JP2856147B2 - Piezoelectric ceramic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a piezoelectric ceramic composition, and more particularly to a piezoelectric ceramic composition capable of converting electric energy into mechanical vibration energy.

[0002]

2. Description of the Related Art Piezoelectric ceramic compositions capable of converting electric energy into mechanical vibration energy have been applied to products in the field of power, such as piezoelectric transformers, piezoelectric actuators and ultrasonic motors. For these applications, the piezoelectric ceramic composition is required to perform electro-mechanical energy conversion with high efficiency over a wide range from a small mechanical output to an extremely large mechanical output depending on the application. Therefore, for these applications, the piezoelectric ceramic composition is required to suppress the energy loss when converting electric energy to mechanical vibration energy. In addition, since a heat treatment step such as solder reflow is required when manufacturing a device, a high Curie point material is required.

Conventionally, as a piezoelectric ceramic composition having a high Curie point, lead ytterbium niobate [Pb (Yb
_1/2 Nb _1/2 ) O ₃ ] and lead titanate [PbTiO ₃ ]
Compositions consisting of components are known. However, when a high voltage is applied to this piezoelectric ceramic composition to obtain a large mechanical output, energy loss occurs due to internal friction caused by the movement of the ferroelectric domain wall, and the vibration level limit is It was at most about 0.1 m / s.

[0004] The term "vibration level" as used herein means an optical displacement as reported in the automatic measurement of the high power characteristic of a piezoelectric vibrator (Seiji Hirose, Institute of Electronics, Information and Communication Engineers, US92-3). The effective vibration velocity v ₀ can be calculated from the measurement of the maximum tip vibration amplitude ξm of the vibrator obtained from the measuring instrument and the resonance frequency f ₀ of the vibrator. As the vibration level increases, the heat generated by the internal energy loss of the vibrator generates room temperature. +2
The vibration speed at which the temperature reaches 0 ° C. is defined as the limit of the vibration level.

[0005]

The above-mentioned conventional piezoelectric ceramic composition is driven at a low vibration level (speed) with an upper limit of about 0.1 m / s, so that a large mechanical output is required. Application to power devices has been difficult.

[0006] The present invention has been made in view of the above points,
Ytterbium lead niobate [Pb (Yb _1/2 Nb _1/2 )
Piezoelectric ceramic having a three-component composition obtained by adding a predetermined composition to a two-component composition consisting of O ₃ ] and lead titanate [PbTiO ₃ ], thereby improving the vibration level limit v ₀ max four times or more. It is intended to provide a composition.

[0007]

In order to achieve the above object, a first aspect of the present invention is directed to a manganese lead antimonate [Pb (Mn _1/3 Sb _2/3 ) O ₃ ], Ytterbium lead niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ];
It consists of lead titanate [PbTiO ₃ ] and has a composition formula [Pb
(Mn _1/3 Sb _2/3 ) O ₃ ] x [Pb (Yb _1/2 Nb _1/2 )
O ₃ ] y [PbTiO ₃ ] z (where x + y + z = 1)
Wherein x, y, and z in the composition formula are x = 0.15, y = 0.6 in the ternary composition diagram.
0, a first point at z = 0.25, x = 0.03, y =
A second point at 0.72, z = 0.25, and x = 0.03,
a third point where y = 0.42, z = 0.55, and x = 0.1
5, characterized by having a composition defined on a line connecting the fourth point of y = 0.30 and z = 0.55 and in a region surrounded by the first to fourth points.

FIG. 1 shows a three-component composition diagram of the piezoelectric ceramic composition of the first invention. In the figure, a, b, c and d
Indicates the first, second, third, and fourth points, respectively. According to the composition in a region 1 (including on the line segment) surrounded by a line connecting these points a to d, The piezoelectric ceramic composition of the first invention is constituted.

[0009] The second invention according to claim 2 is a manganese compound.
Lead niobate [Pb (Mn _1/3 Nb _2/3 ) O ₃ ] and [Pb
(Yb _1/2 Nb _1/2 ) O ₃ ] and [PbTiO ₃ ], and has the composition formula [Pb (Mn _1/3 Nb _2/3 ) O ₃ ] x [Pb
A three-component composition represented by (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO ₃ ] z (where x + y + z = 1), wherein x, y and z in the composition formula are ternary compositions In the figure, x =
A first point of 0.03, y = 0.60, z = 0.37;
Second of x = 0.005, y = 0.625, z = 0.37
And x = 0.005, y = 0.485, z = 0.5
1 and x = 0.03, y = 0.46, z =
It has a composition defined on a line connecting the fourth point of 0.51 and an area surrounded by the first to fourth points.

FIG. 2 shows a three-component composition diagram of the piezoelectric ceramic composition of the second invention. In the figure, a, b, c and d
Indicates the first, second, third, and fourth points, respectively, and according to the composition in a region (including on the line segment) 2 surrounded by a line connecting these points a to d, The piezoelectric ceramic composition of the second invention is constituted.

A third aspect of the present invention is directed to a manganese lead tungstate [Pb (Mn _1/2 W _1/2 ) O ₃ ].
And [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] and [PbTi
O ₃ ] and a composition formula [Pb (Mn _1/2 W _1/2 ) O ₃ ] x
_{[Pb (Yb 1/2 Nb 1/2)} O 3] y [PbTiO 3] z
(Where x + y + z = 1), wherein x, y and z in the composition formula are represented by a ternary composition diagram:
a first point at x = 0.03, y = 0.60, z = 0.37, a second point at x = 0.005, y = 0.625, z = 0.37, and x = 0.005, y = 0.485, z =
A third point of 0.51, x = 0.03, y = 0.46,
It has a composition defined on a line connecting the fourth point of z = 0.51 and in a region surrounded by the first to fourth points.

FIG. 3 shows a three-component composition diagram of the piezoelectric ceramic composition of the third invention. In the figure, a, b, c and d
Indicates the first, second, third, and fourth points, respectively, and according to the composition in a region 3 (including on the line segment) surrounded by a line connecting these points a to d, The piezoelectric ceramic composition of the third invention is constituted.

A fourth aspect of the present invention is directed to a manganese-lead tantalate [Pb (Mn _1/3 Ta _2/3 ) O ₃ ].
And [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] and [PbTi
O ₃ ] and a composition formula [Pb (Mn _1/3 Ta _2/3 ) O ₃ ]
_{x [Pb (Yb 1/2 Nb 1/2} ) O 3] y [PbTiO 3] z
(Where x + y + z = 1), wherein x, y and z in the composition formula are represented by a ternary composition diagram:
a first point at x = 0.06, y = 0.57, z = 0.37, a second point at x = 0.005, y = 0.625, z = 0.37, and x = 0.005, y = 0.485, z =
A third point of 0.51, x = 0.06, y = 0.43,
It has a composition defined on a line connecting the fourth point of z = 0.51 and in a region surrounded by the first to fourth points.

FIG. 4 shows a three-component composition diagram of the piezoelectric ceramic composition of the fourth invention. In the figure, a, b, c and d
Indicates the first, second, third, and fourth points, respectively. According to the composition in a region 4 (including on the line segment) surrounded by a line connecting these points a to d, The piezoelectric ceramic composition of the fourth invention is constituted.

Further, Pb in the composition formula of the three-component composition is
It is characterized by being replaced by any one element of calcium, strontium and barium in an amount of 15 mol% or less, and Pb in the composition formula of the ternary composition is
It is characterized by being reduced within the range of 0.1 to 10 mol%.

In the present invention, lead ytterbium niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] and lead titanate [PbT
iO ₃ ], a manganese lead antimonate [Pb (Mn _1/3 Sb _2/3 ) O ₃ ] and a manganese lead niobate [Pb (Mn _1/2 Nb _1/2 ) O] ₃ ], manganese
Lead tungstate [Pb (Mn _1/2 W _1/2 ) O ₃ ] or manganese lead tantalate [Pb (Mn _1/3 Ta _2/3 ) O]
₃ ] wherein any one of the above compositions is added within a predetermined range.
Since the internal friction can be reduced by the composition of the component composition, a piezoelectric ceramic composition having a vibration level limit of 0.4 m / s or more can be obtained. Further, even if Pb in the composition formula of the above three-component composition is predetermined or reduced, a piezoelectric ceramic composition having a high relative dielectric constant and a vibration level limit of 0.4 m / s or more can be obtained.

[0017]

Next, embodiments of the present invention will be described with reference to the drawings. As a starting material to obtain a material of the present invention, lead oxide (PbO), titanium oxide (TiO _2), manganese carbonate (MnCO _3), antimony oxide (Sb
₂ O ₃ ), ytterbium oxide (Yb ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), tungsten oxide (WO ₃ ), tantalum oxide (TaO), calcium carbonate (CaCO ₃ ), strontium carbonate (SrCO ₃ ) and Barium carbonate (Ba
Each powder of CO ₃ ) was used. Here, MnCO ₃ , CaC
O ₃ , SrCO ₃ and BaCO ₃ are respectively MnO, Ca
The required amounts were obtained in terms of O, SrO and BaO.

The synthesis was divided into two stages. As the first step, first, ytterbium oxide and niobium oxide are wet-mixed with a ball mill for synthesizing YbNbO ₄ , and then the mixed powder is mixed.
Calcination was performed in the air at 125 ° C. for 1 hour to obtain YbNbO ₄ .
As a second step, the YbNbO ₄ and the remaining composition were mixed and calcined at 850 ° C. for 2 hours in the air. The calcined powder was pulverized, granulated, molded, and fired in the air at 1000 ° C. for 2 hours to obtain a sintered block having a length of 60 mm, a width of 30 mm, and a thickness of 10 mm.

This block is cut and polished to 43 × 7
After processing into a rectangular plate of × 1 mm ^t , silver electrodes were baked on both opposing main surfaces, and 4 kV / mm in 100 ° C. insulating oil.
Was applied for one hour to perform a polarization treatment. After standing at room temperature for 24 hours, the fundamental mode of the piezoelectric transverse effect length longitudinal vibration was excited by the constant current drive circuit, and the vibration level limit was measured. Vibration level was expressed by the effective vibration velocity v ₀ of the following formula can be calculated from measurements of the resonance frequency f ₀ of the maximum tip vibration amplitude ξm the vibrator of the vibrator resulting from the optical displacement measuring instrument.

V ₀ = {2πf ₀ } m (1) The vibration level (speed) limit is a temperature induced by internal energy loss of the vibrator by measuring the temperature of a thermocouple provided at a node of vibration of the piezoelectric vibrator. increasing the vibration speed (temperature and the difference between the room temperature of the vibrator) [Delta] T is 20 ° C. _{v 0max}
And this was taken as the vibration level limit.

First, manganese lead antimonate [Pb
(Mn _1/3 Sb _2/3 ) O ₃ ] and ytterbium.
Lead niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ];
It consists of lead titanate [PbTiO ₃ ] and has a composition formula [Pb
(Mn _1/3 Sb _2/3 ) O ₃ ] x [Pb (Yb _1/2
Nb _1/2 ) O ₃ ] y [PbTiO ₃ ] z (where x
+ Y + z = 1) Table 1 shows the correlation among the main component mixture ratio, the Curie temperature, the relative dielectric constant, and the vibration level limit of the three-component composition represented by + y + z = 1). In Table 1, * written on the right of the sample number indicates 3 mol% ≦ x ≦ 15 mol% and 30 mol% ≦
The sample number is out of the range of y ≦ 72 mol% and 25 mol% ≦ z ≦ 55 mol%.

[0022]

[Table 1] In addition, manganese lead niobate [Pb (Mn _1/3 Nb
_2/3 ) O ₃ ] and ytterbium lead niobate [Pb
(Yb _1/2 Nb _1/2 ) O ₃ ] and lead titanate [Pb
TiO ₃ ] and a composition formula [Pb (Mn _1/3 Nb)
_2/3 ) O ₃ ] x [Pb (Yb _1/2 Nb _1/2 )
O ₃ ] y [PbTiO ₃ ] z (where x + y + z =
Table 2 shows the correlation among the main component mixing ratio, Curie temperature, relative dielectric constant and vibration level limit of the three-component composition represented by 1). In Table 2, * on the right side of the sample number indicates 0.
5 mol% ≦ x ≦ 3 mol%, 46 mol% ≦ y ≦ 6
The sample numbers are out of the range of 2.5 mol% and 37 mol% ≦ z ≦ 51 mol%.

[0023]

[Table 2] In addition, manganese lead tungstate [Pb (Mn _1/3
W _2/3 ) O ₃ ] and ytterbium lead niobate [P
b (Yb _1/2 Nb _1/2 ) O ₃ ] and lead titanate [P
bTiO ₃ ] and a composition formula [Pb (Mn _1/3 W
_2/3 ) O ₃ ] x [Pb (Yb _1/2 Nb _1/2 )
O ₃ ] y [PbTiO ₃ ] z (where x + y + z =
Table 3 shows the correlation among the main component mixing ratio, Curie temperature, relative permittivity, and vibration level limit of the three-component composition represented by 1). In Table 3, the asterisk (*) to the right of the sample number indicates a value of 0.
5 mol% ≦ x ≦ 3 mol%, 46 mol% ≦ y ≦ 6
The sample numbers are out of the range of 2.5 mol% and 37 mol% ≦ z ≦ 51 mol%.

[0024]

[Table 3] In addition, manganese lead tantalate [Pb (Mn _1/3 Ta)
_2/3 ) O ₃ ] and ytterbium lead niobate [Pb
(Yb _1/2 Nb _1/2 ) O ₃ ] and lead titanate [Pb
TiO ₃ ] and a composition formula [Pb (Mn _1/3 Ta)
_2/3 ) O ₃ ] x [Pb (Yb _1/2 Nb _1/2 )
O ₃ ] y [PbTiO ₃ ] z (where x + y + z =
Table 4 shows the correlation among the main component mixing ratio, Curie temperature, relative dielectric constant and vibration level limit of the three-component composition represented by 1). In Table 4, * on the right of the sample number indicates 0.
5 mol% ≦ x ≦ 6 mol%, 43 mol% ≦ y ≦ 6
The sample numbers are out of the range of 2.5 mol% and 37 mol% ≦ z ≦ 51 mol%.

[0025]

[Table 4] Here, in Tables 1 to 4 and Tables 5 to 16 described below,
PMS, PMN, PMW, PMT, PYN, PT each manganese, antimony, lead _{[Pb (Mn 1/3} Sb
_2/3 ) O ₃ ], manganese lead niobate [Pb (Mn)
_1/3 Nb _2/3 ) O ₃ ], manganese lead tungstate [Pb (Mn _1/3 W _2/3 ) O ₃ ], manganese lead tantalate [Pb (Mn _1/3 Ta _2/3 ) O ₃ ], ytterbium lead niobate [Pb (Yb _1/3 Nb
_2/3 ) O ₃ ] and lead titanate [PbTiO ₃ ].

Next, the reasons for limiting the compounding ratio of each of the above three-component compositions will be described with reference to Tables 1 to 4. First, PMS, PMN, PMW or PM
The blending ratio x of T (expressed in%) is 3 mol% ≦ x ≦ 15 mol% in Table 1, 0.5 mol% ≦ x ≦ 3 mol% in Tables 2 and 3, respectively, and 0.5 mol in Table 4. % ≦ x ≦ 6 mol% is determined because the mixing ratio is 0 mol% (for example, sample numbers 1 to 4 in Table 1).
), The vibration level limit is low because the loss due to internal friction is large due to the movement of the ferroelectric domain wall, while 15 mol% in Table 1 and 3 mol in Tables 2 and 3
%, And in Table 4, when it exceeds 6 mol%, a heterophase such as pyrochlore is formed, thus causing an elastic loss.

In Table 1, the mixing ratio y of PYN (expressed in%) is 30 mol% ≦ y ≦ 72 mol.
%, In Tables 2 and 3, respectively, 46 mol% ≦ y
≦ 62.5 mol%, and in Table 4, 43 mol% ≦ y
The reason for setting ≦ 62.5 mol% is that if the ratio is out of this range, the ability to convert electrical energy into mechanical energy is extremely reduced, and the vibration level limit is reduced.

The mixing ratio z of PT (however, expressed in%) is given by x + y + z = 1 if the mixing ratio x of any one of PMS, PMN, PMW and PMT and the mixing ratio y of PYN are determined. It is inevitably determined from the following formula. From the above, in Tables 1 to 4, the samples with the sample numbers without * are samples having a high relative dielectric constant and a high vibration level limit, and are thereby driven at a high vibration level or a large amplitude. Application to

Next, in Tables 1 to 4, the constitutions of the three-component compositions (samples 3 to 4 in the regions 1 to 4 and the boundary lines in FIGS. 1 to 4) indicated by the sample numbers without * are shown. A case where lead (Pb) as a component is replaced with calcium (Ca), strontium (Sr) and barium (Ba) will be described.

The following Tables 5, 6 and 7 show the composition formula [Pb (Mn _1/3 Sb _2/3 )] in region 1 and the boundary line in FIG.
O ₃ ] x [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO
₃ ] Lead (Pb), which is a component of the three-component composition represented by z (where x + y + z = 1), is replaced with calcium (C
a), the correlation between the main component mixture ratio and the vibration level limit in the case of substitution with strontium (Sr) and barium (Ba) are shown in Table 8, Table 9 and Table 10 in the composition formula on region 2 and the boundary line in FIG. [Pb (Mn _1/3 Nb _2/3 ) O ₃ ] x [Pb
(Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO ₃ ] z (where x + y + z = 1), wherein Pb, which is a component of the ternary composition, is replaced by Ca, Sr and Ba 2 shows the correlation between the main component mixing ratio and the vibration level limit.

Tables 11, 12 and 13 show the composition formula [Pb (Mn _1/2 W _1/2 )] on the region 3 and the boundary in FIG.
O ₃ ] x [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO
₃ ] shows the correlation between the main component mixing ratio and the vibration level limit when Pb, which is a component of the three-component composition represented by z (x + y + z = 1), is substituted with Ca, Sr, and Ba; Tables 14, 15, and 16 show the composition formula [Pb (Mn _1/3 Ta _2/3 ) O ₃ ] on the region 4 and the boundary line in FIG.
_{x [Pb (Yb 1/2 Nb 1/2} ) O 3] y [PbTiO 3] z
(However, the correlation of the main component mixing ratio and the vibration level limit when Pb which is a component of the three-component composition represented by (x + y + z = 1) is substituted with Ca, Sr and Ba) is shown. In Tables 5 to 16, * on the right of the sample number indicates a sample number in which Pb was replaced with Ca, Sr or Ba in an amount larger than 15 mol%.

[0032]

[Table 5]

[0033]

[Table 6]

[0034]

[Table 7]

[0035]

[Table 8]

[0036]

[Table 9]

[0037]

[Table 10]

[0038]

[Table 11]

[0039]

[Table 12]

[0040]

[Table 13]

[0041]

[Table 14]

[0042]

[Table 15]

[0043]

[Table 16] As can be seen from the above Tables 5 to 16, the Pb of each compound
Can be replaced with Ca, Sr or Ba, or even if Pb is reduced, a high vibration level limit can be obtained. However, when Pb is further replaced with an excessive amount of Ca, Sr or Ba, the piezoelectricity decreases. The efficiency of the electrical-mechanical energy conversion is greatly reduced. Also, when the excess Pb is reduced, the vibration level is reduced due to the generation of a different phase and the reduced piezoelectricity. Therefore, the practical range of the composition is limited to 15 mol% or less of the above-mentioned Ca, Sr or Ba for the substitution amount of Pb, and to the range of 0.1 to 10 mol% for the reduction amount of Pb.

[0044]

As described above, according to the present invention,
Since a high dielectric constant and a vibration level limit of 0.4 m / s or more can be obtained, it can be applied to a piezoelectric device driven at a significantly higher vibration level or a larger amplitude than in the past, and its industrial value is Very large.

[Brief description of the drawings]

FIG. 1 is a three-component composition diagram of a piezoelectric ceramic composition of the first invention.

FIG. 2 is a three-component composition diagram of the piezoelectric ceramic composition of the second invention.

FIG. 3 is a three-component composition diagram of the piezoelectric ceramic composition of the third invention.

FIG. 4 is a diagram showing a three-component composition of the piezoelectric ceramic composition of the fourth invention.

[Explanation of symbols]

 1, 2, 3, 4 area

Claims (6)

(57) [Claims] 1. A manganese lead antimonate [Pb (Mn)
_1/3 Sb _2/3 ) O ₃ ], lead ytterbium niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ], and lead titanate [Pb
TiO ₃ ] and a composition formula [Pb (Mn _1/3 Sb _2/3 )
O ₃ ] x [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO
₃ ] A three-component composition represented by z (where x + y + z = 1), wherein x, y, and z in the composition formula are x = y in the ternary composition diagram.
A first point of 0.15, y = 0.60, z = 0.25;
A second point at x = 0.03, y = 0.72, z = 0.25 and a third point at x = 0.03, y = 0.42, z = 0.55
And the composition defined on a line connecting the fourth point of x = 0.15, y = 0.30 and z = 0.55, and in a region surrounded by the first to fourth points. A piezoelectric ceramic composition comprising: 2. Manganese lead niobate [Pb (Mn _1/3
Nb _2/3 ) O ₃ ] and ytterbium lead niobate [Pb
(Yb _1/2 Nb _1/2 ) O ₃ ] and lead titanate [PbTi
O ₃ ] and a composition formula [Pb (Mn _1/3 Nb _2/3 ) O ₃ ]
_{x [Pb (Yb 1/2 Nb 1/2} ) O 3] y [PbTiO 3] z
(Where x + y + z = 1), wherein x, y, and z in the composition formula are x = y in a ternary composition diagram.
A first point of 0.03, y = 0.60, z = 0.37;
Second of x = 0.005, y = 0.625, z = 0.37
And x = 0.005, y = 0.485, z = 0.5
1 and x = 0.03, y = 0.46, z =
A piezoelectric ceramic composition having a composition defined on a line connecting a fourth point of 0.51 and an area surrounded by the first to fourth points. 3. Manganese lead tungstate [Pb (M
n _1/2 W _1/2 ) O ₃ ], lead ytterbium niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ], and lead titanate [Pb
TiO ₃ ] and a composition formula [Pb (Mn _1/2 W _1/2 )
O ₃ ] x [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO
₃ ] A three-component composition represented by z (where x + y + z = 1), wherein x, y, and z in the composition formula are x = y in the ternary composition diagram.
A first point of 0.03, y = 0.60, z = 0.37;
Second of x = 0.005, y = 0.625, z = 0.37
And x = 0.005, y = 0.485, z = 0.5
1 and x = 0.03, y = 0.46, z =
A piezoelectric ceramic composition having a composition defined on a line connecting a fourth point of 0.51 and an area surrounded by the first to fourth points. 4. Manganese lead tantalate [Pb (Mn)
_1/3 Ta _2/3 ) O ₃ ], lead ytterbium niobate [Pb (Yb _1/2 Nb _1/2 ) O ₃ ], and lead titanate [Pb
TiO ₃ ] and a composition formula [Pb (Mn _1/3 Ta _2/3 )
O ₃ ] x [Pb (Yb _1/2 Nb _1/2 ) O ₃ ] y [PbTiO
₃ ] A three-component composition represented by z (where x + y + z = 1), wherein x, y, and z in the composition formula are x = y in the ternary composition diagram.
A first point of 0.06, y = 0.57, z = 0.37;
Second of x = 0.005, y = 0.625, z = 0.37
And x = 0.005, y = 0.485, z = 0.5
1 and x = 0.06, y = 0.43, z =
A piezoelectric ceramic composition having a composition defined on a line connecting a fourth point of 0.51 and an area surrounded by the first to fourth points. 5. The method of claim 1, wherein Pb in the composition formula of the three-component composition is
The piezoelectric ceramic composition according to any one of claims 1 to 4, wherein the composition is replaced with any one of calcium, strontium, and barium in an amount of 15 mol% or less. 6. Pb in the composition formula of the three-component composition,
The piezoelectric ceramic composition according to any one of claims 1 to 4, wherein the composition is reduced within a range of 0.1 to 10 mol%.