Piezoelectric ceramic composition

Abstract: A three-component piezoelectric ceramic composition having a large piezoelectric constant, a large electro-mechanical coupling coefficient, and high mechanical strength, composed of xPb(Ni w/3 Nb 1-w/3 )O₃-yPbZrO₃-zPbTiO₃, is adapted to place points representing the compositional proportions x, y, and z on lines connecting points A: (x = 0.75, y = 0.01, z = 0.24), B: (x = 0.55, y = 0.01, z = 0.44), C: (x = 0.05, y = 0.45, z = 0.50), and D: (x = 0.05, y = 0.60, z = 0.35) or in the compositional region bounded by the lines in a three-component composition diagram and set the value of w in the range from approximately 0.8 to 1.

Description: The present invention relates to a piezoelectric ceramic composition used for buzzers and piezoelectric actuator elements. Due to their large piezoelectric constant and large electro-mechanical coupling coefficient, Pb(Ni 1/3 Nb 2/3 )O 3 -PbZrO 3 -PbTiO 3 -based piezoelectric ceramics (PNN-PZ-PT), obtained by solid dissolving Pb(Ni 1/3 Nb 2/3 )O 3 in Pb(Zr, Ti)O 3 , a typical type of piezoelectric ceramics, are widely used for buzzers and piezoelectric actuator elements (JP-B-45-37907). A similar ceramic material is known from JP 0745883 A, JP 57145384 A and US 4765919. Not all PNN-PZ-PT-based ceramics, however, have satisfactory mechanical strength and thus may crack or chip when machined into a piezoelectric element, such as a buzzer. According to the present invention a piezoelectric ceramic composition is provided, which has a large piezoelectric constant and a large electro-mechanical coupling coefficient and offers satisfactory mechanical strength, thereby solving the above-described problem. A piezoelectric ceramic composition for the purpose of the specification is a three-component system composed of xPb(Ni w/3 Nb 1-w/3 )O 3 -yPbZrO 3 -zPbTiO 3 , wherein points representing the compositional proportions x, y, and z are on lines connecting points A: (x = 0.75, y = 0.01, z = 0.24), B: (x = 0.55, y = 0.01, z = 0.44), C: (x = 0.05, y = 0.45, z = 0.50), and D: (x = 0.05, y = 0.60, z = 0.35) and are in the compositional region bounded by the lines in the three-component composition diagram of FIG. 1, and the value of w ranges from 0.85 to 0.95. In other words, a PNN-PZ-PT-based piezoelectric ceramic composition of the present invention as claimed implies that the Ni-Nb ratio thereof is less than a stoichiometric ratio of 1/2. The piezoelectric ceramic composition is also characterized by up to fifteen molar percent of Pb atoms replaced by atoms of at least one element selected from the group of Ca, Sr, and Ba. Reducing the ratio of Ni to Nb to below the stoichiometric ratio of 1/2 as claimed causes the diameter of particles constituting ceramics to be reduced and the mechanical strength thereof to be increased. What is more, increased mechanical strength does not adversely affect the piezoelectric constant and the electro-mechanical coupling coefficient. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a three-component composition diagram showing the proportions of the components of a PNN-PZ-PT piezoelectric ceramic composition of the present invention. Referring now to embodiments, advantages of the present invention are specifically described below. A predetermined amount of components of a piezoelectric ceramic composition, such as PbO, TiO 2 , ZrO 2 , SrCO 3 , CaCO 3 , BaCO 3 , NiO, and Nb 2 O 5 , was measured, and water was added to the measured substances and mixed them using a ball mill. The resulting mixture was dried, incompletely calcined at about 700 to 900°C for about two hours, and water-ground using a ball mill to obtain an adjusted powder. Binders, such as water and polyvinyl alcohol, were added to the resulting adjusted powder, and then the mixture was pressed and calcined at about 1100 to 1300°C for approximately two hours to obtain piezoelectric ceramics of a predetermined composition. The piezoelectric ceramics were worked to prepare samples for three-point bending strength testing and electrical characteristic measurements. For instance, samples for three-point bending strength testing were prepared by forming some of the piezoelectric ceramics into 30 mm x 5 mm x 0.3 mm rectangles. Also, samples for electrical characteristic measurements were prepared by forming the remaining piezoelectric ceramics into disks 10 mm in diameter and 1 mm thick, polishing the disks, depositing silver electrodes onto both sides of the disks by baking, and polarizing the disks in insulating oil at about 80°C for 30 minutes, with an electric field with a strength of 2 to 3 kV/mm imposed on the oil. Comparison samples were formed from piezoelectric ceramics outside the scope of the present invention as claimed in the same way as the samples of the embodiment. The above-described samples of the embodiment and the comparison samples underwent three-point bending strength testing and measurements of the electro-mechanical coupling coefficient for vibration in a radius direction. The results are shown in Table 1. Sample No. x y z w A a Three-point bending strength N/cm 2 (kgf/cm 2 ) Electromechanical coupling coefficient Kp (%) *1 0.70 0.10 0.20 0.95 Sr 0.02 11270 (1150) 18.4 2 0.60 0.10 0.30 0.95 Sr 0.02 11172 (1140) 45.3 3 0.40 0.20 0.40 0.95 Sr 0.02 10486 (1070) 65.8 *4 0.30 0.20 0.50 0.95 Sr 0.02 10486 (1070) 17.8 5 0.20 0.40 0.40 0.95 Sr 0.02 10290 (1050) 62.3 *6 0.20 0.50 0.30 0.95 Sr 0.02 10192 (1040) 23.4 *7 0.03 0.50 0.47 0.95 Sr 0.02 8722 (890) 56.7 *8 0.40 0.20 0.40 1.00 Sr 0.02 8820 (900) 70.1 9 0.40 0.20 0.40 0.85 Sr 0.02 10486 (1170) 55.2 *10 0.40 0.20 0.40 0.80 Sr 0.02 12152 (1240) 32.4 *11 0.03 0.50 0.47 0.85 Sr 0.02 8918 (910) 51.2 12 0.20 0.40 0.40 0.95 - - 10388 (1060) 57.8 13 0.20 0.40 0.40 0.95 Sr Ba Ca 0.04 0.04 0.04 10486 (1070) 48.1 *14 0.20 0.40 0.40 0.95 Sr 0.20 10388 (1060) 29.7 In Table 1, symbols x, y, z, and w represent the molar proportions of components of xPb(Ni w/3 Nb 1-w/3 )O 3 -yPbZrO 3 -zPbTiO 3 , and symbols A and a represent the type of element replacing Pb (i. e., Sr, Ba, or Ca) and the molar percentage of the element, respectively. The asterisked marked sample numbers in the table indicate piezoelectric ceramics (comparison samples) outside the scope of the present invention as claimed. As shown in Table 1, a piece of piezoelectric ceramic (sample No. 8) whose w value is substantially 1 or more was found to be low in three-point bending strength, and a piece of piezoelectric ceramic (sample No. 10) whose w value is substantially 0.8 or less was found to have a low electro-mechanical coupling coefficient Kp. The electro-mechanical coupling coefficient Kp was found to be reduced if the percentage of Pb atoms replaced with those of at least one type of element selected among Ca, Sr, and Ba substantially exceeds 0.15 (15%) (sample No. 14). The electro-mechanical coupling coefficient Kp was found to be significantly reduced if the composition of PNN-PZ-PT is not as shown in Fig. 1 (samples No. 1, 4, 6, 7, and 11). Setting the value of w to below 1 was found to unsatisfactorily improve mechanical strength, particularly if in the compositional proportion of PNN, x is less than 0.05 (samples No. 7 and 11). As described above, having a large piezoelectric constant, a large electro-mechanical coupling coefficient Kp, and high mechanical strength, the piezoelectric ceramic composition of the present invention as claimed enables piezoelectric elements having advantages necessary for buzzers and piezoelectric actuator elements to be produced in high yield by inhibiting the occurrence of defects, such as cracks and chips, during machining operation.

Claims: A three-component piezoelectric ceramic composition composed of xPb xPb(Ni w/3 Nb 1-w/3 )O 3 -yPbZrO 3 -zPbTiO 3 , in which up to fifteen molar percent of Pb atoms are replaced with at least one element selected from the group of Ca, Sr and Ba, and x+y+z=1, wherein points representing the compositional proportions x, y and z are on lines connecting points A: (x = 0.75, y = 0.01, z = 0.24), B: (x = 0.55, y = 0.01, z = 0.44), C: (x = 0.05, y = 0.45, z = 0.50), and D: (x = 0.05, y = 0.60, z = 0.35) or in the compositional region bounded by those lines in a three-component composition diagram, and the value of w ranges from 0.85 to 0.95. The piezoelectric ceramic composition according to claim 1, wherein up to fifteen molar percent of said Pb are replaced with Sr. The piezoelectric ceramic composition according to claim 1, wherein up to fifteen molar percent of said Pb are replaced with a combination of Ca, Sr and Ba. The piezoelectric ceramic composition according to one of the claims 1-3, wherein x is 0.20-0.60. The piezoelectric ceramic composition according to one of the claims 1-4, wherein y is 0.10-0.40. The piezoelectric ceramic composition according to one of the claims 1-5, wherein z is 0.3 -0.4.

Inventors: HASE KIYOSHI, SHIRATSUYU KOSUKE, TOMONO KUNISABURO, HASE, KIYOSHI, SHIRATSUYU, KOSUKE, TOMONO, KUNISABURO, Hase, Kiyoshi, c/o Murata Man. Co., Ltd., Shiratsuyu, Kosuke, c/o Murata Man. Co., Ltd., Tomono, Kunisaburo, c/o Murata Man. Co., Ltd.
Applicants: MURATA MANUFACTURING CO, MURATA MANUFACTURING CO., LTD.
Application year: 1995
Main classification: H01L41
IPC codes: H01L41, C04B35