PIEZOELECTRIC OXIDE MATERIAL

Abstract: Disclosed is a piezoelectric oxide material comprising a basic composition having the general formula: (Pb 1-a Ca a )[(Me 1/3 Nb 2/3 ) x Ti 1-x )O₃ wherein Me is either one of Mg and Zn. 0.10 < X ≦ 0.30, and 0.10 < a ≦ 0.35, which is suitable for use in ultrasonic probes of various devices mentioned in the specification.

Description: Piezoelectric oxide material This invention relates to a piezoelectric oxide material. More particularly, it relates to a piezoelectric oxide material suitable for fabrication of piezoelectric ceramic vibrators and the like which are employed as probes in medical ultrasonic diagnosis systems, which have recently found wide-spread commercial utility, and ultrasonic flaw detecting apparatus adapted to locate defects, etc. in metals and the like. The ultrasonic conversion elements of these systems and apparatus use longitudinal-mode waves (K33 vibrations) of 0.5 to 10 MHz as vibration modes thereof. Since the efficiency of electroacoustics that converts electric energy to ultrasonic vibrations and ultrasonic vibrations to electric energy is proportional to the square of the electromechanical coupling factor K33, better sensitivity is available with a material having a greater K33 value. Since, however, it becomes more difficult to suppress occurrence of spurious vibrations due to the effect of transverse waves when the transverse-mode wave has a larger K31 value, a material having a large K33 value and small K31 value is therefore desired. Ultrasonic diagnosis systems, which are used most extensively these days, are of the pulse reflection system. In the pulse reflection system, it is necessary to transmit and receive short pulses if one wants to enhance the resolution. Accordingly, it is desired to lower the mechanical quality factor(Qm) of the probe material so that the breaking time of each pulse can be shortened. On the other hand, there is a recent trend to make the pulse drive circuit (i.e., pulser) of each ultrasonic diagnosis system operable over a wide band. Accordingly, it is now under way to lower the impedance of such a pulse drive circuit. Since the impedance matching has to be achieved between the material of a probe and its corresponding pulser circuit, there is an outstanding demand for the development of a piezoelectric material having a high dielectric constant of about 300 to 2000. As probe materials of the above sort, there have conventionally been used quartz, biNbO3, and composite ternary system ceramics such as barium titanate type ceramics and lead zirconium titanate type ceramics. Quartz and tiNbO3 are however unsuitable as probe materials of the above sort, because they have small electromechanical coupling factors (K33) and large Qm values. On the other hand, composite ternary system ceramics such as barium titanate type ceramics and PZT-type ceramics are accompanied by some limitations in machining them into vibrators in order to minimize the transverse effect of K31 since their K31 values, which are of vibration modes giving the transverse effect, are as high as 20 to 40 % and the K33/K31 ratios remain as low as 2 to 3, although their dielectric constants are high and their electromechanical coupling factors K33 are as high as 40 to 65 %. On the other hand, there have also been known materials baving K33/K31 ratios as great as 5 to 10, such as PbTiO3, PbNb2O6, etc. However, the dielectric constants of these materials are as low as 150 to 300, whereby making them difficult to meet the recent trend toward use of low impedance pulser circuits for ultrasonic diagnosis systems. Besides, PbTiO3 type materials and PbNb2O6 type materials have to be subjected to their poling processing at elevated temperatures and under high electric fields. These materials are thus difficult to provide large size vibrators due to breakdown which take place during such poling processing. This invention aims to solve the above-described drawbacks. Accordingly, it is an object of this invention to provide a piezoelectric ceramic material having a K33/K31 ratio of 5 or greater because its electromechanical coupling factor K33 is as high as 50 % or greater (up to about 60 %, practically) and its electromechanical coupling factor giving the transverse effect K31 is as low as 10 % or smaller (up to about 1 %, practically), a Qm value of 200 or smaller and a dielectric constant as great as 300 to 1200, facilitating its poling processing and suitable as a material for ultrasonic probes. According to this invention, there is provided a piezoelectric oxide material comprising a basic composition having the general formula: (Pbl-acaa) [ (Mel/3Nb2/3)xTil x ] 3 wherein Me is either one of Mg and Zn, 0.10 < x < 0.30, and 0.10 < a < 0.35. This invention will be described below in detail with reference to the accompanying drawings. In the drawings, which show illustrative characteristics of certain piezoelectric ceramic materials according to this invention; Fig. 1 is a curvilinear diagram showing characteristic features of a pulse-echo signal obtained by a flaw dectcting apparatus which employed a material of a Comparative Example; Fig. 2 is a curvilinear diagram illustrating characteristic features of a pulse-echo signal obtained by a defect detecting apparatus which employed a piezoelectric ceramic material according to this invention; and Fig. 3 is a curvilinear diagram showing the dependence of electromechanical coupling factors on poling voltage. In the basic composition of (Pb1Caa) [ (Me1/3Nb2/3)x TilxiO3 wherein Me is either one of Mg and Zn, the value a is limited to 0.10 C a < 0.35, preferably 0.20 < a < 0.30, because the coupling factor K33 and dielectric constant become 50 % or smaller and 300 or less respectively if a < 0.10, while, if a > 0.35, the Curie point becomes 150 0C or lower and it thus becomes more likely that the material would be depolarized during the cutting step upon machining the material into a probe after its poling or in the course of the soldering step of leads. The value x is limited to 0.10 < x < 0.30, preferably 0.15 < x < 0.25, because, whenx < 0.10, the ceramic has not only a small couplingfactor K33 of 50 % or small but also a low dielectric constant of 300 or lower and the impedance matching with the pulse drive circuit will become harder if the ceramic is employed to form a probe and, when x > 0.30, its Curie temperature becomes l500C or lower and its K31 value increases, thereby making the ceramic not different so much from PZT ceramics. The piezoelectric oxide material according to this invention can generally be produced with ease by the powder metallurgical process. For example, such raw material oxides as PbO, TiO2, CaCO3, MnCO3, ZnO, Nb203, MgO and the like are proportioned and then mixed well in a ball mill or the like. Here, the raw materials may be such compounds that can be converted to their corresponding oxides by their heating or the like. For example, hydroxides, carbonates, oxalates, etc. may also be used. Thereafter, the thus-proportioned mix is calcined at temperatures of about 600 to goo C, followed by its grinding in a ball mill or the like so as to provide a fine powder mix. Then, a binder such as water or polyvinyl alchol is added at a prescribed proportion to the fine powder mix and then dry-formed at a pressure of 0.5 to 2 tons/cm2 or so. The thus-formed compact is thereafter sintered at temperatures in the range of 1100 to 12000C or so. Since there is a danger that a part of PbO, one of the batch constituents, may evaporate during the sintering, it is preferred to conduct the sintering of the compact in a closed furnace. It is generally sufficient for the sintering of the compact to hold the compact for about 0.5 to. 3 hours at the maximum temperature. Accordingly, the present invention can bring about such effects as will be described below. First of all, conventional PZT materials and ternary system materials involved some problems due to spurious vibrations resulted from transverse vibrations (K31, Kp) when applied for fabrication of vibrators making use of longitudinal vibrations (K33, Kt), because the ratios of their longitudinal coupling factors K33 to transverse coupling factors K31 ranged from 2 to 3. However, the material according to this invention has small spurious vibrations and is thus advantageous from the practical viewpoint, since its longitudinal coupling factor K33 takes a value as large as 50 % or greater while its transverse coupling factor K31 is a small value of 10 % or lower. Secondly, the material of this invention has a relatively large dielectric constant which ranges from 300 to 1200, it facilitates the matching in impedance with the pulse drive circuit of an ultrasonic diagnosis system. Thirdly, the material of this invention has a small Qm value and hence permits fast attenuation for pulses, in other words, shotens the breaking times of pulses. It thus permits transmission and reception of short pulses, whereby it improves the resolution of an ultrasonic diagnosis system. Fourthly, the material of this invention permits to carry out its poling processing at 1000C and 30 to 50 KV/cm. Accordingly, large substrates may be fabricated with ease. As has been described above, the material of this invention can bring about effects that conventional piezoelectric materials were unable to achieve. Thus, the material of this invention is clearly superior to conventional piezoelectric materials. Examples of this invention will next be described. Examples A disk of 20 mm in diameter and 0.5 mm in thickness and a square rod of 2 mm wide, 2 mm high and 6 mm long were cut out from each sample, see Table 1, which had undergone its sintering. Silver paste was baked at 7000C on both surfaces of each of the disk and rod. They were thereafter subjected to a poling treatment by immersing them in silicone oil of 50 to l000C and applying a DC electric field of 20 to 40 KV/cm. Their piezoelectric characteristics were measured by the IRE standard circuit method. These measurement results are given in Table 1, along with the composition of samples. Table 1 Sample (Pb1-aCaa)[(Me1/3Nb2/3)xTi1-x103 Dielectric Coupling Coupling Curie a Me x constant factor factor K33/K31 Qm point mol(%) mol(%) K33(%) K31(%) Tc( C) Example 1 11 Mg 15 311 50.9 5.9 8.63 126 340 2 15 " 15 360 51.3 6.2 8.27 131 319 3 20 " 15 383 51.6 7.3 7.07 133 292 4 25 " 15 395 52.7 7.4 7.12 153 264 5 30 " 15 412 53.2 7.6 7.0 169 238 6 35 " 15 622 54.0 7.9 6.48 188 210 7 15 " 11 326 51.1 5.4 9.46 135 340 8 15 " 20 398 51.4 7.4 6.95 92 293 9 15 " 25 401 52.2 8.9 5.87 83 265 10 15 " 30 440 52.6 9.7 5.42 70 238 11 25 " 11 388 52.0 5.8 8.97 166 287 12 25 " 20 426 53.9 7.8 6.91 142 238 13 25 " 25 700 54.0 8.2 6.59 110 210 14 25 " 30 911 54.1 8.9 6.08 106 186 15 30 Mg 30 1200 54.0 9.6 56.3 70 160 16 11 Zn 15 306 50.1 5.2 9.63 133 360 17 15 " 15 343 50.8 5.7 8.91 139 339 18 20 " 15 350 51.4 6.3 8.16 140 311 Table 1 (continued) Sample (Pb1-aCaa)[(Me1/3Nb2/3)xTi1-x103 Dielectric Coupling Coupling Curie a Me x constant factor factor K33/K31 Qm point mol(%) mol(%) K33(%) K31(%) Tc( C) Example 19 25 Zn 15 367 51.7 6.6 7.83 159 281 20 30 " 15 411 52.3 7.6 6.93 170 258 21 35 " 15 603 52.8 7.6 6.95 192 231 22 15 " 11 320 50.8 5.1 9.96 137 360 23 15 " 20 387 50.9 6.3 8.07 90 311 24 15 " 25 399 51.6 7.6 6.79 82 285 25 15 " 30 430 52.0 8.6 6.05 69 258 Comparative example 1 10 Mg 10 270 47.3 5.6 3.92 223 223 2 0 " 5 201 32.2 8.8 3.66 306 480 3 40 " 30 1021 42.2 14.0 3.01 103 123 4 35 " 40 998 37.7 13.7 2.75 111 110 5 40 " 30 2900 - - - - 80 6 Pb(Ti0.53Zr0.47)O3+1.0mol% MnO2 1500 65 33.0 1.97 1010 325 7 Pb(Ti0.975La0.025)TiO3+1.0mol% MnO2 190 45 7.5 8.0 1050 470 Among these samples, the samples of Example 8 and Comparative Example 6 were used to fabricate disk-shaped vibrators having the diameter of 20 mm and resonance frequency of 2 MHz, respectively. Using the same backing material and coating material, they were assembled into ultrasonic probes under the same conditions. Certain characteristic features of pulse-echo signal obtained respectively from the use of the above ultrasonic probes will hereinafter be described. Figs. 1 and 2 are exemplary diagrams recorded upon locating defets in a steel material. The diagrams of Figs. 1 and 2 were obtained respectively by means of the probes resulted from the use of the materials of Comparative Example 6, and Example 8 respectively. The material of Comparative Example 6 had the high K31 value of 33 % and the great Qm value of 1010. Accordingly, as diagrammatically illustrated in Fig. 1, the input pulse 1 contains ringing 2 and the probe has a broad dead band. In addition, the echo signal 3 reflected by a flaw contains many peaks and the resolution has thus been lowered. On the other hand, the material of Example 8 has the small K31 value of 7.4 % and the low Qm value of 92. As illustrated in Fig. 2, the input pulse 1 contains almost no ringing and the probe has a narrow dead band. Besides, the echo signal 3 reflected by a flaw does not contain many peaks and the probe thus exhibits high resolution characteristics. The material according to this invention, which is similar to the material of Example 8, has a narrow dead band and is thus effective in locating flaws hidden under the surface of a steel material. Accordingly, the material of this invention is suitable for fabrication of ultrasonic probes having high resolution characteristics. Regarding the samples of Example 12 and Comparative Example, the dependence of their coupling factors K33 at 100 0C on poling electric fields are shown in Fig. 3 (Corresponding to the culçes a and b, respectively). As readily envisaged from the diagram, K33 is saturated at 30 KV/cm or higher in the case of the sample of Example 12 which pertains to the present invention whereas the conventional PbTiO3 type material of Comparative Example 7 was not saturated unless an electric field of 100 KV/cm or higher was applied. In addition, the K33 value of the sample of Comparative Example 7 was as low as 45 % or less. Thus, the poling of the material according to this invention has been singnificantly facilitated compared with the conventional PbTiO3 material and is thus useful for actual applications. Consequently, the piezoelectric ceramic material according to this invention is suitable for use in the folloging application fields: 1) Medical ultrasonic diagnosis systems: Conventional PZT-type materials and composite ternary system materials imposed some limitatios to the structures of vibrators due to spurious vibrations by transverse waves because they had large transverse coupling factors K31. The material according to this invention has a K31 value smaller than those of conventional PZT-type materials and is thus less susceptible of developing spurious vibrations due to transverse waves. Furtehrmore, the material according to this invention has a small Qm value, whereby allowing each pulse to attenuate promptly, in other words, making the breaking time of each pulse shorter and allowing transmission and reception of short pulses. Since the dielectric constant of the material of this invention is relatively large, i.e., ranges from 300 to 1200, it is rathcr easier to achieve the impedance matching between a pulser drive circuit and its corresponding probe. 2) Ultrasonic metal flaw detecting apparatus: More conventional X-ray flaw detecting apparatus have recently been replaced by ultrasonic flaw detecting apparatus which uses ultrasonic waves to locate weld flaws, voids, etc. in metals in the non-destructive fashion. PZT-type materials have heretofore been used as materials for their probes. Since they had large transverse K31 values, they were unable to btain waveforms of correct modes by reflected ultrasonic waves. The material according to this invention has a small K31 value and is thus advantageous for use in such an application. 3) Hydrophones and sonars: The material according to this invention is also suitable for vibrators used in the devices such as hydrophones and sonars. This is particularly becuase it has smaller transverse effect d31. The hydrostatic piezoelectric coefficient dh and the voltage coeffiecient gh which represent figures of merits of the hydropones can be calculated by the following equations: dh = d33 + 2d31 (1) gh = dh/e (2) In the conventional PZT-type material, the value of becomes smaller because the symbol of d31 is negative and therefore the sum of the doubled d31 and the d33 is small with the result that dh is 30 to 50 (x 10 12 C/N), and further because the specific dielectric constant is so large as to make the vlaue of gh ' small. On the other hand, in the material according to this invention which has large d33 and very small d31, the value of dh becomes larger and therefore the material is suitable for the material to be used for the hydrophones, etc. Moreover, the material accoridng to this invention has mechanical strength which is approximately twice larger than the conventional PZT material. Accordingly, it shows good performance even when the hydropones or sonars are operated at a high powder. As has been described above, it is readily appreciated that the piezoelectric ceramic material according to this invention permits to expand the application field to fields where use of conventional piezoelectric ceramic materials encountered one or more problems.

Claims: Claims: 1. A piezoelectric oxide material comprising a basic composition having the general formula: 1.Ca-) [(Mer@ Nb@@) Ti@)10@ wherein Me is either one of Mg and Zn, 0.10 < x < 0.30, and 0.10 < a < 0.35. 2. The piezoelectric oxide material according to Claim 1, wherein 0.15 < x < 0.25, and 0.20 < a < 0.30. 3. The piezoelectric oxide material according to Claim 1, wherein Me is Mg, 0.10 < x < 0.25 and 0.20 < a < 0.30. 4. The piezoelectric oxide material according to Claim 1, wherein Me is Zn, 0.l5 < x < 0.30 and 0.20 < a < 0.30. 5. The piezoelectric oxide material according to Claim 1, which is used for a probe of a medical ultrasonic diagnosis system. 6. The piezoelectric oxide material according to Claim 1, which is used for a probe of an ultrasonic metal flaw detecting apparatus. 7. The piezoelectric oxide material according to Claim 1, which is used for a vibrator of a hydrophone or a sonar.

Inventors: SUZUKI, SYUZI, TAKAHASHI, TAKASHI, YAMASHITA, YOUHACHI, YOSHIDA, SEIICHI
Applicants: KABUSHIKI KAISHA TOSHIBA
Application year: 1983
Main classification: C04B35
IPC codes: C04B35, H01B3, H01L41