JP4044944B2 - Piezoelectric ceramic materials - Google Patents

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JP4044944B2
JP4044944B2 JP2005153541A JP2005153541A JP4044944B2 JP 4044944 B2 JP4044944 B2 JP 4044944B2 JP 2005153541 A JP2005153541 A JP 2005153541A JP 2005153541 A JP2005153541 A JP 2005153541A JP 4044944 B2 JP4044944 B2 JP 4044944B2
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敦灼 董
佑樹 浜口
雄一 舞田
春男 山森
和利 高橋
良充 寺嶋
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Honda Electronics Co Ltd
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Description

本発明は、鉛を用いない圧電セラミックス材に関する。   The present invention relates to a piezoelectric ceramic material that does not use lead.

従来より、圧電セラミックス材としては、チタン酸バリウム(BaTiO3)、チタン酸鉛(PbTiO3)、チタン酸ジルコン酸鉛(Pb(ZrTi)O3)などが知られている。中でも、チタン酸ジルコン酸鉛を主組成とした圧電セラミックス材が多く使用されている。このチタン酸ジルコン酸鉛は、添加物を適宜選択することで、機械的品質係数Qmや比誘電率ε33 T0、圧電歪定数d33等を変化させうることなどから、洗浄機用や加工機用の超音波振動子や超音波センサ、圧力センサ、周波数フィルタなどに利用されている。 Conventionally, as a piezoelectric ceramic material, barium titanate (BaTiO 3 ), lead titanate (PbTiO 3 ), lead zirconate titanate (Pb (ZrTi) O 3 ), and the like are known. Among them, many piezoelectric ceramic materials mainly composed of lead zirconate titanate are used. Since this lead zirconate titanate can change the mechanical quality factor Qm, relative dielectric constant ε 33 T / ε 0 , piezoelectric strain constant d 33, etc. by appropriately selecting additives, it is used for a washing machine. And ultrasonic transducers for ultrasonic processing machines, ultrasonic sensors, pressure sensors, frequency filters, and the like.

しかし、チタン酸ジルコン酸鉛系の圧電セラミックス材は、焼成や焼結工程で鉛化合物が分解して鉛が大気中に放出されたり、粉末製造成形工程で鉛が水中に放出されたりするため公害対策を取る必要がある。また、廃棄物から鉛が溶出する虞もある。   However, lead zirconate titanate-based piezoelectric ceramic materials are polluted because lead compounds are decomposed during firing and sintering processes and lead is released into the atmosphere, and lead is released into water during powder manufacturing and molding processes. It is necessary to take measures. Moreover, there is a possibility that lead is eluted from the waste.

そこで近年、鉛を含まない圧電材料の研究開発がなされており、例えば、Bi0.5Na0.5TiO3(BNT)系の圧電セラミックス材が知られている(特許文献1)。 In recent years, therefore, research and development have been conducted on piezoelectric materials that do not contain lead. For example, a Bi 0.5 Na 0.5 TiO 3 (BNT) -based piezoelectric ceramic material is known (Patent Document 1).

特開平11−180769号公報JP-A-11-180769

しかしながら、特許文献1の圧電セラミックス材では、大きな変位を得るために、比誘電率ε33 T/ε0が大きく、かつK33,d33の大きないわゆるソフト系の圧電セラミックス材を得ることを企図している。このため、比誘電率ε33 T/ε0が大きいものの、柔らかいために機械的品質係数Qmが低いので、洗浄機用や加工機用のボルト締めランジュバン型超音波振動子や魚群探知機用などの超音波振動子に用いる素子とするには、適さないものであった。 However, in the piezoelectric ceramic material of Patent Document 1, in order to obtain a large displacement, it is intended to obtain a so-called soft piezoelectric ceramic material having a large relative dielectric constant ε 33 T / ε 0 and a large K 33 and d 33. is doing. For this reason, although the relative permittivity ε 33 T / ε 0 is large, the mechanical quality factor Qm is low due to its softness, so that it is a bolt-clamped Langevin type ultrasonic vibrator for a washing machine or a processing machine, a fish detector, etc. Therefore, it was not suitable for an element used in the ultrasonic vibrator.

本発明は、かかる問題点に鑑みてなされたものであって、無鉛の圧電セラミックス材でありながら、機械的品質係数Qmが高く、例えば超音波振動子などの使用に適する特性を有する圧電セラミックス材を提供することを目的とする。   The present invention has been made in view of such problems, and is a lead-free piezoelectric ceramic material that has a high mechanical quality factor Qm and has characteristics suitable for use, for example, an ultrasonic vibrator. The purpose is to provide.

その解決手段は、元素Bi,Na,Ba,Ti,Mn,Nb、及びOを含み、一般式:(1−x−y)(Bi0.5Na0.5)TiO3−xBaTiO3−y(Bi0.5Na0.5)(Mn1/3Nb2/3)O3で表される圧電セラミックス材であって、x,yが下記式(1)(2)を満たす圧電セラミックス材である。
0.01≦x≦0.20 …式(1)
0<y≦0.05 …式(2)
Its solution is, elements include Bi, Na, Ba, Ti, Mn, Nb, and O, the general formula: (1-x-y) (Bi 0.5 Na 0.5) TiO 3 -xBaTiO 3 -y (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2/3 ) O 3 , a piezoelectric ceramic material in which x and y satisfy the following formulas (1) and (2).
0.01 ≦ x ≦ 0.20 (1)
0 <y ≦ 0.05 Formula (2)

本発明の圧電セラミックス材は、元素Bi,Na,Ba,Ti,Mn,Nb、及びOを含む無鉛の圧電セラミックス材である。しかも、上述の一般式で表したときに、x、yが上述の条件式(1),(2)を満たす組成を有している。この圧電セラミックス材は、機械的品質係数Qmが高く、比誘電率ε33 T/ε0も比較的大きい値を有するなど、その他の特性も超音波振動子に用いた場合に適切な特性を備えるものとなる。 The piezoelectric ceramic material of the present invention is a lead-free piezoelectric ceramic material containing elements Bi, Na, Ba, Ti, Mn, Nb, and O. Moreover, when expressed by the above general formula, x and y have a composition satisfying the above conditional expressions (1) and (2). This piezoelectric ceramic material has other characteristics such as a high mechanical quality factor Qm and a relatively large value of relative dielectric constant ε 33 T / ε 0 when used in an ultrasonic vibrator. It will be a thing.

なお、x及びyは、(Bi0.5Na0.5)TiO3とBaTiO3と(Bi0.5Na0.5)(Mn1/3Nb2/3)O3の存在比(モル比)を示す係数である。 X and y are coefficients indicating the abundance ratio (molar ratio) of (Bi 0.5 Na 0.5 ) TiO 3 , BaTiO 3 and (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2/3 ) O 3 .

本発明にかかる圧電セラミックス材の実施例を比較例と共に説明する。
市販の高純度化学試薬Bi23、NaHCO3,BaCO3,TiO2,MnCO3,Nb25を、一般式:(1−x−y)(Bi0.5Na0.5)TiO3−xBaTiO3−y(Bi0.5Na0.5)(Mn1/3Nb2/3)O3となるように所定量秤量したのち混合し、公知の手法により、仮焼、粉砕、造粒、成形、焼結、寸法加工、電極焼付け、分極を行い、実施例1〜10及び比較例1〜6にかかる試料(圧電セラミックス材、12mmφ×0.8mmt)を作製した。
この試料について、インピーダンスアナライザ(HP4194:アジレント・テクノロジー社製)を用いて、機械的品質係数Qm等を計測した。その結果を表1に示す。
なお、各表及び以下において、(Bi0.5Na0.5)TiO3をBNT、BaTiO3をBT、(Bi0.5Na0.5)(Mn1/3Nb2/3)O3をBNMNと略記することがある。
Examples of the piezoelectric ceramic material according to the present invention will be described together with comparative examples.
Commercially available high-purity chemical reagents Bi 2 O 3 , NaHCO 3 , BaCO 3 , TiO 2 , MnCO 3 , and Nb 2 O 5 are represented by the general formula: (1-xy) (Bi 0.5 Na 0.5 ) TiO 3 —xBaTiO 3 −y (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2/3 ) O 3 is weighed in a predetermined amount, mixed and calcined, pulverized, granulated, molded, sintered, Dimensional processing, electrode baking, and polarization were performed to produce samples (piezoelectric ceramic material, 12 mmφ × 0.8 mmt) according to Examples 1 to 10 and Comparative Examples 1 to 6.
About this sample, mechanical quality factor Qm etc. were measured using impedance analyzer (HP4194: made by Agilent Technologies). The results are shown in Table 1.
In each table and below, (Bi 0.5 Na 0.5 ) TiO 3 may be abbreviated as BNT, BaTiO 3 as BT, and (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2/3 ) O 3 as BNMN. .

Figure 0004044944
Figure 0004044944

この表1に示す実施例1〜10及び比較例1〜6のうち、BNMNの存在比(モル比)yをy=0.001に固定した場合(実施例1〜5、比較例1,2)について、表2に整理して再掲する。   Among Examples 1 to 10 and Comparative Examples 1 to 6 shown in Table 1, when the abundance ratio (molar ratio) y of BNMN is fixed at y = 0.001 (Examples 1 to 5, Comparative Examples 1 and 2) ) Are shown again in Table 2.

Figure 0004044944
Figure 0004044944

この表2によれば、y=0.001に固定した場合、BTの存在比(モル比)xが、下記式(1)を満たす場合(実施例1〜5)には、電気機械結合係数ktをkt≧40%、機械的品質係数QmをQm≧300、比誘電率ε33 T/ε0をε33 T/ε0≧400、誘電損失tanδをtanδ≦1.2%、キュリー温度TcをTc≧250℃のいずれをも満たすことができる。かくして、上記式(1)を満たすならば、超音波振動子への利用に適する、電気機械結合係数kt、機械的品質係数Qm、比誘電率ε33 T/ε0やキュリー温度Tcが比較的大きく、各特性のバランスの良い圧電セラミックス材となることが判る。
0.01≦x≦0.20 …式(1)
According to Table 2, when y = 0.001, when the abundance ratio (molar ratio) x of BT satisfies the following formula (1) (Examples 1 to 5), the electromechanical coupling coefficient kt is kt ≧ 40%, mechanical quality factor Qm is Qm ≧ 300, relative permittivity ε 33 T / ε 0 is ε 33 T / ε 0 ≧ 400, dielectric loss tan δ is tan δ ≦ 1.2%, Curie temperature Tc Any of Tc ≧ 250 ° C. can be satisfied. Thus, if the above equation (1) is satisfied, the electromechanical coupling coefficient kt, the mechanical quality factor Qm, the relative dielectric constant ε 33 T / ε 0 and the Curie temperature Tc are relatively suitable for use in an ultrasonic transducer. It can be seen that the piezoelectric ceramic material has a large and well-balanced characteristic.
0.01 ≦ x ≦ 0.20 (1)

具体的には、0.01≦x≦0.20の範囲内で有れば、kt≧40%とできる。しかし、x=0.005(比較例1)の場合には、kt<40%となり、十分な特性が得られないことが判る。また、x=0.25(比較例2)の場合には、kt<40%となる上、Tc<250℃となり、十分な特性が得られないことが判る。   Specifically, if it is within a range of 0.01 ≦ x ≦ 0.20, kt ≧ 40% can be obtained. However, in the case of x = 0.005 (Comparative Example 1), kt <40%, which indicates that sufficient characteristics cannot be obtained. When x = 0.25 (Comparative Example 2), kt <40% and Tc <250 ° C., indicating that sufficient characteristics cannot be obtained.

ついで、表1に示す実施例1〜10及び比較例1〜6のうち、BTの存在比(モル比)xをx=0.15に固定した場合(実施例4,6〜10、比較例3,4)について、表3に整理して再掲する。   Next, among Examples 1 to 10 and Comparative Examples 1 to 6 shown in Table 1, when the abundance ratio (molar ratio) x of BT is fixed at x = 0.15 (Examples 4, 6 to 10, Comparative Examples) 3 and 4) are listed and re-displayed in Table 3.

Figure 0004044944
Figure 0004044944

この表3によれば、x=0.15に固定した場合、BNMNの存在比(モル比)yが、下記式(2)を満たす場合(実施例4,6〜10)には、電気機械結合係数ktをkt≧40%、機械的品質係数QmをQm≧300、比誘電率ε33 T/ε0をε33 T/ε0≧400、誘電損失tanδをtanδ≦1.2%、キュリー温度TcをTc≧250℃のいずれをも満たすことができる。かくして、上記式(2)を満たすならば、超音波振動子に適する、電気機械結合係数kt、機械的品質係数Qm、比誘電率ε33 T/ε0やキュリー温度Tcが比較的大きく、各特性のバランスの良い圧電セラミックス材となることが判る。
0<y≦0.05 …式(2)
According to Table 3, when x = 0.15 is fixed and the abundance ratio (molar ratio) y of BNMN satisfies the following formula (2) (Examples 4, 6 to 10), the electric machine Coupling coefficient kt is kt ≧ 40%, mechanical quality factor Qm is Qm ≧ 300, relative permittivity ε 33 T / ε 0 is ε 33 T / ε 0 ≧ 400, dielectric loss tan δ is tan δ ≦ 1.2%, Curie The temperature Tc can satisfy any of Tc ≧ 250 ° C. Thus, if the above equation (2) is satisfied, the electromechanical coupling coefficient kt, the mechanical quality factor Qm, the relative dielectric constant ε 33 T / ε 0 and the Curie temperature Tc, which are suitable for the ultrasonic vibrator, are relatively large, It can be seen that the piezoelectric ceramic material has a good balance of properties.
0 <y ≦ 0.05 Formula (2)

具体的には、0<y≦0.05の範囲内で有れば、kt≧40%とできる。しかし、y=0(比較例3)の場合には、kt<40%、Qm<300となり、十分な特性が得られないことが判る。この場合、特にQmが低い(Qm=112)。つまり、BNMNを添加しない比較例3に比して、わずかでも添加した(y>0とした)実施例4等では、Qmを大幅に上昇させ得ることが判る。また、BNMNを多く添加した比較例2(y=0.060)の場合にも、Qm<300となり、十分な特性が得られないことが判る。   Specifically, when it is within the range of 0 <y ≦ 0.05, kt ≧ 40% can be obtained. However, in the case of y = 0 (Comparative Example 3), it can be seen that kt <40% and Qm <300, and sufficient characteristics cannot be obtained. In this case, Qm is particularly low (Qm = 112). That is, it can be seen that Qm can be significantly increased in Example 4 or the like in which even a slight amount is added (y> 0) as compared with Comparative Example 3 in which BNMN is not added. Further, in the case of Comparative Example 2 (y = 0.060) in which a large amount of BNMN is added, it can be seen that Qm <300, and sufficient characteristics cannot be obtained.

さらに表1によれば、x=0.005,y=0、従って、1−x−y=0.995とした比較例5の試料では、Qm<300(具体的にはQm=107)となった。また、x=0.25,y=0.060、従って、1−x−y=0.690とした比較例6の試料では、Tc<250(具体的にはTc=235)となった。従って、上記の式(1)及び(2)を満たさない試料では、満足な特性を得られないことが、この比較例5,6からも判る。   Further, according to Table 1, in the sample of Comparative Example 5 in which x = 0.005, y = 0, and therefore 1−xy = 0.995, Qm <300 (specifically, Qm = 107). became. Further, in the sample of Comparative Example 6 in which x = 0.25, y = 0.060, and 1-xy = 0.690, Tc <250 (specifically, Tc = 235). Therefore, it can also be seen from Comparative Examples 5 and 6 that satisfactory characteristics cannot be obtained with samples that do not satisfy the above formulas (1) and (2).

かくして、この表1,2,3に示す結果より、一般式:(1−x−y)(Bi0.5Na0.5)TiO3−xBaTiO3−y(Bi0.5Na0.5)(Mn1/3Nb2/3)O3で表される圧電セラミックス材において、0.01≦x≦0.20とするとともに、0<y≦0.050とするのが好ましいことが判る。そして、この組成を有する圧電セラミックス材は、例えば、洗浄機用や加工機用のボルト締めランジュバン型超音波振動子などの強力超音波応用機器や、魚群探知機用などの超音波振動子に用いる素子として適するものである。 Thus, from the results shown in Tables 1, 2, and 3, the general formula: (1-xy) (Bi 0.5 Na 0.5 ) TiO 3 —xBaTiO 3 —y (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2 / 3 ) In the piezoelectric ceramic material represented by O 3, it is found that 0.01 ≦ x ≦ 0.20 and preferably 0 <y ≦ 0.050. The piezoelectric ceramic material having this composition is used for, for example, powerful ultrasonic application equipment such as a bolt-clamped Langevin type ultrasonic vibrator for a cleaning machine or a processing machine, or an ultrasonic vibrator for a fish detector or the like. It is suitable as an element.

以上において、本発明を表1(表2,3)に示す各実施例に即して説明したが、本発明は上記実施例に示す組成の圧電セラミックス材に限定されるものではなく、その要旨を逸脱しない範囲で、適宜変更して適用できることはいうまでもない。   In the above, the present invention has been described in accordance with each example shown in Table 1 (Tables 2 and 3). However, the present invention is not limited to the piezoelectric ceramic material having the composition shown in the above example, and the gist thereof is described. Needless to say, the present invention can be changed and applied as appropriate without departing from the scope of the present invention.

Claims (1)

元素Bi,Na,Ba,Ti,Mn,Nb、及びOを含み、
一般式:(1−x−y)(Bi0.5Na0.5)TiO3−xBaTiO3−y(Bi0.5Na0.5)(Mn1/3Nb2/3)O3で表される圧電セラミックス材であって、
x,yが下記式(1)(2)を満たす圧電セラミックス材。
0.01≦x≦0.20 …式(1)
0<y≦0.05 …式(2)
Including the elements Bi, Na, Ba, Ti, Mn, Nb, and O;
A piezoelectric ceramic material represented by the general formula: (1-xy) (Bi 0.5 Na 0.5 ) TiO 3 —xBaTiO 3 —y (Bi 0.5 Na 0.5 ) (Mn 1/3 Nb 2/3 ) O 3 And
A piezoelectric ceramic material in which x and y satisfy the following formulas (1) and (2).
0.01 ≦ x ≦ 0.20 (1)
0 <y ≦ 0.05 Formula (2)
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US8471442B2 (en) 2009-05-08 2013-06-25 Taiyo Yuden Co., Ltd. Piezoelectric ceramic, method for producing same, and piezoelectric device
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