JP2012254912A - Piezoelectric ceramic, and stacked piezoelectric device - Google Patents
Piezoelectric ceramic, and stacked piezoelectric device Download PDFInfo
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本発明は、圧電効果を有する圧電セラミックスおよび圧電セラミックスを用いた圧電素子に関する。 The present invention relates to a piezoelectric ceramic having a piezoelectric effect and a piezoelectric element using the piezoelectric ceramic.
近年、鉛を含まない圧電セラミックスの開発が進み、センサ、アクチュエータ、フィルタ等様々な用途への応用が検討されている。鉛を含まない圧電セラミックスとして、例えば、特許文献１が提案されている。 In recent years, development of piezoelectric ceramics that do not contain lead has progressed, and application to various uses such as sensors, actuators, filters, etc. has been studied. As a piezoelectric ceramic not containing lead, for example, Patent Document 1 has been proposed.
特許文献１には、主成分が一般式（Ｂａ１−ｘＣａｘ）ｙＴｉＯ３（ただし、０．０１≦ｘ≦０．２５、０．９６≦ｙ≦１．０４）で表され、鉛を含有せず、室温付近で歪み量の温度依存性が小さい圧電セラミックスが開示されている。 In Patent Document 1, the main component is represented by the general formula (Ba 1-x Ca x ) y TiO 3 (where 0.01 ≦ x ≦ 0.25, 0.96 ≦ y ≦ 1.04), and lead. There has been disclosed a piezoelectric ceramic that does not contain bismuth and has a small temperature dependence of the strain amount near room temperature.
また、特許文献１には、内部にＮｉ電極を有する積層型圧電素子も開示されている。ＮｉまたはＮｉ合金は、融点が１４００度程度と高く、チタン酸バリウム系の圧電セラミックスの焼成温度に近いため、内部電極として好適に使用でき、さらに貴金属に比較して低コストであるという特徴を有する。 Patent Document 1 also discloses a laminated piezoelectric element having a Ni electrode inside. Ni or Ni alloy has a high melting point of about 1400 ° C., and is close to the firing temperature of barium titanate-based piezoelectric ceramics. Therefore, Ni or Ni alloy can be suitably used as an internal electrode and has a feature that it is less expensive than noble metals. .
特許文献１に記載されている圧電セラミックス（Ｂａ１−ｘＣａｘ）ｙＴｉＯ３（ただし、０．０１≦ｘ≦０．２５、０．９６≦ｙ≦１．０４）において、ｙ＞１の組成域では圧電ｄ３１定数が１５０ｐＣ／Ｎ未満と低く、実用化には不十分であるという課題がある。一方、ｙ≦１の組成域では、焼成を試行したところ、焼成過程で異常粒成長を起こしやすく、均質な焼結体が得られず、十分な圧電特性が得られないという課題が見出された。 In the piezoelectric ceramics (Ba 1-x Ca x ) y TiO 3 described in Patent Document 1 (where 0.01 ≦ x ≦ 0.25, 0.96 ≦ y ≦ 1.04), y> 1 In the composition range, the piezoelectric d 31 constant is as low as less than 150 pC / N, which is insufficient for practical use. On the other hand, in the composition range of y ≦ 1, when firing was attempted, there was a problem that abnormal grain growth was likely to occur during the firing process, a homogeneous sintered body could not be obtained, and sufficient piezoelectric characteristics could not be obtained. It was.
また、特許文献１に記載の圧電セラミックスにＮｉあるいはＮｉ合金の内部電極を設け、積層型圧電素子を構成する場合、酸素分圧が１×１０−２Ｐａより低い還元雰囲気中で焼成することが必要となる。これは、ＮｉあるいはＮｉ合金を内部電極とした場合、大気あるいは酸素雰囲気中で焼成すると、ＮｉがＮｉＯに酸化されてしまうためである。しかしながら、特許文献１の圧電セラミックスを、還元雰囲気中で焼成したところ、還元反応が起こり、半導体化し、絶縁抵抗が低い圧電セラミックスとなるという課題が見出された。 Further, when an internal electrode of Ni or Ni alloy is provided on the piezoelectric ceramic described in Patent Document 1 to form a multilayer piezoelectric element, firing may be performed in a reducing atmosphere having an oxygen partial pressure lower than 1 × 10 −2 Pa. Necessary. This is because when Ni or Ni alloy is used as the internal electrode, Ni is oxidized to NiO when fired in the air or in an oxygen atmosphere. However, when the piezoelectric ceramics of Patent Document 1 are fired in a reducing atmosphere, a problem has been found in which a reduction reaction occurs to make a semiconductor and become a piezoelectric ceramic with low insulation resistance.
したがって、本発明は、圧電特性を保持するとともに、還元雰囲気中での焼成においても高い絶縁抵抗率を有する圧電セラミックスおよび積層型圧電素子を提供することを目的とする。 Accordingly, an object of the present invention is to provide a piezoelectric ceramic and a laminated piezoelectric element that retains piezoelectric characteristics and has high insulation resistivity even when firing in a reducing atmosphere.
本発明は、組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｔｉ１−ｙ）Ｏ３（２／３＋ｊ／３−ｙ／２）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、１．０００≦ｊ≦１．０４０）で表される主成分に対して、副成分としてＡｌを１．０００ｍｏｌ％以下（０を含まず）、含有することを特徴とする圧電セラミックスである。 The present invention is a composition formula (Ba 1-x, Ca x ) j (Li y, Ti 1-y) O 3 (2/3 + j / 3-y / 2) ( but, 0.005 ≦ x <0.100 , 0 <y ≦ 0.020, 1.000 ≦ j ≦ 1.040), containing 1.000 mol% or less (not including 0) of Al as a subcomponent. It is a characteristic piezoelectric ceramic.
また、本発明は、組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ−ｚ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、０＜ｚ≦０．００３、１．０００≦ｊ≦１．０４０）で表される主成分に対して、副成分としてＡｌを１．０００ｍｏｌ％以下（０を含まず）、含有することを特徴とする圧電セラミックスである。 Further, the present invention is a composition formula (Ba 1-x, Ca x ) j (Li y, Mn z, Ti 1-y-z) O 3 (2/3 + j / 3-y / 2-z / 3) ( However, subcomponents with respect to the main component represented by 0.005 ≦ x <0.100, 0 <y ≦ 0.020, 0 <z ≦ 0.003, 1.000 ≦ j ≦ 1.040) The piezoelectric ceramic is characterized by containing Al in an amount of 1.000 mol% or less (excluding 0).
また、上記の圧電セラミックスは、絶縁抵抗率が１．０００×１０９Ω・ｍ以上であることが好ましい。 The piezoelectric ceramic preferably has an insulation resistivity of 1.000 × 10 9 Ω · m or more.
また、上記の圧電セラミックスは、圧電歪定数ｄ３１が１５０ｐＣ／Ｎ以上であることが好ましい。 The piezoelectric ceramic preferably has a piezoelectric strain constant d 31 of 150 pC / N or more.
また、上記の圧電セラミックスは、０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１最大値が、前記圧電歪定数ｄ３１最小値の１．２５倍以内であることが好ましい。 In the piezoelectric ceramic, the maximum value of the piezoelectric strain constant d 31 in the temperature range of 0 ° C. or more and 50 ° C. or less is preferably within 1.25 times the minimum value of the piezoelectric strain constant d 31 .
また、上記の圧電セラミックスは、酸素分圧が１×１０−８Ｐａ以上１×１０−２Ｐａ以下の雰囲気中で焼成されていることが好ましい。 The piezoelectric ceramic is preferably fired in an atmosphere having an oxygen partial pressure of 1 × 10 −8 Pa to 1 × 10 −2 Pa.
また、本発明は、上記の圧電セラミックスからなる圧電層と、ＮｉまたはＮｉ合金よりなる内部電極層が交互に積層されていることを特徴とする積層型圧電素子である。 According to another aspect of the present invention, there is provided a multilayer piezoelectric element in which piezoelectric layers made of the above piezoelectric ceramics and internal electrode layers made of Ni or Ni alloy are alternately laminated.
本発明によれば、圧電特性を保持するとともに、還元雰囲気中での焼成においても高い絶縁抵抗率を有する圧電セラミックスおよび積層型圧電素子を提供することが可能となる。 According to the present invention, it is possible to provide piezoelectric ceramics and multilayer piezoelectric elements that retain piezoelectric characteristics and have high insulation resistivity even when firing in a reducing atmosphere.
本発明の実施の形態に係る圧電セラミックスについて説明する。本実施の形態では、まず、Ｂａ、Ｃａ、Ｔｉ、Ｌｉ、Ｍｎの化合物からなる粉末をそれぞれ用意し、Ａｌの化合物からなる粉末をＡｌ換算で１．０００ｍｏｌ％以下（０を含まず）含有するように所定量を秤量し、混合したものを出発原料とする。この出発原料の粉末の形態は、特に限定されず、後述する工程を経て得られる圧電セラミックスが、組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、０≦ｚ≦０．００３、１．０００≦ｊ≦１．０４０）で表される主成分に対して、副成分としてＡｌを１．０００ｍｏｌ％以下（０を含まず）であればよく、製造や保管の容易さや価格等を考慮して選択するのが好ましい。例えば、炭酸バリウム（ＢａＣＯ３）粉末、炭酸カルシウム（ＣａＣＯ３）粉末、二酸化チタン（ＴｉＯ２）粉末、炭酸リチウム（Ｌｉ２ＣＯ３）粉末、炭酸マンガン（ＭｎＣＯ３）粉末、酸化アルミニウム（Ａｌ２Ｏ３）粉末等を使用することが可能である。 The piezoelectric ceramic according to the embodiment of the present invention will be described. In this embodiment, first, powders made of a compound of Ba, Ca, Ti, Li, and Mn are respectively prepared, and the powder made of an Al compound is contained in an amount of 1.000 mol% or less (excluding 0) in terms of Al. Thus, a predetermined amount is weighed and mixed to obtain a starting material. The form of the powder of the starting material is not particularly limited, and the piezoelectric ceramic obtained through the steps described below is composed of a composition formula (Ba 1-x , Ca x ) j (Li y , Mn z , Ti 1-y ) O. 3 (2/3 + j / 3−y / 2−z / 3) (where 0.005 ≦ x <0.100, 0 <y ≦ 0.020, 0 ≦ z ≦ 0.003, 1.000 ≦ j With respect to the main component represented by .ltoreq.1.040), Al should be 1.000 mol% or less (not including 0) as a subcomponent, and is selected in consideration of ease of manufacture and storage, price, and the like. Is preferred. For example, barium carbonate (BaCO 3 ) powder, calcium carbonate (CaCO 3 ) powder, titanium dioxide (TiO 2 ) powder, lithium carbonate (Li 2 CO 3 ) powder, manganese carbonate (MnCO 3 ) powder, aluminum oxide (Al 2 O) 3 ) It is possible to use powder or the like.
Ｌｉ、Ａｌを含有することにより、還元雰囲気中における焼成時の圧電セラミックスの還元を防ぎ、絶縁抵抗率を１．０００×１０９Ω・ｍ以上とすることができる。 また、Ｍｎは含有しなくともよいが、含有することで絶縁抵抗率をさらに向上させることができる。 By containing Li and Al, reduction of the piezoelectric ceramic during firing in a reducing atmosphere can be prevented, and the insulation resistivity can be 1.000 × 10 9 Ω · m or more. Moreover, although Mn does not need to contain, an insulation resistivity can further be improved by containing.
また、組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、０≦ｚ≦０．００３、１．０００≦ｊ≦１．０４０）で表される主成分に対して、副成分としてＡｌを１．０００ｍｏｌ％以下（０を含まず）とする本実施の形態において、Ｌｉ、Ｍｎ、Ａｌを、上記の範囲とすることにより、以下の効果を奏する。すなわち、圧電歪定数ｄ３１を１５０ｐＣ／Ｎ以上、０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１最大値を、前記圧電歪定数ｄ３１最小値の１．２５倍以内とし、実使用環境における温度特性を良好にすることができる。 Further, the composition formula (Ba 1-x, Ca x ) j (Li y, Mn z, Ti 1-y) O 3 (2/3 + j / 3-y / 2-z / 3) ( however, 0.005 ≦ x <0.100, 0 <y ≦ 0.020, 0 ≦ z ≦ 0.003, 1.000 ≦ j ≦ 1.040), and 1.000 mol of Al as a subcomponent. In the present embodiment, which is set to not more than% (not including 0), the following effects can be obtained by setting Li, Mn, and Al in the above ranges. That is, the piezoelectric constant d 31 150 pC / N or more, the piezoelectric constant d 31 maximum in the temperature range of 0 ℃ above 50 ° C. or less, and within 1.25 times of the piezoelectric strain constant d 31 minimum, actual use The temperature characteristics in the environment can be improved.
組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｔｉ１−ｙ−ｚ）Ｏ３（２／３＋ｊ／３−ｙ／２）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、１．０００≦ｊ≦１．０４０）、または組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ−ｚ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）（ただし、０．００５≦ｘ＜０．１００、０＜ｙ≦０．０２０、０＜ｚ≦０．００３、１．０００≦ｊ≦１．０４０）で表される主成分において、１．０００≦ｊ≦１．０４０としたのは、ｊ＜１．０００の組成域では焼成過程で異常粒成長が生じ、均質なセラミックスが得られないためであり、一方でｊ＞１．０４０の組成域では焼結性が低下するため圧電特性が劣化してしまうという問題があるためである。 Composition formula (Ba 1-x , Ca x ) j (Li y , Ti 1-yz ) O 3 (2/3 + j / 3−y / 2) (where 0.005 ≦ x <0.100, 0 <Y ≦ 0.020, 1.000 ≦ j ≦ 1.040), or composition formula (Ba 1-x , Ca x ) j (Li y , Mn z , Ti 1-yz ) O 3 (2 / 3 + j / 3−y / 2−z / 3) (0.005 ≦ x <0.100, 0 <y ≦ 0.020, 0 <z ≦ 0.003, 1.000 ≦ j ≦ 1.040) ) In the composition range of j <1.000, abnormal grain growth occurs during the firing process, and a homogeneous ceramic cannot be obtained. On the other hand, in the composition range where j> 1.040, there is a problem in that the piezoelectric properties deteriorate because the sinterability decreases. .
前述の出発原料を加圧成形し、酸素分圧が１×１０−８Ｐａ以上１×１０−２Ｐａ以下の還元雰囲気中で焼成することにより本発明の圧電セラミックスを得ることができる。 The piezoelectric ceramic of the present invention can be obtained by pressure-molding the above starting material and firing in a reducing atmosphere having an oxygen partial pressure of 1 × 10 −8 Pa to 1 × 10 −2 Pa.
上述の製法により作製した圧電セラミックスは、絶縁抵抗率が１．０００×１０９Ω・ｍ以上、圧電歪定数ｄ３１が１５０ｐＣ／Ｎ以上、０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１最大値が、前記圧電歪定数ｄ３１最小値の１．２５倍以内となる。 The piezoelectric ceramic produced by the above-described manufacturing method has a piezoelectric strain constant d in a temperature range of 1.000 × 10 9 Ω · m or more, a piezoelectric strain constant d 31 of 150 pC / N or more, and 0 ° C. or more and 50 ° C. or less. The maximum value of 31 is within 1.25 times the minimum value of the piezoelectric strain constant d 31 .
なお、本実施の形態の圧電セラミックスを圧電層として、内部電極を設けた内部電極層を交互に積層した積層型圧電素子としてもよく、本実施の形態の圧電セラミックスは還元雰囲気中で焼成できるため、ＮｉまたはＮｉ合金を含有する内部電極を用いることができる。 The piezoelectric ceramic according to the present embodiment may be a piezoelectric layer, and a laminated piezoelectric element in which internal electrode layers having internal electrodes are alternately stacked may be used. The piezoelectric ceramic according to the present embodiment can be fired in a reducing atmosphere. An internal electrode containing Ni or Ni alloy can be used.
（実施例１）
本発明の実施例１における圧電セラミックスは、以下の製造工程により作製した。まず、組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ−ｚ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）において、ｊ＝１とし、ｘ、ｙ、ｚの各配合比が表１、表２、表３となるように、炭酸バリウム（ＢａＣＯ３）粉末、炭酸カルシウム（ＣａＣＯ３）粉末、二酸化チタン（ＴｉＯ２）粉末、炭酸リチウム（Ｌｉ２ＣＯ３）粉末、炭酸マンガン（ＭｎＣＯ３）粉末をそれぞれ秤量し、エタノールを加え、ボールミルにより２４時間の湿式混合を行った。
Example 1
The piezoelectric ceramic in Example 1 of the present invention was manufactured by the following manufacturing process. First, the composition formula (Ba 1-x, Ca x ) j (Li y, Mn z, Ti 1-y-z) O 3 in (2/3 + j / 3 -y / 2-z / 3), j = 1 And barium carbonate (BaCO 3 ) powder, calcium carbonate (CaCO 3 ) powder, titanium dioxide (TiO 2 ) powder, carbonic acid so that the mixing ratios of x, y, and z are as shown in Table 1, Table 2, and Table 3, respectively. Lithium (Li 2 CO 3 ) powder and manganese carbonate (MnCO 3 ) powder were weighed, ethanol was added, and wet mixing was performed for 24 hours with a ball mill.
得られた混合物を乾燥後、８００℃〜１１００℃で仮焼し、得られた仮焼粉末１００ｍｏｌに、酸化アルミニウム（Ａｌ２Ｏ３）粉末をａｍｏｌ、表１、表２、表３の配合比となるように添加し、エタノールを加え、ボールミルにより２４時間の湿式混合を行ったものを出発原料とした。仮焼温度は、各出発原料の組成により調整し、好適な仮焼温度でそれぞれ仮焼した。 The obtained mixture was dried and calcined at 800 ° C. to 1100 ° C., and 100 mol of the obtained calcined powder was mixed with amol, aluminum oxide (Al 2 O 3 ) powder in a mixing ratio of Table 1, Table 2, Table 3. The starting material was obtained by adding ethanol and performing wet mixing for 24 hours with a ball mill. The calcining temperature was adjusted according to the composition of each starting material, and calcined at a suitable calcining temperature.
得られた出発原料を乾燥させた後、ポリビニルアルコールをバインダーとして混合して造粒し、圧力１００ＭＰａの一軸加圧成形により、直径２０ｍｍ、厚さ５ｍｍの形状に成形した。この成形体を酸素分圧が１０−３Ｐａの雰囲気中、１１００℃〜１３５０℃で３時間焼成し、圧電セラミックスの円板状焼結体を作製した。焼成温度は、各出発原料の組成により調整し、好適な焼成温度によりそれぞれ焼成した。 After the obtained starting material was dried, it was granulated by mixing polyvinyl alcohol as a binder, and formed into a shape having a diameter of 20 mm and a thickness of 5 mm by uniaxial pressure molding with a pressure of 100 MPa. This compact was fired at 1100 ° C. to 1350 ° C. for 3 hours in an atmosphere having an oxygen partial pressure of 10 −3 Pa to produce a disk-shaped sintered body of piezoelectric ceramics. The firing temperature was adjusted according to the composition of each starting material, and fired at a suitable firing temperature.
前述の円板状焼結体をさらに１ｍｍの厚さに加工して円板状試料を作製し、その両面に銀電極を焼き付け、８０℃のシリコンオイル中で２ｋＶ／ｍｍの直流電界を３０分間印加することによって分極処理を行った。 The above disk-shaped sintered body is further processed to a thickness of 1 mm to prepare a disk-shaped sample, silver electrodes are baked on both sides thereof, and a direct electric field of 2 kV / mm is applied in silicon oil at 80 ° C for 30 minutes Polarization treatment was carried out by applying.
分極処理した前述の円板状試料を室温で２４時間放置することによって圧電特性を安定化させた後、デジタルエレクトロメータを用いた直流２端子法により絶縁抵抗率を測定した。 The above-mentioned disk-shaped sample subjected to the polarization treatment was allowed to stand at room temperature for 24 hours to stabilize the piezoelectric characteristics, and then the insulation resistivity was measured by a direct current two-terminal method using a digital electrometer.
さらに前述の円板状試料を切断加工して長さ１０ｍｍ、幅２ｍｍ、厚さ１ｍｍの矩形状試料を作製し、１ｋＶ／ｍｍの電界を印加したときの矩形状試料の歪み率から圧電歪定数ｄ３１を測定した。 Further, the above disk-shaped sample is cut to produce a rectangular sample having a length of 10 mm, a width of 2 mm, and a thickness of 1 mm, and the piezoelectric strain constant is determined from the strain rate of the rectangular sample when an electric field of 1 kV / mm is applied. It was measured d 31.
上述の方法により測定した２５℃における圧電歪定数ｄ３１、０℃以上５０℃以下の温度範囲における圧電ｄ３１定数の変化率（Δｄ３１）、および絶縁抵抗率の値を表１、表２、表３に示す。なお、圧電歪定数ｄ３１、Δｄ３１の欄に※が表示されている試料は、絶縁抵抗率が低いことから分極処理ができず、圧電ｄ３１定数が測定できなかった。 Tables 1 and 2 show values of piezoelectric strain constant d 31 at 25 ° C., change rate (Δd 31 ) of piezoelectric d 31 constant in a temperature range of 0 ° C. to 50 ° C., and insulation resistivity measured by the above method. Table 3 shows. Note that the samples with * in the columns of the piezoelectric strain constants d 31 and Δd 31 could not be subjected to polarization processing because of their low insulation resistivity, and the piezoelectric d 31 constant could not be measured.
表１、表２、表３に示すように、本発明の範囲内である実施例の各試料においては、絶縁抵抗率は１．０００×１０９Ω・ｍ以上、圧電歪定数ｄ３１は１５０ｐＣ／Ｎ以上、Δｄ３１は２５％以下（０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１最大値が、前記圧電歪定数ｄ３１最小値の１．２５倍以内）であった。比較例の各試料においては、いずれも絶縁抵抗率および圧電歪定数ｄ３１の値の同時に満足することができなかった。 As shown in Table 1, Table 2, and Table 3, in each sample of the examples within the scope of the present invention, the insulation resistivity is 1.000 × 10 9 Ω · m or more, and the piezoelectric strain constant d 31 is 150 pC. / N or more and Δd 31 was 25% or less (the maximum value of the piezoelectric strain constant d 31 in the temperature range of 0 ° C. or more and 50 ° C. or less was within 1.25 times the minimum value of the piezoelectric strain constant d 31 ). In each sample of the comparative example, none of the values of the insulation resistivity and the piezoelectric strain constant d 31 could be satisfied at the same time.
（実施例２）
本発明の実施例２における圧電セラミックスは、以下の製造工程により作製した。組成式（Ｂａ１−ｘ、Ｃａｘ）ｊ（Ｌｉｙ、Ｍｎｚ、Ｔｉ１−ｙ−ｚ）Ｏ３（２／３＋ｊ／３−ｙ／２−ｚ／３）において、ｘ＝０．０３０、ｙ＝０．００６、ｚ＝０．００１とし、ｊの各配合比を、０．９９０〜１．０５０となるように、炭酸バリウム（ＢａＣＯ３）粉末、炭酸カルシウム（ＣａＣＯ３）粉末、二酸化チタン（ＴｉＯ２）粉末、炭酸リチウム（Ｌｉ２ＣＯ３）粉末、炭酸マンガン（ＭｎＣＯ３）粉末をそれぞれ秤量し、エタノールを加え、ボールミルにより２４時間の湿式混合を行った。
(Example 2)
The piezoelectric ceramic in Example 2 of the present invention was manufactured by the following manufacturing process. The composition formula (Ba 1-x, Ca x ) j (Li y, Mn z, Ti 1-y-z) O 3 in (2/3 + j / 3 -y / 2-z / 3), x = 0.030 , Y = 0.006, z = 0.001, and the mixing ratio of j is 0.990 to 1.050, barium carbonate (BaCO 3 ) powder, calcium carbonate (CaCO 3 ) powder, dioxide dioxide Titanium (TiO 2 ) powder, lithium carbonate (Li 2 CO 3 ) powder, and manganese carbonate (MnCO 3 ) powder were weighed, ethanol was added, and wet mixing was performed for 24 hours with a ball mill.
得られた混合物を乾燥後、実施例１と同様に仮焼し、得られた仮焼粉末１００ｍｏｌに、酸化アルミニウム（Ａｌ２Ｏ３）粉末を０．３００ｍｏｌ添加し、エタノールを加え、ボールミルにより２４時間の湿式混合を行ったものを出発原料とした。 The obtained mixture was dried and calcined in the same manner as in Example 1. To 100 mol of the obtained calcined powder, 0.300 mol of aluminum oxide (Al 2 O 3 ) powder was added, ethanol was added, and the mixture was mixed with a ball mill. A material obtained by wet mixing for a time was used as a starting material.
得られた出発原料を乾燥させた後、実施例１で示したのと同様の方法で、成形、焼成し、圧電セラミックスの焼結体を作製後、焼結体表面について顕微鏡観察を行った。図１は、実施例２における焼結体表面の顕微鏡観察写真で、図１（ａ）は、ｊ＝０．９９０の場合、図１（ｂ）は、ｊ＝１．０００の場合、図１（ｃ）は、ｊ＝１．０４０の場合である。 After the obtained starting material was dried, it was molded and fired in the same manner as shown in Example 1 to produce a piezoelectric ceramic sintered body, and then the surface of the sintered body was observed with a microscope. FIG. 1 is a microscopic photograph of the surface of the sintered body in Example 2. FIG. 1 (a) shows a case where j = 0.990, FIG. 1 (b) shows a case where j = 1.000. (C) is a case where j = 1.040.
図１に示すように、ｊ≧１の領域においては粒径が均一な焼結体が得られるのに対して、ｊ＝０．９９０の試料では、局部的に粗大化した異常粒が生成し、均質な焼結体が得られなかった。 As shown in FIG. 1, in the region where j ≧ 1, a sintered body having a uniform particle size is obtained, whereas in the sample where j = 0.990, locally coarsened abnormal particles are generated. A homogeneous sintered body could not be obtained.
作製した焼結体について、実施例１と同様の方法で、絶縁抵抗率、圧電歪定数ｄ３１、およびΔｄ３１を測定した。 With respect to the produced sintered body, the insulation resistivity, the piezoelectric strain constant d 31 , and Δd 31 were measured in the same manner as in Example 1.
上述の方法により測定した２５℃における圧電歪定数ｄ３１、０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１の変化率（Δｄ３１）、および絶縁抵抗率の値を表４に示す。なお、ｊ＝０．９９０の試料は、均質な焼結体が得られなかったため、表４に測定値を示していない。 Table 4 shows the values of the piezoelectric strain constant d 31 at 25 ° C., the rate of change (Δd 31 ) of the piezoelectric strain constant d 31 in the temperature range from 0 ° C. to 50 ° C., and the insulation resistivity measured by the method described above. In addition, since a homogeneous sintered body was not obtained for the sample with j = 0.990, the measured values are not shown in Table 4.
表４に示すように、本発明の範囲内の各試料においては、絶縁抵抗率は１．０００×１０９Ω・ｍ以上、圧電歪定数ｄ３１は１５０ｐＣ／Ｎ以上、Δｄ３１は２５％以下（０℃以上５０℃以下の温度範囲における圧電歪定数ｄ３１最大値が、前記圧電歪定数ｄ３１最小値の１．２５倍以内）となった。比較例の各試料においては、いずれも絶縁抵抗率および圧電歪定数ｄ３１の値の同時に満足することができなかった。 As shown in Table 4, in each sample within the scope of the present invention, the insulation resistivity is 1.000 × 10 9 Ω · m or more, the piezoelectric strain constant d 31 is 150 pC / N or more, and Δd 31 is 25% or less. (The maximum value of the piezoelectric strain constant d 31 in the temperature range of 0 ° C. to 50 ° C. is within 1.25 times the minimum value of the piezoelectric strain constant d 31 ). In each sample of the comparative example, none of the values of the insulation resistivity and the piezoelectric strain constant d 31 could be satisfied at the same time.
以上説明したとおり、本発明によれば、圧電特性を保持するとともに、還元雰囲気中での焼成においても高い絶縁抵抗率を有する圧電セラミックスおよび積層型圧電素子を提供することが可能となった。 As described above, according to the present invention, it is possible to provide piezoelectric ceramics and multilayer piezoelectric elements that retain piezoelectric characteristics and have high insulation resistivity even in firing in a reducing atmosphere.
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