JP5468984B2 - Sintering aid for lead-free piezoelectric ceramics, lead-free piezoelectric ceramics and manufacturing method thereof - Google Patents
Sintering aid for lead-free piezoelectric ceramics, lead-free piezoelectric ceramics and manufacturing method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims description 32
- 238000005245 sintering Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 26
- 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 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 24
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 18
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 239000010955 niobium Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 (Li Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Description
本発明は、アクチュエータや超音波振動子、あるいは圧力センサ等に利用するアルカリ金属含有ニオブ酸化物からなる圧電セラミックス及びその製造方法に関するものである。 The present invention relates to a piezoelectric ceramic made of an alkali metal-containing niobium oxide used for an actuator, an ultrasonic vibrator, a pressure sensor or the like, and a method for manufacturing the same.
これまで、電気エネルギーと機械エネルギーを変換する圧電セラミックスには、鉛を含むPZT系組成の圧電セラミックスが用いられてきた。 Up to now, PZT-based piezoelectric ceramics containing lead have been used for piezoelectric ceramics that convert electrical energy and mechanical energy.
しかし、近年の環境意識の高まりを受け、圧電材料として鉛化合物を含まない圧電セラミックスの組成物が注目され研究開発が行われている。 However, in response to the recent increase in environmental awareness, piezoelectric ceramic compositions that do not contain lead compounds are attracting attention and research and development as piezoelectric materials.
（Li、Na、K）（Nb、Ta、Sb）O3等のアルカリ金属含有ニオブ酸化物は高い圧電特性を持ち、圧電セラミックスとして実用化の可能性が高い。例えば特許文献１記載の｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３（但し、１≦ａ≦１．０５、０．３≦ｘ≦０．７、０．０２≦ｙ≦０．１、０≦ｚ≦０．５、及び、０．０１≦ｗ≦０．１）は、焼結体の粒径を制御することにより、高い圧電特性を実現している。 Alkali metal-containing niobium oxides such as (Li, Na , K) (Nb, Ta, Sb) O 3 have high piezoelectric properties and are likely to be put into practical use as piezoelectric ceramics. For example, {Li y (Na 1−x K x ) 1−y } a (Nb 1−z−w Ta z Sb w ) O 3 (where 1 ≦ a ≦ 1.05, 0.3) described in Patent Document 1 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.1, 0 ≦ z ≦ 0.5, and 0.01 ≦ w ≦ 0.1) by controlling the particle size of the sintered body High piezoelectric characteristics are realized.
しかし、（Li、Na、K）（Nb、Ta、Sb）O3等のアルカリ金属含有ニオブ酸化物は、アルカリ成分の揮発等の理由により焼結性が悪い。そのため通常の常圧焼結法により緻密な焼結体を得ることは難しく、また組成の一部が欠落するため、安定して一定の特性を持つ圧電セラミックスが得られない。 However, alkali metal-containing niobium oxides such as (Li, Na, K) (Nb, Ta, Sb) O 3 have poor sinterability due to volatilization of alkali components. For this reason, it is difficult to obtain a dense sintered body by a normal atmospheric pressure sintering method, and a part of the composition is lost, so that a piezoelectric ceramic having stable and constant characteristics cannot be obtained.
本発明は、このような事情を鑑みてなされたものであり、安定して緻密な焼結体となるアルカリ金属含有ニオブ酸化物からなる圧電セラミックスおよびその製造方法を提供することを目的としている。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a piezoelectric ceramic made of an alkali metal-containing niobium oxide that becomes a stable and dense sintered body, and a method for producing the same.
（１）上記の課題を解決するため、本発明のニオブ酸系非鉛圧電セラミックスは、｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３（但し０≦ｘ≦０．２、０≦ｙ≦１、０≦ｚ≦０．４、０≦ｗ≦０．２）で表されるアルカリ金属含有ニオブ酸化物を主成分とし、前記主成分に対して、酸化ビスマスと酸化亜鉛からなる圧電セラミックス用焼結助剤を添加することを特徴としている。 (1) In order to solve the above-mentioned problems, the niobic acid-based lead-free piezoelectric ceramic of the present invention is {Li x (K 1-y Na y ) 1-x } (Nb 1-zw Ta z Sb w ) The main component is an alkali metal-containing niobium oxide represented by O 3 (where 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 1, 0 ≦ z ≦ 0.4, 0 ≦ w ≦ 0.2), It is characterized by adding a sintering aid for piezoelectric ceramics composed of bismuth oxide and zinc oxide to the main component.
（２）また本発明に係わる圧電セラミックス用焼結助剤は、前記主成分に対して、酸化ビスマスをＡｗｔ％（但し０＜Ａ≦２）及び酸化亜鉛をＢｗｔ％（但し０＜Ｂ≦２）であることを特徴とする。 (2) In the sintering aid for piezoelectric ceramics according to the present invention, Awt% (provided 0 <A ≦ 2) of bismuth oxide and Bwt% (provided 0 <B ≦ 2) of zinc oxide with respect to the main component. ).
（３）また本発明は、１０５０℃以上１１００℃以下の温度範囲で焼成することを特徴としている。これは、１１００℃より高温では、カリウムの揮発が促進するためである。これにより、アルカリ成分の揮発を抑え緻密化した焼結体が得られる。 (3) Moreover, this invention is characterized by baking in the temperature range of 1050 degreeC or more and 1100 degrees C or less. This is because the volatilization of potassium is accelerated at a temperature higher than 1100 ° C. Thereby, the sintered compact which suppressed the volatilization of the alkali component and was densified is obtained.
（４）本発明は、主成分である｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３（但し０≦ｘ≦０．２、０≦ｙ≦１、０≦ｚ≦０．４、０≦ｗ≦０．２）を仮焼する仮焼工程と、前記仮焼工程を経て得られた主成分の仮焼粉と、焼結助剤として酸化ビスマスをＡｗｔ％（但し０＜Ａ≦２）及び酸化亜鉛をＢｗｔ％（但し０＜Ｂ≦２）とを混合する混合工程と、前記混合工程で得られた混合紛を焼成して焼結体とする焼成工程とを含むことを特徴としている。 (4) In the present invention, {Li x (K 1-y Na y ) 1-x } (Nb 1-zw Ta z Sb w ) O 3 (where 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 1, 0 ≦ z ≦ 0.4, 0 ≦ w ≦ 0.2), calcining powder of the main component obtained through the calcining step, and sintering A mixing step of mixing Awt% (provided 0 <A ≦ 2) of bismuth oxide and Bwt% (provided 0 <B ≦ 2) of zinc oxide as auxiliary agents, and firing the mixed powder obtained in the mixing step And a firing step for forming a sintered body.
本発明によれば、焼結助剤として金属酸化物を添加することで、通常の常圧焼結法でも安定的で緻密なニオブ酸化物系非鉛圧電セラミックスおよびその製造方法を提供することができる。 According to the present invention, by adding a metal oxide as a sintering aid, it is possible to provide a stable and dense niobium oxide-based lead-free piezoelectric ceramic and a method for producing the same even in a normal atmospheric pressure sintering method. it can.
本願発明者は、鉛を含まない非鉛圧電セラミックスを作製するために、常圧焼結法によるアルカリ金属含有ニオブ酸化物の開発を試みた。その過程において、本願発明者は安定して一定の圧電特性を持つ圧電セラミックスを得るために、成形体を緻密に焼結する要請があることに着目し、特定の焼結助剤を添加して、アルカリ金属含有ニオブ酸化物からなる圧電セラミックスを作製することを見出した。以下に、本発明の実施形態を説明する。 The inventor of the present application tried to develop an alkali metal-containing niobium oxide by an atmospheric pressure sintering method in order to produce lead-free non-lead piezoelectric ceramics. In the process, the inventor of the present application pays attention to the need to densely sinter the molded body in order to obtain a piezoelectric ceramic having stable and constant piezoelectric characteristics, and adds a specific sintering aid. The inventors have found that a piezoelectric ceramic made of an alkali metal-containing niobium oxide is produced. Hereinafter, embodiments of the present invention will be described.
（アルカリ金属含有ニオブ酸化物からなる圧電セラミックスの構成）
本発明のアルカリ金属含有ニオブ酸化物からなる圧電セラミックスとは、｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３で表されるアルカリ金属含有ニオブ酸化物が主成分で、焼結助剤として酸化ビスマスをＡｗｔ％（但し０＜Ａ≦２）及び酸化亜鉛をＢｗｔ％（但し０＜Ｂ≦２）を添加し、焼結したものである。
(Configuration of piezoelectric ceramics made of alkali metal-containing niobium oxide)
The piezoelectric ceramic consisting of alkali metal-containing niobium oxides of the present invention, an alkali represented by {Li x (K 1-y Na y) 1-x} (Nb 1-z-w Ta z Sb w) O 3 The main component is a metal-containing niobium oxide, which is sintered by adding Awt% (provided 0 <A ≦ 2) of bismuth oxide and Bwt% (provided 0 <B ≦ 2) of zinc oxide as sintering aids. It is.
母材の組成は、｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３と表したとき、０≦ｘ≦０．２、０≦ｙ≦１、０≦ｚ≦０．４、０≦w≦０．２の条件を満たすのが好適である。 The composition of the base material is expressed as {Li x (K 1−y Na y ) 1−x } (Nb 1−z−w Ta z Sb w ) O 3 , 0 ≦ x ≦ 0.2, 0 ≦ It is preferable that the conditions of y ≦ 1, 0 ≦ z ≦ 0.4, and 0 ≦ w ≦ 0.2 are satisfied.
アルカリ金属含有ニオブ酸化物からなる圧電セラミックス等の母材の圧電特性を維持しつつ、セラミックス部材を緻密化させるには、反応性が高く融点の低い酸化亜鉛や酸化ビスマスを添加し、粒界相に液相を作り焼結を促進するのが効果的である。例えば、５価のＮｂに対し、３価のＢｉ等の価数の異なるイオンを添加するとＮｂサイトで置換され、酸素イオンの空孔が生成され、この酸素空孔は焼結中のイオンの拡散を増加させる。この結果として焼結性が高まり、効果的に緻密化する。 To maintain the piezoelectric properties of a base material such as a piezoelectric ceramic made of an alkali metal-containing niobium oxide and to densify the ceramic member, zinc oxide or bismuth oxide having a low reactivity and a low melting point is added, and the grain boundary phase is added. It is effective to promote the sintering by forming a liquid phase. For example, when ions with different valences, such as trivalent Bi, are added to pentavalent Nb, the Nb sites are substituted, and oxygen ion vacancies are generated. These oxygen vacancies diffuse ions during sintering. Increase. As a result, the sinterability is enhanced and the densification is effectively performed.
本発明で用いられる焼結助剤は、酸化ビスマス及び酸化亜鉛からなり、アルカリ金属含有ニオブ酸化物を緻密化させるのに適している。本焼結助剤を本願母材のアルカリ金属含有ニオブ酸化物からなる圧電セラミックスの製造工程において添加することで、アルカリ金属含有ニオブ酸化物は１０５０℃以上１１００℃以下の焼成温度で緻密化される。 The sintering aid used in the present invention is composed of bismuth oxide and zinc oxide, and is suitable for densifying the alkali metal-containing niobium oxide. By adding the sintering aid in the manufacturing process of the piezoelectric ceramic made of the alkali metal-containing niobium oxide of the base material of the present application, the alkali metal-containing niobium oxide is densified at a firing temperature of 1050 ° C. or higher and 1100 ° C. or lower. .
焼結助剤となる酸化ビスマス及び酸化亜鉛は、酸化ビスマスをＡｗｔ％（但し０＜Ａ≦２）の範囲で、酸化亜鉛をＢｗｔ％（但し０＜Ｂ＜２）の範囲で添加することが好ましい。酸化ビスマス及び酸化亜鉛を緻密化に最も効果のある添加量加えることで、アルカリ金属含有ニオブ酸化物からなる圧電セラミックスを安定的に緻密化させ、かつ安定的に一定の圧電特性が得られる。 Bismuth oxide and zinc oxide as sintering aids may be added in the range of bismuth oxide in the range of Awt% (where 0 <A ≦ 2) and zinc oxide in the range of Bwt% (where 0 <B <2). preferable. By adding the addition amount of bismuth oxide and zinc oxide which is most effective for densification, the piezoelectric ceramic made of an alkali metal-containing niobium oxide can be densified stably and a constant piezoelectric characteristic can be obtained.
（アルカリ金属含有ニオブ酸化物からなる圧電セラミックスの製造方法）
酸化ビスマス及び酸化亜鉛からなる焼結助剤を用いて、緻密なアルカリ金属含有ニオブ酸化物からなる圧電セラミックスを通常の常圧焼結法により安定的に製造する方法を示す。まず、Ｌｉ２ＣＯ３、Ｎａ２ＣＯ３、Ｋ２ＣＯ３、Ｎｂ２Ｏ５、Ｓｂ２Ｏ５、Ｔａ２Ｏ５の粉末を秤量し、溶媒とともにミルで混合する。そして、混合粉末を乾燥させ、メッシュパスにより造粒する。次いで、粉末を７５０℃以上９５０℃以下で仮焼し、アルカリ金属含有ニオブ酸化物の仮焼粉を作製する。そして、バインダと共に所定量の酸化ビスマス、酸化亜鉛を加えて混合する。なお、混合の際にはボールミル等により、平均粒径が１．０μｍ以下になるまで粉砕をする。その後、乾燥、造粒して得られた粉末を所望の形状に成形して１０５０℃以上１１００℃で焼成すれば、アルカリ金属含有ニオブ酸化物からなる圧電セラミックスの緻密な焼結体が得られる。上記のように、酸化ビスマス及び酸化亜鉛を添加することで、圧電セラミックスを緻密化させることが出来る。
(Method for producing piezoelectric ceramics comprising alkali metal-containing niobium oxide)
A method for stably producing a piezoelectric ceramic made of a dense alkali metal-containing niobium oxide by a normal atmospheric pressure sintering method using a sintering aid made of bismuth oxide and zinc oxide will be described. First, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Nb 2 O 5 , Sb 2 O 5 , and Ta 2 O 5 powders are weighed and mixed together with a solvent in a mill. Then, the mixed powder is dried and granulated by a mesh pass. Next, the powder is calcined at 750 ° C. or more and 950 ° C. or less to prepare an alkali metal-containing niobium oxide calcined powder. Then, a predetermined amount of bismuth oxide and zinc oxide are added and mixed together with the binder. In mixing, the mixture is pulverized by a ball mill or the like until the average particle size becomes 1.0 μm or less. Then, if the powder obtained by drying and granulating is formed into a desired shape and fired at 1050 ° C. or higher and 1100 ° C., a dense sintered body of piezoelectric ceramic made of an alkali metal-containing niobium oxide can be obtained. As described above, the piezoelectric ceramic can be densified by adding bismuth oxide and zinc oxide.
本願母材の一般式｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３において、化学量論比がＬｉ０．０６（Ｋ０．５０Ｎａ０．５０）０．９４｝ＮｂＯ３となるように、純度９９％以上の高純度のＬｉ２ＣＯ３、Ｎａ２ＣＯ３、Ｋ２ＣＯ３、Ｎｂ２Ｏ５を配合した。配合した原料をボールミルによりイソプロピルアルコール中で２４時間粉砕、混合、乾燥して原料混合紛を作製した。次に、この原料混合紛を８５０℃にて２〜５時間仮焼し仮焼粉を得た。この仮焼紛をボールミルにて２４時間粉砕させ、平均粒径１．０μｍ以下の仮焼粉を得た。 In this application the general formula of the matrix {Li x (K 1-y Na y) 1-x} (Nb 1-z-w Ta z Sb w) O 3, stoichiometry Li 0.06 (K 0. 50 Na 0.50 ) 0.94 } NbO 3 was mixed with high purity Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Nb 2 O 5 with a purity of 99% or more. The blended raw material was pulverized in isopropyl alcohol for 24 hours by a ball mill, mixed and dried to prepare a raw material mixed powder. Next, this raw material mixed powder was calcined at 850 ° C. for 2 to 5 hours to obtain calcined powder. The calcined powder was pulverized with a ball mill for 24 hours to obtain a calcined powder having an average particle size of 1.0 μm or less.
焼結助剤として酸化ビスマスを０〜３．０ｗｔ％、及び酸化亜鉛を０〜３．０ｗｔ％の範囲内で、その他にバインダとしてグリセリンを３．０ｗｔ％を上記主成分からなる仮焼粉に対し添加した。配合した粉末をボールミルによりイソプロピルアルコール中で２４時間混合し、粒度分布計（堀場製作所製，ＬＡ９２０）で測定して、平均粒径が１．０μｍ以下の混合粉を得た。その後、乾燥、造粒し加圧成形を行った。加圧成形は、造粒した粉砕物を一軸プレス成形によりペレット状に成形したものを、さらに冷間等方圧プレス（ＣＩＰ）により１２０ＭＰaの圧力で再成形した。 The calcined powder comprising the above main components of 0 to 3.0 wt% of bismuth oxide as a sintering aid and 0 to 3.0 wt% of zinc oxide, and 3.0 wt% of glycerin as a binder. It added to. The blended powder was mixed in isopropyl alcohol for 24 hours with a ball mill and measured with a particle size distribution meter (LA920, manufactured by Horiba, Ltd.) to obtain a mixed powder having an average particle size of 1.0 μm or less. Then, it dried, granulated, and pressure-molded. In the pressure molding, the granulated pulverized product formed into a pellet by uniaxial press molding was further re-molded at a pressure of 120 MPa by cold isostatic pressing (CIP).
このようにして得られた成形体をアルミナの小鉢に入れ、電気加熱ヒーター炉にて、大気中、１０００〜１１５０℃にて１〜２時間の常圧焼結を行った。 The molded body thus obtained was put in an alumina small bowl and subjected to atmospheric pressure sintering at 1000 to 1150 ° C. for 1 to 2 hours in the air in an electric heater furnace.
焼結体の密度は、アルキメデス法により測定した。特性測定においては、各条件で形成されたペレット状の焼結体の両主面に銀ペーストを印刷し、焼成することで電極を形成し、5ｋＶ／ｍｍの条件で、焼結体の厚み方向に分極させた。このように、焼成された試料に電極を設けて分極し、比誘電率等を測定した。 The density of the sintered body was measured by the Archimedes method. In the characteristic measurement, a silver paste is printed on both principal surfaces of the pellet-shaped sintered body formed under each condition, and an electrode is formed by firing. The thickness direction of the sintered body is 5 kV / mm. Was polarized. As described above, the fired sample was provided with an electrode and polarized, and the relative dielectric constant and the like were measured.
表１は、各添加量の焼結助剤を加えたアルカリ金属含有ニオブ酸化物からなる圧電セラミックスについて、密度、比誘電率を測定した結果を示す表である。嵩密度が十分緻密化したと考えられる４．３ｇ／cm3、かつ分極した試料について可とし、密度が４．３ｇ／cm3に満たない、又は分極不可能及び測定不可能な試料については否と判断した。 Table 1 is a table showing the results of measuring the density and relative dielectric constant of a piezoelectric ceramic made of an alkali metal-containing niobium oxide to which each additive amount of a sintering aid is added. Acceptable for 4.3 g / cm 3 , which is considered to have a sufficiently dense bulk density, and polarized samples, but not for samples whose density is less than 4.3 g / cm 3 , or are unpolarizable and unmeasurable. It was judged.
表１で示されているように本特許の請求範囲の焼結体は、嵩密度が高い。また、比較例である焼結助剤を添加していない試料では、１１００℃での焼結体は１０５０℃での焼結体に比べ嵩密度が低下しているが、本発明の焼結体は１１００℃で焼成した試料も高い密度を維持している。 As shown in Table 1, the sintered body claimed in this patent has a high bulk density. In addition, in the sample not added with the sintering aid as a comparative example, the sintered body at 1100 ° C. has a lower bulk density than the sintered body at 1050 ° C., but the sintered body of the present invention. The sample fired at 1100 ° C. maintains a high density.
表中の「−」は分極不可能または測定不能だったことを示している。これらの試料については、分極時にリーク電流が流れ、分極が困難であった。 “−” In the table indicates that polarization is not possible or measurement is impossible. For these samples, leakage current flowed during polarization, and polarization was difficult.
以上のように、アルカリ金属含有ニオブ酸化物からなる圧電セラミックスの母材である｛Ｌｉｘ（Ｋ１−ｙＮａｙ）１−ｘ｝（Ｎｂ１−ｚ−ｗＴａｚＳｂｗ）Ｏ３に対して、焼結助剤として酸化ビスマスおよび酸化亜鉛を添加することによって、常圧焼結法により安定的に緻密なアルカリ金属含有ニオブ酸化物からなる圧電セラミックスを得られることが確認できた。 As described above, {Li x (K 1−y Na y ) 1−x } (Nb 1−z−w Ta z Sb w ) O 3 , which is a base material of a piezoelectric ceramic made of an alkali metal-containing niobium oxide. On the other hand, it has been confirmed that by adding bismuth oxide and zinc oxide as sintering aids, a piezoelectric ceramic composed of a dense alkali metal-containing niobium oxide can be obtained stably by atmospheric pressure sintering.
Claims (3)
少なくとも酸化ビスマスと酸化亜鉛とを有し、
前記主成分に対して、前記酸化ビスマスは１．４ｗｔ％以上２．０ｗｔ％以下、前記酸化亜鉛は０．６ｗｔ％以上２．０ｗｔ％以下添加され、
１０５０℃以上１１００℃以下の温度で焼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。 {Li x (K 1-y Na y ) 1-x } (Nb 1-z-w Ta z Sb w ) O 3 (where 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 1, 0 ≦ z ≦ 0 .4, 0 ≦ w ≦ 0.2) as a sintering aid for use in the production of an alkali metal-containing niobium oxide,
Having at least bismuth oxide and zinc oxide ,
With respect to the main component, the bismuth oxide is added in an amount of 1.4 wt% to 2.0 wt%, and the zinc oxide is added in an amount of 0.6 wt% to 2.0 wt%.
A sintering aid for piezoelectric ceramics, which is fired at a temperature of 1050 ° C. or higher and 1100 ° C. or lower .
前記主成分に対して、焼結助剤として酸化ビスマスが１．４ｗｔ％以上２．０ｗｔ％以下、酸化亜鉛が０．６ｗｔ％以上２．０ｗｔ％以下添加され、
１０５０℃以上１１００℃以下の温度で焼成されることを特徴とするアルカリ金属含有ニオブ酸化物からなる圧電セラミックス。 {Li x (K 1-y Na y ) 1-x } (Nb 1-z-w Ta z Sb w ) O 3 (where 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 1, 0 ≦ z ≦ 0 .4, 0 ≦ w ≦ 0.2) as a main component.
With respect to the main component, bismuth oxide as a sintering aid is added in an amount of 1.4 wt% to 2.0 wt%, and zinc oxide is added in an amount of 0.6 wt% to 2.0 wt%.
A piezoelectric ceramic comprising an alkali metal-containing niobium oxide, which is fired at a temperature of 1050 ° C. or higher and 1100 ° C. or lower .
前記仮焼工程を経て得られた主成分の仮焼粉に対して、焼結助剤として酸化ビスマスを１．４ｗｔ％以上２．０ｗｔ％以下、酸化亜鉛を０．６ｗｔ％以上２．０ｗｔ％以下添加して混合する混合工程と、
前記混合工程で得られた混合紛を１０５０℃以上１１００℃以下の温度で焼成して焼結体とする焼成工程とを含むことを特徴とするアルカリ金属含有ニオブ酸化物からなる圧電セラミックスの製造方法。 {Li x (K 1-y Na y ) 1-x } (Nb 1-z-w Ta z Sb w ) O 3 (where 0 ≦ x ≦ 0.2, 0 ≦ y ≦ 1, 0 ≦ z ≦ 0 .4, 0 ≦ w ≦ 0.2),
With respect to the calcined powder of the main component obtained through the calcining step, bismuth oxide is 1.4 wt% or more and 2.0 wt% or less and zinc oxide is 0.6 wt% or more and 2.0 wt% as a sintering aid . A mixing step of adding and mixing below ,
A method of producing a piezoelectric ceramic comprising an alkali metal-containing niobium oxide, comprising a firing step of firing the mixed powder obtained in the mixing step at a temperature of 1050 ° C. to 1100 ° C. to obtain a sintered body. .
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