるいはＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３で表せる複合ペロブスカイトを添加することで圧電定数を高くすることができる。 Further, by adding a composite perovskite expressed by Bi (Mg 2/3 Nb 1/3 ) O 3 or Ba (Mg 1/3 Nb 2/3 ) O 3 to the alkali niobate-based perovskite, the piezoelectric constant is increased. can do.
Ｂｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３の添加量αは、Ｂｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３を単独で添加する場合は。０．０００５≦α≦０．００５であることで圧電定数が高くなる。Ｂａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３の添加量βは、Ｂａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３を単独で添加する場合は。０．００１０≦β≦０．０１２５であることで圧電定数が高くなる。添加する際の結晶相の変化の傾向は類似しており、これらを両方添加する場合は、それらが合わさって作用すると考えられ、圧電定数が高くなるαおよびβの範囲は、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲となる。 It is Bi (Mg 2/3 Nb 1/3) amount of O 3 alpha, when adding Bi (Mg 2/3 Nb 1/3) O 3 alone. The piezoelectric constant increases when 0.0005 ≦ α ≦ 0.005. The Ba (Mg 1/3 Nb 2/3) amount of O 3 beta, when adding Ba (Mg 1/3 Nb 2/3) O 3 alone. The piezoelectric constant becomes high when 0.0010 ≦ β ≦ 0.0125. The tendency of the change of the crystal phase upon addition is similar, and when both of these are added, it is considered that they act together, and the range of α and β in which the piezoelectric constant increases is α and β ( When α and β are expressed, α and β are point A (0.0005, 0), point B (0.005, 0), point C (0.005, 0.005), point D (0 , 0.0125) and the point E (0, 0.001).
また、上述の組成式（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３で表せる成分１００質量部に対して、ＭｎＯ２は０．０１〜０．５０質量部含有させることにより圧電磁器が緻密になり、圧電定数も高くなる。 In addition, the above-described composition formula (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2/3 ) By adding 0.01 to 0.50 parts by mass of MnO 2 with respect to 100 parts by mass of the component expressed by O 3 , the piezoelectric ceramic becomes dense and the piezoelectric constant increases.
また、この主な成分であるニオブ酸アルカリ系ペロブスカイトに対して、Ｂａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３を添加した際に、焼結体の粒子が大きく成長することを見出した。このような組成では、安定した焼成が可能であり、また焼成温度も低くできる。 Further, it has been found that when Ba (Mg 1/3 Nb 2/3 ) O 3 is added to the alkali niobate-based perovskite which is the main component, the particles of the sintered body grow greatly. With such a composition, stable firing is possible and the firing temperature can be lowered.
ニオブ酸アルカリ系ペロブスカイトの粒子成長には、主成分のアルカリ金属元素、特に焼成時のＬｉの挙動が大きく影響している。このことは、ニオブ酸アルカリ系ペロブスカイト中のＬｉ量を増加させることにより粒成長を促進させることからも分かる。しかし、Ｌｉの比率を増やすだけでは、粒子径はあまり大きくならず、緻密な焼結体も得られなかった。 The behavior of alkali metal elements as a main component, particularly Li during firing, has a great influence on the particle growth of alkali niobate-based perovskites. This can be understood from the fact that the grain growth is promoted by increasing the amount of Li in the alkali niobate-based perovskite. However, simply increasing the Li ratio did not increase the particle size, and a dense sintered body could not be obtained.
通常、セラミックスでは結晶粒子が物質拡散により粒成長し焼結している。結晶粒子の径は、通常の圧電セラミックスで１０μｍ以下である。特許文献１に記載されているように、たとえ粒子径を数十μｍオーダーへ粒成長させることができても粒子間に大きな１０〜２０μｍの以上の空孔が形成され、緻密体を作製することができなかった。これに対して、本発明の圧電磁器では、吸水率０．１％以下の緻密体が作成でき、上述のような大きな空孔も見られない。
Usually, in ceramics, crystal grains grow and sinter due to material diffusion. The diameter of the crystal particles is 10 μm or less with ordinary piezoelectric ceramics. As described in
すなわち、上述の組成で、α＝０、０．００７５≦β≦０．０１２５であることにより、上述の液相生成による粒子成長の機構が適切に起こり、１００μｍ以上の大きな粒子が生成でき、焼成温度も１０００℃以下で安定して製造できる。このような効果を得られる理由は以下のように考えられる。まず、焼成において、上述の組成で作製した合成粉末中に含まれるアルカリ金属元素のＬｉが低温で液相を生成するが、その際にＭｇが存在するため、より低温で液相が生成される。この液相が成形体中で局所的に発生し、その中で結晶核が形成される。また、この組成では物質拡散が非常に早く、形成された結晶核を元にして結晶粒子が急激に成長する。その際、成長を始めた粒子の外周部にＬｉや遷移元素の液相成分が偏在し、粒子外周部の液相を介して周囲の小粒子を取り込み大きな粒子が形成
されると考えられる。また、大きな粒子周辺部の液相部で小粒子を取り込み、非常に急激な粒子成長を起こすため一気に大きな粒子が生成されるため粒子間に空隙が発生しないと考えられる。このような粒子は９０μｍ以上の大きさになる。αが０．００３０以上、βが０．００５０以下、あるいはβが０．０２００以上では、結晶粒子は１０μｍ程度、あるいはそれ以下の粒径となる。
That is, with the above composition, α = 0, 0.0075 ≦ β ≦ 0.0125, the above-described mechanism of particle growth by liquid phase generation occurs appropriately, and large particles of 100 μm or more can be generated, The temperature can be stably produced at 1000 ° C. or less. The reason why such an effect can be obtained is considered as follows. First, in firing, the alkali metal Li contained in the synthetic powder produced with the above composition generates a liquid phase at a low temperature, but since Mg exists at that time, the liquid phase is generated at a lower temperature. . This liquid phase is locally generated in the compact and crystal nuclei are formed therein. Also, with this composition, material diffusion is very fast, and crystal grains grow rapidly based on the formed crystal nuclei. At that time, it is considered that the liquid phase components of Li and transition elements are unevenly distributed in the outer peripheral portion of the particle that has started to grow, and large particles are formed by taking in the surrounding small particles through the liquid phase in the outer peripheral portion of the particle. In addition, it is considered that voids are not generated between the particles because small particles are taken up in the liquid phase portion around the large particles and cause very rapid particle growth, so that large particles are generated at a stretch. Such particles have a size of 90 μm or more. When α is 0.0030 or more, β is 0.0050 or less, or β is 0.0200 or more, the crystal particles have a particle size of about 10 μm or less.
本発明の圧電磁器は、粉砕時のＺｒＯ２ボールからＺｒ等が混入する場合もあるが、微量であれば特性上問題ない。本発明の圧電磁器は、組成式を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分１００質量部に対して、ＭｎをＭｎＯ２換算で０．０１〜０．５質量部加えた組成が９９質量％以上を占め、それ以外の組成は１％質量未満、より好ましくは０．５％質量未満である。 In the piezoelectric ceramic according to the present invention, Zr or the like may be mixed from the ZrO 2 ball at the time of pulverization. The piezoelectric ceramic of the present invention has a composition formula of (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2/3 ) O 3 , 0.46 ≦ x ≦ 0.56, 0.045 ≦ y ≦ 0.060, and α and β were expressed as (α, β). When α and β are point A (0.0005, 0), point B (0.005, 0), point C (0.005, 0.005), point D (0, 0.0125) and point The composition obtained by adding 0.01 to 0.5 parts by mass of Mn in terms of MnO 2 accounts for 99% by mass or more with respect to 100 parts by mass of the component within the range connecting E (0, 0.001). Is less than 1% by weight, more preferably less than 0.5% by weight.
本発明の組成を有する圧電磁器は、例えば、原料として、Ｎａ２ＣＯ３、Ｋ２ＣＯ３、Ｌｉ２ＣＯ３、Ｎｂ２Ｏ５、ＢａＣＯ３ＭｇＣＯ３およびＭｎＯ２からなる各種酸化物あるいは塩を用いることができる。原料はこれに限定されず、焼成により酸化物を生成する炭酸塩、硝酸塩等の金属塩を用いても良い。 The piezoelectric ceramic having the composition of the present invention includes, for example, various oxides or salts made of Na 2 CO 3 , K 2 CO 3 , Li 2 CO 3 , Nb 2 O 5 , BaCO 3 MgCO 3 and MnO 2 as raw materials. Can be used. A raw material is not limited to this, You may use metal salts, such as carbonate and nitrate which produce | generate an oxide by baking.
これらの原料を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分１００質量部に対して、ＭｎをＭｎＯ２換算で０．１〜０．５質量部となるように秤量し、混合後の平均粒度分布（Ｄ５０）が０．３〜１μｍの範囲になるように粉砕する。この混合物を８５０〜１０００℃で仮焼し、仮焼後の平均粒度分布（Ｄ５０）が０．３〜１μｍの範囲になるように粉砕し、再度所定の有機バインダを加え湿式混合し造粒する。 (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2 / 3 ) When expressed as O 3 , 0.46 ≦ x ≦ 0.56, 0.045 ≦ y ≦ 0.060, and when α and β are expressed as (α, β), α and β are , Point A (0.0005, 0), point B (0.005, 0), point C (0.005, 0.005), point D (0, 0.0125) and point E (0, 0. Mn is weighed so as to be 0.1 to 0.5 parts by mass in terms of MnO 2 with respect to 100 parts by mass of the component within the range connecting 001), and the average particle size distribution (D 50 ) after mixing is 0. .Crush to 3 to 1 μm. This mixture is calcined at 850 to 1000 ° C., pulverized so that the average particle size distribution (D 50 ) after calcining is in the range of 0.3 to 1 μm, and a predetermined organic binder is added again to perform wet mixing and granulation. To do.
このようにして得られた粉体を、公知のプレス成形等により所定形状に成形し、大気中等の酸化性雰囲気において９５０〜１０５０℃の温度範囲で２〜５時間焼成し、本発明の組成を有する圧電磁器が得られる。 The powder thus obtained is molded into a predetermined shape by a known press molding or the like, and calcined at a temperature range of 950 to 1050 ° C. for 2 to 5 hours in an oxidizing atmosphere such as in the atmosphere to obtain the composition of the present invention. The piezoelectric ceramic which has is obtained.
図１（ａ）に、本発明の圧電素子の実施形態の一例であるアクチュエータの概略縦断面図を示す。このアクチュエータは、上述の組成の圧電磁器からなる２つの圧電基体１が積層されている。各圧電基体１の一方の主面に電極２が形成され、他方の主面には電極３が形成されている。アクチュエータ内で電極２、３は積層方向に交互に形成されている。分極は各圧電基体１の主面に垂直に電極３から電極２の方向に施してある。
FIG. 1A is a schematic longitudinal sectional view of an actuator which is an example of an embodiment of a piezoelectric element of the present invention. In this actuator, two
このようなアクチュエータは、上述のように作製した単結晶体の圧電磁器の結晶配向を調べて、その方向に合わせて単結晶体を切断し、分極を施して圧電基体１を作製し、電極２、３と接着して積層することにより作製できる。このようなアクチュエータは、電極２と電極３との間に電圧を加えることにより圧電基体１がｄ３３方向に変位する、すなわち、厚みが増える方向に変形し、アクチュエータとして働く。
Such an actuator examines the crystal orientation of a single crystal piezoelectric ceramic produced as described above, cuts the single crystal in accordance with the direction, applies polarization to produce the
図１（ｂ）に、本発明の圧電素子の実施形態の一例である圧力センサ素子の概略斜視図を示す。この圧力センサは、上述の組成の圧電磁器からなる圧電基体１１の対向する一対
の主面に、それぞれに電極１２、１３を形成され、互いに対向させた一対の電極１２、１３を備えている。また、分極は主面と垂直な方向に施してある。このような圧力センサでは、主面間に加わる圧力により、各主面に電荷が生じるため、この電荷を測定することにより、主面間に加わっている圧力を測定することができる。
FIG. 1B shows a schematic perspective view of a pressure sensor element which is an example of an embodiment of the piezoelectric element of the present invention. This pressure sensor includes a pair of
出発原料として純度９９．９％のＮａ２ＣＯ３粉末、Ｋ２ＣＯ３粉末、Ｌｉ２ＣＯ３粉末、Ｎｂ２Ｏ５粉末、ＢａＣＯ３粉末、ＭｇＣＯ３粉末およびＭｎＯ２粉末を準備した。これらの粉末を、（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３のｘ、ｙ、αおよびβを表１に示す量にした成分１００質量部に対して、ＭｎをＭｎＯ２換算で表１に示す量になるように秤量混合した。 As starting materials, Na 2 CO 3 powder, K 2 CO 3 powder, Li 2 CO 3 powder, Nb 2 O 5 powder, BaCO 3 powder, MgCO 3 powder and MnO 2 powder having a purity of 99.9% were prepared. These powders were transformed into (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2 / 3 ) Mn was weighed and mixed to 100 parts by mass of components having x, y, α, and β of O 3 in the amounts shown in Table 1 so as to have the amounts shown in Table 1 in terms of MnO 2 .
秤量した原料粉末を、純度９９．９％のＺｒＯ２ボール、イオン交換水と共に５００ｍｌポリポットに投入し、１６時間回転ミルで混合した。 The weighed raw material powder was put into a 500 ml polypot together with ZrO 2 balls having a purity of 99.9% and ion-exchanged water, and mixed in a rotary mill for 16 hours.
混合後のスラリーを大気中で乾燥し、＃４０メッシュを通し、その後、大気中で９５０℃、３時間保持して仮焼し、この合成粉末を純度９９．９％のＺｒＯ２ボールとイオン交換水と共に５００ｍｌポリポットに投入し、２０時間粉砕して粉末を得た。 The mixed slurry is dried in the air, passed through a # 40 mesh, and then calcined at 950 ° C. for 3 hours in the air, and this synthetic powder is ion exchanged with a ZrO 2 ball having a purity of 99.9%. It was put into a 500 ml polypot together with water and pulverized for 20 hours to obtain a powder.
この粉末に適量の有機バインダを添加して造粒し、金型プレスで１５０ＭＰａの圧力で成形し、大気中において、９５０〜１０５０℃（表２の試料については焼成温度を記した）でキープ時間を３時間とし、その前後の昇温温度・降温速度を３００℃／時間とするプロファイルで本焼成し、直径１０ｍｍ、厚み３ｍｍの円柱状の圧電磁器を得た。 An appropriate amount of an organic binder is added to this powder, granulated, and molded with a mold press at a pressure of 150 MPa. Was fired with a profile in which the temperature increase / decrease rate before and after that was 300 ° C./hour to obtain a cylindrical piezoelectric ceramic having a diameter of 10 mm and a thickness of 3 mm.
粒子径は、断面を鏡面研磨加工して、その後、塩酸と硝酸との混合酸溶液でエッティング処理を行なった後、走査型電子顕微鏡の観察で粒子径を測定した。 The particle size was measured by observing with a scanning electron microscope after mirror-polishing the cross section and performing an etching treatment with a mixed acid solution of hydrochloric acid and nitric acid.
次に、圧電磁器を厚み２ｍｍに研磨した後、両主面（円柱の上下面）にＡｇ電極を形成して、２００℃で分極処理を行い、圧電素子を作製した。得られた圧電素子はｄ３３メーターで圧電ｄ３３定数を測定した。さらに、圧電素子を恒温槽に入れ、温度を変化させながら静電容量を測定し、静電容量が極大かつ最大となる温度をキュリーＴｃ温度とした。 Next, after polishing the piezoelectric ceramic to a thickness of 2 mm, Ag electrodes were formed on both main surfaces (the upper and lower surfaces of the cylinder), and a polarization treatment was performed at 200 ° C. to produce a piezoelectric element. The resulting piezoelectric elements was measured piezoelectric constant d 33 with d 33 meter. Furthermore, the piezoelectric element was placed in a thermostatic chamber, the capacitance was measured while changing the temperature, and the temperature at which the capacitance reached the maximum and maximum was taken as the Curie Tc temperature.
圧電特性は、｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３組成のｘの値はｘ＝０．５０の試料Ｎｏ．４の圧電定数が最も高く、ｘ＝０．５０から外れるにしたがって、圧電定数は小さくなっていった。これは、ニオブ酸アルカリ系ペロブスカイト単体の組成の場合と同様に、この組成領域でＭＰＢとなっていることによる。 Piezoelectric characteristics are as follows. The x value of the {(K 1-x Na x ) 1-y Li y } NbO 3 composition is x = 0.50. The piezoelectric constant of 4 was the highest, and the piezoelectric constant became smaller as it deviated from x = 0.50. This is due to the fact that it is MPB in this composition region as in the case of the composition of the alkali niobate perovskite alone.
ｙについてもｙ＝０．０５の試料Ｎｏ．４の圧電定数が最も高く、ｙ＝０．０５から外れるにしたがって、圧電定数は小さくなっていった。これは、ニオブ酸アルカリ系ペロブスカイト単体の組成の場合と同様に、この組成領域でＭＰＢとなっていることによる。 Also for y, sample No. 8 with y = 0.05. The piezoelectric constant of 4 was the highest, and the piezoelectric constant decreased as it deviated from y = 0.05. This is due to the fact that it is MPB in this composition region as in the case of the composition of the alkali niobate perovskite alone.
組成式を（１−α−β）｛（Ｋ１−ｘＮａｘ）１−ｙＬｉｙ｝ＮｂＯ３＋αＢｉ（Ｍｇ２／３Ｎｂ１／３）Ｏ３＋βＢａ（Ｍｇ１／３Ｎｂ２／３）Ｏ３と表したとき、０．４６≦ｘ≦０．５６、０．０４５≦ｙ≦０．０６０であるとともに、αおよびβを（α、β）と表したとき、αおよびβが、点Ａ（０．０００５、０）、点Ｂ（０．００５、０）、点Ｃ（０．００５、０．００５）、点Ｄ（０、０．０１２５）および点Ｅ（０、０．００１）を結ぶ範囲内である成分１００質量部に対して、ＭｎをＭｎＯ２換算で０．０１〜０．５質量部含有する本発明の範囲の試料は圧電定数ｄ３３が１６４以上と大きくなった。
The composition formula is (1-α-β) {(K 1-x Na x ) 1-y Li y } NbO 3 + αBi (Mg 2/3 Nb 1/3 ) O 3 + βBa (Mg 1/3 Nb 2/3 ) When expressed as O 3 , 0.46 ≦ x ≦ 0.56 and 0.045 ≦ y ≦ 0.060, and when α and β are expressed as (α, β), α and β are Point A (0.0005, 0), Point B (0.005, 0), Point C (0.005, 0.005), Point D (0, 0.0125) and Point E (0, 0.001) ) with respect to 100 parts by weight of component is within the range connecting, samples of the scope of the present invention containing 0.01 to 0.5 parts by mass of Mn in MnO 2 terms of as large as the piezoelectric constant d 33 is 16 4 or more It was.
上述の範囲の中でさらにα＝０、０．００７５≦β≦０．０１２５であるは粒子径が１００μｍ以上と大きく、焼成温度を１０００℃以下と低くすることができた。 Within the above range, α = 0, 0.0075 ≦ β ≦ 0.0125, the particle diameter was as large as 100 μm or more, and the firing temperature could be lowered to 1000 ° C. or less.
また、実施例で作製した試料を、蛍光Ｘ線分析装置で組成分析した。その結果、各試料の磁器の組成は、調合した原料組成と同じであった。 In addition, the composition of the sample prepared in the example was analyzed with a fluorescent X-ray analyzer. As a result, the composition of the porcelain of each sample was the same as the prepared raw material composition.
１、１１・・・圧電基体（圧電磁器）
２、３、１２、１３・・・電極
Ｐ・・・分極方向
1, 11 ... Piezoelectric substrate (piezoelectric ceramic)
2, 3, 12, 13 ... electrode P ... polarization direction
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