JP2006256925A - Sintering aid for piezoelectric ceramic and piezoelectric ceramic - Google Patents
Sintering aid for piezoelectric ceramic and piezoelectric ceramic Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 11
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は圧電セラミックス用焼結助剤および圧電セラミックスに関する。 The present invention relates to a sintering aid for piezoelectric ceramics and piezoelectric ceramics.
圧電トランスや超音波モータ等、圧電材料を用いたデバイスが種々開発されている。例えば、圧電トランスは、駆動部に入力した電気エネルギーを機械的振動エネルギーに変換し、発電部において再び電気エネルギーに変換することによって、入力電圧の昇圧または降圧を行うデバイスである。この圧電トランスは、近時、広く表示デバイスとして用いられるようになった液晶表示装置のバックライト（冷陰極管）用のインバータとして用いられている。 Various devices using piezoelectric materials such as piezoelectric transformers and ultrasonic motors have been developed. For example, a piezoelectric transformer is a device that boosts or lowers an input voltage by converting electrical energy input to a drive unit into mechanical vibration energy and converting it back into electrical energy in a power generation unit. This piezoelectric transformer has recently been used as an inverter for a backlight (cold cathode tube) of a liquid crystal display device that has come to be widely used as a display device.
圧電トランスには、一般的にジルコン酸チタン酸鉛（ＰＺＴ）系の圧電セラミックスが用いられているが、ＰＺＴ系セラミックスは高温で焼成すると、鉛成分が蒸発して組成がずれ、所望の特性を得られなくなることや、蒸発する鉛による環境汚染が問題となるために、できるだけ低温で焼成を行うことが望まれており、そのために種々の焼結助剤が検討されている（例えば、特許文献１参照）。 Piezoelectric transformers generally use lead zirconate titanate (PZT) -based piezoelectric ceramics, but when PZT-based ceramics are fired at high temperatures, the lead component evaporates and shifts in composition, resulting in desired characteristics. Since it cannot be obtained and environmental pollution due to evaporating lead becomes a problem, it is desired to perform firing at as low a temperature as possible, and various sintering aids have been studied for that purpose (for example, patent documents) 1).
このような焼結助剤の選択は、母材となるＰＺＴ系圧電セラミックスの組成に依存して、その組成と添加量を適切に選択する必要があるため、公知の焼結助剤がそのまま全てのＰＺＴ系圧電セラミックスに適用できるわけではない。つまり、その選択が不適切な場合には、焼結温度を下げることはできても、圧電特性が低下してしまうという問題を生ずる場合がある。また、圧電トランスは主に共振現象を利用して駆動するが、駆動中に圧電セラミックスが有する誘電損失に起因して発熱が起こり、これによって圧電特性が低下するという現象が起こるため、温度変化による特性低下の小さい材料が望まれており、そのような特性も焼結助剤の影響を大きく受ける。
本発明はかかる事情に鑑みてなされたものであり、低温焼成を可能とし、かつ、駆動により温度が上昇した場合にも良好な圧電特性が得られる圧電セラミックスを得るための圧電セラミックス用焼結助剤を提供することを目的とする。また本発明は、この焼結助剤を用いてなる圧電セラミックスを提供することを目的とする。 The present invention has been made in view of such circumstances, and sintering aids for piezoelectric ceramics for obtaining piezoelectric ceramics that can be fired at a low temperature and can obtain good piezoelectric characteristics even when the temperature is increased by driving. The purpose is to provide an agent. Another object of the present invention is to provide a piezoelectric ceramic using the sintering aid.
本発明によれば、ＰＺＴ系圧電セラミックスの製造に用いられる焼結助剤であって、
少なくとも酸化鉛と酸化亜鉛を有し、残部が酸化ホウ素からなり、これらの金属酸化物の金属組成比がモル％で、１０≦Ｐｂ≦４０，２０≦Ｚｎ≦９０，０≦Ｂ≦４０である助剤群、および、酸化銅から構成されることを特徴とする圧電セラミックス用焼結助剤、が提供される。
According to the present invention, a sintering aid used in the production of PZT-based piezoelectric ceramics,
It has at least lead oxide and zinc oxide, the balance is made of boron oxide, and the metal composition ratio of these metal oxides is mol%, and 10 ≦ Pb ≦ 40, 20 ≦ Zn ≦ 90, 0 ≦ B ≦ 40. A sintering aid for piezoelectric ceramics, characterized in that it comprises an auxiliary agent group and copper oxide, is provided.
また、本発明によれば上記焼結助剤を用いてなる圧電セラミックス、すなわち、ＰＺＴ系圧電セラミックス材料に、少なくとも酸化鉛と酸化亜鉛を有し、残部が酸化ホウ素からなり、これらの金属酸化物の金属組成比がモル％で、１０≦Ｐｂ≦４０，２０≦Ｚｎ≦９０，０≦Ｂ≦４０である助剤群、および、酸化銅から構成される焼結助剤を添加し、所定温度で焼成して得られる圧電セラミックスであって、
前記ＰＺＴ系圧電セラミックス材料に対する前記助剤群の添加量は１．５重量％以上５重量％以下であり、かつ、前記ＰＺＴ系圧電セラミックス材料と前記助剤群の合計量に対する前記酸化銅の添加量は０．０１重量％以上０．５重量％以下であることを特徴とする圧電セラミックス、が提供される。
According to the present invention, the piezoelectric ceramic using the sintering aid, that is, the PZT-based piezoelectric ceramic material has at least lead oxide and zinc oxide, and the balance is made of boron oxide. And a sintering aid composed of copper oxide, and a predetermined temperature at which the metal composition ratio is 10% Pb ≦ 40, 20 ≦ Zn ≦ 90, and 0 ≦ B ≦ 40. Piezoelectric ceramics obtained by firing with
The addition amount of the auxiliary agent group to the PZT piezoelectric ceramic material is 1.5 wt% or more and 5 wt% or less, and the addition of the copper oxide to the total amount of the PZT piezoelectric ceramic material and the auxiliary agent group A piezoelectric ceramic characterized in that the amount is 0.01 wt% or more and 0.5 wt% or less is provided.
本発明によれば、例えば９５０℃以下の焼成でも、密度が大きく、良好な圧電特性を示す圧電セラミックスを製造することができる。また、本発明に係る焼結助剤を用いてなる圧電セラミックスは、特に圧電トランスや超音波モータ（超音波振動子）等の共振駆動型の圧電素子に適した場合に、駆動によって温度が上昇した場合にも、良好な駆動特性が得られる。この場合において、ＰＺＴ系圧電セラミックスと電極材料とを同時焼成して作製されるデバイスでは、電極材料として純銀（Ａｇ）を用いることができるようになるため、製造コストを下げることができるという効果も得られる。 According to the present invention, it is possible to produce a piezoelectric ceramic having a high density and good piezoelectric characteristics even when firing at, for example, 950 ° C. or less. In addition, the piezoelectric ceramic using the sintering aid according to the present invention rises in temperature by driving particularly when it is suitable for a resonance driving type piezoelectric element such as a piezoelectric transformer or an ultrasonic motor (ultrasonic vibrator). In this case, good driving characteristics can be obtained. In this case, in a device manufactured by simultaneously firing a PZT-based piezoelectric ceramic and an electrode material, pure silver (Ag) can be used as the electrode material, so that the manufacturing cost can be reduced. can get.
本発明に係る、ジルコン酸チタン酸鉛（ＰＺＴ）系圧電セラミックスの製造に用いられる焼結助剤（以下、単に「焼結助剤」という）は、少なくとも酸化鉛（ＰｂＯ）と酸化亜鉛（ＺｎＯ）を有し、残部が酸化ホウ素（Ｂ２Ｏ３）からなり、これらの金属酸化物の金属組成比がモル％で、１０≦Ｐｂ≦４０，２０≦Ｚｎ≦９０，０≦Ｂ≦４０である助剤群、および、酸化銅（ＣｕＯ）から構成される。なお、酸化鉛としてＰｂ３Ｏ４を用いることもできる。 The sintering aid (hereinafter simply referred to as “sintering aid”) used in the production of lead zirconate titanate (PZT) piezoelectric ceramics according to the present invention is at least lead oxide (PbO) and zinc oxide (ZnO). ) And the balance is made of boron oxide (B 2 O 3 ), and the metal composition ratio of these metal oxides is mol%, and 10 ≦ Pb ≦ 40, 20 ≦ Zn ≦ 90, 0 ≦ B ≦ 40 It consists of a certain auxiliary agent group and copper oxide (CuO). Note that Pb 3 O 4 can also be used as lead oxide.
ＰＺＴ系圧電セラミックス材料は、所謂、ソフト系，ハード系のどちらであってもよく、基本成分である鉛（Ｐｂ），ジルコニウム（Ｚｒ），（チタン）Ｔｉに加えて、マンガン（Ｍｎ）、ストロンチウム（Ｓｒ）、ニオブ（Ｎｂ）、タンタル（Ｔａ）等の成分を含んでいてもよい。 The PZT-based piezoelectric ceramic material may be so-called soft or hard, and in addition to lead (Pb), zirconium (Zr), and (titanium) Ti which are basic components, manganese (Mn) and strontium Components such as (Sr), niobium (Nb), and tantalum (Ta) may be included.
焼結助剤を構成する助剤群の、ＰＺＴ系圧電セラミックス材料の母材（つまり、焼結助剤を含まない組成の材料）に対する添加量は、１．５重量％以上５重量％以下とする。かつ、ＰＺＴ系圧電セラミックス材料の母材と助剤群の合計量に対する酸化銅の添加量は、０．０１重量％以上０．５重量％以下とする。 The addition amount of the auxiliary agent group constituting the sintering auxiliary agent to the base material of the PZT-based piezoelectric ceramic material (that is, the material not including the sintering auxiliary agent) is 1.5 wt% or more and 5 wt% or less. To do. And the addition amount of the copper oxide with respect to the total amount of the base material and auxiliary agent group of a PZT type piezoelectric ceramic material shall be 0.01 to 0.5 weight%.
助剤群および酸化銅のＰＺＴ系圧電セラミックスの母材に対する添加量を上記範囲とすることにより、後述する実施例に示すように、圧電トランス等に適用した場合に駆動によって温度が上昇しても良好な圧電特性を示すＰＺＴ系圧電セラミックスが得られる。また、ＰＺＴ系圧電セラミックスの製造工程においては、例えば９５０℃以下の焼成温度で製造することができる。このような低温焼成が可能となることにより、安価な炉を用いた製造が可能となり、炉の運転時の消費エネルギーを少なくすることができる。また、ＰＺＴ系圧電セラミックスでは、焼成温度が高くなると、Ｐｂ成分が揮発し、所望の組成物を得ることが困難となって、特性がばらつきやすくなるという問題があるが、この問題を解決することができる。さらに、ＰＺＴ系圧電セラミックスと電極材料とを同時焼成して作製されるデバイスでは、電極材料として純銀（Ａｇ）を用いることができるようになるため、製品コストを下げることができる。 By setting the additive amount of the auxiliary agent and copper oxide to the base material of the PZT-based piezoelectric ceramic within the above range, as shown in the examples described later, even when the temperature rises due to driving when applied to a piezoelectric transformer or the like, A PZT-based piezoelectric ceramic exhibiting good piezoelectric characteristics can be obtained. Moreover, in the manufacturing process of a PZT type piezoelectric ceramic, it can manufacture at a calcination temperature of 950 degrees C or less, for example. By enabling such low-temperature firing, it is possible to manufacture using an inexpensive furnace, and energy consumption during operation of the furnace can be reduced. In addition, in the PZT-based piezoelectric ceramics, when the firing temperature is high, the Pb component volatilizes, making it difficult to obtain a desired composition, and there is a problem that the characteristics are likely to vary. Can do. Furthermore, in a device manufactured by simultaneously firing a PZT-based piezoelectric ceramic and an electrode material, pure silver (Ag) can be used as the electrode material, so that the product cost can be reduced.
一方、焼結助剤の添加量が上記範囲から外れる場合において、その添加量が前記範囲よりも少ない場合には、焼結助剤としての効果が得られない。つまり、所望の密度や圧電特性を得ようとすると、焼成温度を下げることができない。また、焼結助剤の添加量が上記範囲よりも多くなると、低温での焼結は可能となるが、圧電特性が著しく低下してしまい、実用に供することが困難となる。特に、ＰＺＴ系圧電セラミックス材料の母材と助剤群の合計量に対する酸化銅の添加量が０．５重量％超の場合には、導電性が発現してしまい、分極ができなくなるという問題が生じる。 On the other hand, when the addition amount of the sintering aid is out of the above range, if the addition amount is less than the above range, the effect as the sintering aid cannot be obtained. In other words, the firing temperature cannot be lowered if desired density and piezoelectric characteristics are obtained. Further, when the amount of the sintering aid added is larger than the above range, sintering at a low temperature becomes possible, but the piezoelectric characteristics are remarkably deteriorated, making it difficult to put to practical use. In particular, when the amount of copper oxide added is more than 0.5% by weight based on the total amount of the base material and the auxiliary agent group of the PZT-based piezoelectric ceramic material, there is a problem that conductivity is developed and polarization cannot be performed. Arise.
ＰＺＴ系圧電セラミックスの製造方法としては、母材を構成するＰｂ，Ｚｒ，Ｔｉ等の各金属元素を含む化合物（例えば、酸化物、炭酸塩、硝酸塩等）を所定の比率で混合し、この混合物を８５０℃〜９００℃で酸素の存在下（大気雰囲気でもよいし、強制的な酸素供給により酸素リッチな雰囲気としてもよい）で仮焼し、得られた仮焼粉末を必要に応じて再粉砕し、所定のメッシュに通す等して粒度調整（分級）し、これに焼結助剤を構成する各金属元素を含む化合物（例えば、酸化物、炭酸塩、硝酸塩等）を添加して再混合した後、プレス成形法、押出成形法、ドクターブレード法等の各種方法で成形し、９００℃〜９５０℃で焼成する方法が好適に用いられる。 As a method for producing PZT-based piezoelectric ceramics, a compound (for example, oxide, carbonate, nitrate, etc.) containing each metal element such as Pb, Zr, Ti, etc. constituting the base material is mixed at a predetermined ratio, and this mixture Is calcined at 850 ° C. to 900 ° C. in the presence of oxygen (air atmosphere or oxygen-rich atmosphere by forced oxygen supply), and the obtained calcined powder is reground as necessary Then, the particle size is adjusted (classified) by passing through a predetermined mesh, etc., and a compound containing each metal element constituting the sintering aid (for example, oxide, carbonate, nitrate, etc.) is added and remixed. After that, a method of forming by various methods such as a press molding method, an extrusion molding method, a doctor blade method and the like and firing at 900 ° C. to 950 ° C. is suitably used.
なお、仮焼粉末の調製条件は、９０％以上のペロブスカイト相が生成するように、かつ、得られる仮焼粉末の粒成長が進みすぎないように、仮焼温度および仮焼時間を設定することが好ましい。ペロブスカイト相の生成量は、例えば、仮焼粉末のＸＲＤパターンから判断することができる。なお、ＰＺＴ系圧電セラミックスの母材の仮焼粉末と焼結助剤の仮焼粉末とを別々に調製し、こうして調製した各粉末を混合、成形、焼結する方法や、ＰＺＴ系圧電セラミックスの母材原料と焼結助剤原料とを混合、仮焼、成形、焼成する方法を採ってもよい。 The preparation conditions for the calcined powder are to set the calcining temperature and calcining time so that 90% or more of the perovskite phase is generated and the grain growth of the obtained calcined powder does not proceed excessively. Is preferred. The amount of perovskite phase produced can be determined, for example, from the XRD pattern of the calcined powder. It should be noted that the PZT-based piezoelectric ceramic base calcined powder and the sintering auxiliary calcined powder are prepared separately, and each of the thus-prepared powders is mixed, molded, and sintered. A method of mixing, calcining, forming, and firing the base material and the sintering aid material may be employed.
本発明の実施例および比較例について説明する。
出発原料として、ＭｎＣＯ３，ＰｂＯ，ＳｒＣＯ３，ＺｒＯ２，ＴｉＯ２，Ｎｂ２Ｏ５の各粉末を、組成が（Ｐｂ０．９３Ｓｒ０．０５）（Ｚｒ０．５２Ｔｉ０．４５Ｍｎ０．０１Ｎｂ０．０２）Ｏ３となるように秤量し、これに所定量のイオン交換水（または蒸留水、純水）を加えてボールミルにより粉砕混合し、その後１１０℃で乾燥した。得られた粉末を、大気中、９００℃で２時間仮焼し、母材仮焼粉末を得た。
Examples of the present invention and comparative examples will be described.
As a starting material, each powder of MnCO 3 , PbO, SrCO 3 , ZrO 2 , TiO 2 , Nb 2 O 5 has a composition of (Pb 0.93 Sr 0.05 ) (Zr 0.52 Ti 0.45 Mn 0 .01 Nb 0.02 ) O 3, and a predetermined amount of ion-exchanged water (or distilled water, pure water) was added thereto and pulverized and mixed with a ball mill, and then dried at 110 ° C. The obtained powder was calcined in the atmosphere at 900 ° C. for 2 hours to obtain a base material calcined powder.
次に、助剤群を構成するＰｂＯ，Ｂ２Ｏ３，ＺｎＯの各粉末を図１（ａ）に示す組成ダイヤグラム中の番号１〜２２の各組成となるように秤量し、先に作製した母材仮焼粉末に表１に示す添加量となるように添加し、これにＣｕＯを表１に示す添加量となるように秤量して添加し、所定量のイオン交換水および可塑剤を加えてボールミルにより混合した。その後、得られたスラリーを１１０℃で乾燥し、メッシュパスすることで、顆粒粉末を得た。 Next, each powder of PbO, B 2 O 3 , ZnO constituting the auxiliary agent group was weighed so as to have each composition of Nos. 1 to 22 in the composition diagram shown in FIG. Add to the base material calcined powder so as to have the addition amount shown in Table 1, add CuO to the addition amount shown in Table 1, and add a predetermined amount of ion exchange water and plasticizer. And mixed with a ball mill. Thereafter, the resulting slurry was dried at 110 ° C. and passed through a mesh to obtain granule powder.
なお、図１（ｂ）に助剤群の必須組成比率、つまりモル％で、１０≦Ｐｂ≦４０，２０≦Ｚｎ≦９０，０≦Ｂ≦４０の領域Ｓを示す。図１（ａ）と図１（ｂ）を比較することにより、試料１〜３，７，１１，１５，１９〜２２は、本発明の条件を満たさない比較例であり、その他の試料４〜６，８，１０，１２〜１４，１６〜１８は本発明の条件を満足する実施例である。試料９ａ〜９ｅは、助剤群の組成の観点からは本発明の条件を満足するが、添加量の観点から実施例に属する９ｂ〜９ｄと、比較例に属する９ａ，９ｅに分けられる。 FIG. 1B shows the region S where 10 ≦ Pb ≦ 40, 20 ≦ Zn ≦ 90, and 0 ≦ B ≦ 40 in terms of the essential composition ratio of the auxiliary agent group, that is, mol%. By comparing FIG. 1 (a) and FIG. 1 (b), Samples 1 to 3, 7, 11, 15, 19 to 22 are comparative examples that do not satisfy the conditions of the present invention, and other samples 4 to 6, 8, 10, 12-14, 16-18 are examples which satisfy the conditions of the present invention. Samples 9a to 9e satisfy the conditions of the present invention from the viewpoint of the composition of the auxiliary agent group, but are divided into 9b to 9d belonging to the examples and 9a and 9e belonging to the comparative examples from the viewpoint of the addition amount.
こうして作製した各組成を有する粉末を、一軸プレス成形装置を用いて直径２０ｍｍφ、厚さ１．５ｍｍに成形し、さらに１２０ＭＰａで冷間静水圧成形（ＣＩＰ）し、全ての成形体を大気中、９００℃で２時間焼成した。得られた焼結体は全て直径が約１６ｍｍであった。各焼結体を厚さが１ｍｍとなるようにラッピング処理し、アルキメデス法により嵩密度を求めた。その後、図２に示すように、焼結体１０の一面全体にアース電極１１が、他面に入力電極１２と出力電極１３がそれぞれ形成されるように銀ペーストを印刷し、８５０℃で１０分間、焼き付け処理し、さらに１２０℃のシリコーンオイル中で、１０分、２ｋＶ／ｍｍの条件で焼結体を厚み方向に分極させ、圧電トランスを作製した。
The powders having the respective compositions thus produced were molded into a diameter of 20 mmφ and a thickness of 1.5 mm using a uniaxial press molding apparatus, and further subjected to cold isostatic pressing (CIP) at 120 MPa, and all the molded bodies were in the atmosphere. Firing was performed at 900 ° C. for 2 hours. All the obtained sintered bodies had a diameter of about 16 mm. Each sintered body was lapped so as to have a thickness of 1 mm, and the bulk density was determined by Archimedes method. Thereafter, as shown in FIG. 2, a silver paste is printed so that the
この圧電トランスの出力特性は、圧電トランスの温度を測定しながら、出力電力を少しずつ増加させて、電力投入（周波数：共振周波数近傍（約１５０−１７０ｋＨｚ）、負荷：整合負荷）をする前の温度（つまり、トランス駆動を始める前の温度）との温度差が２０℃になった時点での出力を測定し、その出力が４．０Ｗ以上のものを合格とした。なお、焼結助剤を用いずに母剤仮焼粉末のみを用いて作製した焼結体（その焼成条件は１１００℃、２時間）で圧電トランスを作製した場合の出力値は４．２Ｗであった。前記基準出力の値（＝４．０Ｗ）はこの値よりも小さいが、十分に実用に供することができる特性であると判断し、基準値とした。 The output characteristics of this piezoelectric transformer are as follows. While measuring the temperature of the piezoelectric transformer, the output power is increased little by little and the power is turned on (frequency: near resonance frequency (about 150-170 kHz), load: matching load). The output when the temperature difference from the temperature (that is, the temperature before starting the transformer drive) reached 20 ° C. was measured, and the output was 4.0 W or more and passed. Note that the output value when a piezoelectric transformer is produced with a sintered body produced using only the base material calcined powder without using a sintering aid (the firing condition is 1100 ° C. for 2 hours) is 4.2 W. there were. Although the value of the reference output (= 4.0 W) is smaller than this value, it is determined that the characteristic can be sufficiently put to practical use, and is set as a reference value.
測定結果を表１に併記する。表１に示されるように、焼結助剤を構成する助剤群の組成が図１（ｂ）に示される領域Ｓの範囲内にあり、かつ、助剤群の圧電セラミックス母材に対する添加率が１．５ｗｔ％以上５ｗｔ％以下の試料（ＣｕＯの添加率は一律で本発明で規定する範囲内）では、４．０Ｗ以上の高い出力が得られており、作動温度が上昇しても良好な特性を示すことが確認された。 The measurement results are also shown in Table 1. As shown in Table 1, the composition of the auxiliary agent group constituting the sintering auxiliary agent is within the range of the region S shown in FIG. 1B, and the addition ratio of the auxiliary agent group to the piezoelectric ceramic base material Is 1.5 wt% or more and 5 wt% or less (CuO addition rate is uniformly within the range specified in the present invention), a high output of 4.0 W or more is obtained, and even if the operating temperature rises, it is good It was confirmed that it showed the characteristic.
また試料９ａでは、助剤群の圧電セラミックス母材に対する添加率が１．５ｗｔ％未満で少なかったために密度が上がらず、これに起因して出力特性が低下したと考えられた。試料９ａ以外の比較例に係る試料では、７．６ｇ／ｃｍ３以上の高い密度が得られているにもかかわらず出力特性が低くなった。これは焼結助剤が焼結温度の低下にのみ作用することなく、圧電セラミックス母材の組成変動を引き起こす等して、圧電特性を低下させたと推測された。 Moreover, in the sample 9a, since the addition rate with respect to the piezoelectric ceramic base material of the auxiliary agent group was less than 1.5 wt%, the density did not increase, and it was considered that the output characteristics were lowered due to this. In the samples according to the comparative examples other than the sample 9a, the output characteristics were low although a high density of 7.6 g / cm 3 or more was obtained. This was presumed that the sintering aid did not act only on the reduction of the sintering temperature, but caused the piezoelectric characteristics to be lowered, for example, by causing composition fluctuations of the piezoelectric ceramic base material.
なお、ＣｕＯの添加率が０ｗｔ％の場合には、９００℃での焼成では密度が上がらず、４．０Ｗ以上の出力が得られる圧電トランスを作製するためには、９５０℃超の焼成温度が必要であった。また、ＣｕＯの添加率が５ｗｔ％超の場合には、９００℃での焼成で７．６〜７．７ｇ／ｃｍ３の密度が得られたが、導電率が高くなってしまい、分極処理ができなかった。 When the addition rate of CuO is 0 wt%, firing at 900 ° C. does not increase the density, and in order to produce a piezoelectric transformer that can output 4.0 W or more, a firing temperature exceeding 950 ° C. It was necessary. In addition, when the addition rate of CuO exceeds 5 wt%, a density of 7.6 to 7.7 g / cm 3 was obtained by firing at 900 ° C., but the conductivity increased and the polarization treatment was reduced. could not.
本発明は、圧電トランス、超音波モータ等の電気エネルギーを機械振動エネルギーに変換する圧電デバイスに用いられる圧電セラミックスに好適である。 The present invention is suitable for piezoelectric ceramics used in piezoelectric devices that convert electrical energy into mechanical vibration energy, such as piezoelectric transformers and ultrasonic motors.
１０；円板型焼結体
１１；アース電極
１２；入力電極
１３；出力電極
10; Disc type sintered
Claims (2)
少なくとも酸化鉛と酸化亜鉛を有し、残部が酸化ホウ素からなり、これらの金属酸化物の金属組成比がモル％で、１０≦Ｐｂ≦４０，２０≦Ｚｎ≦９０，０≦Ｂ≦４０である助剤群、および、酸化銅から構成されることを特徴とする圧電セラミックス用焼結助剤。 A sintering aid used in the manufacture of PZT-based piezoelectric ceramics,
It has at least lead oxide and zinc oxide, the balance is made of boron oxide, and the metal composition ratio of these metal oxides is mol%, and 10 ≦ Pb ≦ 40, 20 ≦ Zn ≦ 90, 0 ≦ B ≦ 40. A sintering aid for piezoelectric ceramics, comprising an auxiliary agent group and copper oxide.
前記ＰＺＴ系圧電セラミックス材料に対する前記助剤群の添加量は１．５重量％以上５重量％以下であり、かつ、前記ＰＺＴ系圧電セラミックス材料と前記助剤群の合計量に対する前記酸化銅の添加量は０．０１重量％以上０．５重量％以下であることを特徴とする圧電セラミックス。 The PZT-based piezoelectric ceramic material has at least lead oxide and zinc oxide, the remainder is made of boron oxide, and the metal composition ratio of these metal oxides is mol%, and 10 ≦ Pb ≦ 40, 20 ≦ Zn ≦ 90, A piezoelectric ceramic obtained by adding an auxiliary group of 0 ≦ B ≦ 40 and a sintering auxiliary composed of copper oxide and firing at a predetermined temperature,
The addition amount of the auxiliary agent group to the PZT piezoelectric ceramic material is 1.5 wt% or more and 5 wt% or less, and the addition of the copper oxide to the total amount of the PZT piezoelectric ceramic material and the auxiliary agent group Piezoelectric ceramics characterized in that the amount is 0.01 wt% or more and 0.5 wt% or less.
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| JP2008100887A (en) * | 2006-10-20 | 2008-05-01 | Fujifilm Corp | Raw material powder for film deposition, film structure, method for producing them and piezoelectric element |
| JP2014529902A (en) * | 2011-08-30 | 2014-11-13 | エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ | Piezoelectric device and method for manufacturing piezoelectric device |
| EP3085678A4 (en) * | 2014-08-29 | 2017-08-23 | Kyocera Corporation | Piezoelectric ceramic, manufacturing method therefor, and electronic component |
| CN116606136A (en) * | 2023-05-19 | 2023-08-18 | 歌尔微电子股份有限公司 | Piezoelectric ceramic material, preparation method thereof and piezoelectric device |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008100887A (en) * | 2006-10-20 | 2008-05-01 | Fujifilm Corp | Raw material powder for film deposition, film structure, method for producing them and piezoelectric element |
| JP2014529902A (en) * | 2011-08-30 | 2014-11-13 | エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ | Piezoelectric device and method for manufacturing piezoelectric device |
| US9570669B2 (en) | 2011-08-30 | 2017-02-14 | Epcos Ag | Piezoelectric component and method for producing a piezoelectric component |
| US10483454B2 (en) | 2011-08-30 | 2019-11-19 | Tdk Electronics Ag | Piezoelectric component and method for producing a piezoelectric component |
| EP3085678A4 (en) * | 2014-08-29 | 2017-08-23 | Kyocera Corporation | Piezoelectric ceramic, manufacturing method therefor, and electronic component |
| CN116606136A (en) * | 2023-05-19 | 2023-08-18 | 歌尔微电子股份有限公司 | Piezoelectric ceramic material, preparation method thereof and piezoelectric device |
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