Piezoelectric porcelain

BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to piezoelectric porcelains suitably for a member of a piezoelectric actuator, a piezoelectric buzzer and so on which utilize piezoelectric distortion.
(2) Related Art Statement
Lead zirconate titanate has a large piezoelectric distortion and can be used at a high temperature. Moreover, if a part of zirconate or titanate is substituted by the other elements, various kinds of properties can be obtained. Particularly, piezoelectric porcelains of three component series having composition of PbTiO.sub.3 -PbZrO.sub.3 -Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3, in which a part of zirconate or titanate is substituted by magnesium and niobium, has a relatively large piezoelectric constant d.sub.31.
Recently, in fields of precision machines, an optical instruments and so on, precise position control is needed. To this end, a piezoelectric element utilizing a piezoelectric distortion has been developed. As for such elements, a piezoelectric porcelain having a high piezoelectric constant d.sub.31 is desired so as to make a distortion amount of the element larger. However, from the point of view mentioned above, a piezoelectric constant d.sub.31 of the piezoelectric porcelain of three component series having a composition of PbTiO.sub.3 -PbZrO.sub.3 -Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 mentioned above is -225 pm/V and thus it is not sufficient for this purpose.
Further, in Japanese Patent Laid-Open Publication No. 3-40964, it is disclosed that an excellent property such as a piezoelectric constant d.sub.31 =-307.9 pm/V can be realized in a piezoelectric porcelain of three component series having a composition of Pb(Mg.sub.1/3 Nb.sub.2/3).sub.0.225 (Ni.sub.1/3 Ta.sub.2/3).sub.0.15 Ti.sub.0.375 Zr.sub.0.25 O.sub.3.
However, in the piezoelectric porcelain having the composition disclosed in Japanese Patent Laid-Open Publication No. 3-40964, a Curie point is 177.degree. C. which is very low. If the Curie point of the piezoelectric porcelain is low in a piezoelectric element, a limit of temperature, to which the piezoelectric porcelain is driven, becomes low. That is to say, if a Curie point of the piezoelectric porcelain is low, the following disadvantages occur.
Generally, since a piezoelectric porcelain after firing shows no piezoelectricity, it is necessary to perform a poling thereto under applying a DC voltage. However, if the piezoelectric porcelain after the poling mentioned above is once used at a temperature above a Curie point, the piezoelectric porcelain shows no piezoelectricity again. Therefore, it is necessary to perform a poling again for the piezoelectric porcelain. In this manner, the piezoelectric porcelain having a composition of Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 -Pb(Ni.sub.1/3 Ta.sub.2/3)O.sub.3 -PbTiO.sub.3 -PbZrO.sub.3 has a high piezoelectric property, but the use of the piezoelectric porcelain mentioned above is limited to low temperatures.
SUMMARY OF THE INVENTION
An object of the invention is to eliminate the drawbacks mentioned above, and to provide a piezoelectric porcelain of three component series in which a piezoelectric constant d.sub.31 is improved.
According to a first aspect of the invention, piezoelectric porcelains have a composition of aPb[Mg.sub.1/3 (Nb.sub.1-X Ta.sub.X).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, coefficients a, b and c being mol % and a+b+c=100, wherein said coefficients a, b and c and a value X satisfy following conditions (1).about.(4);
15.ltoreq.a.ltoreq.45 (1)
32.ltoreq.b.ltoreq.45 (2)
10.ltoreq.c.ltoreq.50 (3)
0.1.ltoreq.X.ltoreq.0.9 (4).
Another object of the invention is to eliminate the drawbacks mentioned above, and to provide a piezoelectric porcelain in which a piezoelectric constant d.sub.31 is improved and also a high Curie point can be maintained.
According to a second aspect of the invention, piezoelectric porcelains have a composition of aPb[(Mg.sub.1-X Ni.sub.X).sub.1/3 (Nb.sub.1-Y Ta.sub.Y).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, coefficients a, b and c being mol % and a+b+c=100, wherein said coefficients a, b and c and a value X satisfy following conditions (21).about.(26);
15.ltoreq.a.ltoreq.45 (21)
32.ltoreq.b.ltoreq.45 (22)
10.ltoreq.c.ltoreq.50 (23)
0.1.ltoreq.X.ltoreq.0.9 (24)
0.1.ltoreq.Y.ltoreq.0.9 (25)
Y-X.gtoreq.0.05 (26).
According to a third aspect of the invention, piezoelectric porcelains have a composition of aPb[(Mg.sub.1-X Ni.sub.X).sub.1/3 (Nb.sub.1-Y Ta.sub.Y).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, coefficients a, b and c being mol % and a+b+c=100, wherein said coefficients a, b and c and a value X satisfy following conditions (41).about.(46);
15.ltoreq.a.ltoreq.45 (41)
32.ltoreq.b.ltoreq.45 (42)
10.ltoreq.c.ltoreq.50 (43)
0.2.ltoreq.X.ltoreq.0.9 (44)
0.2.ltoreq.Y.ltoreq.0.9 (45)
X-Y.gtoreq.0.05 (46).
In the first aspect of the invention, the present inventors find that, in a piezoelectric porcelain having a composition of PbTiO.sub.3 -PbZrO.sub.3 -Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3, a relative dielectric constant of the piezoelectric porcelain is improved and a piezoelectric constant d.sub.31 of the piezoelectric porcelain is improved extra-ordinarily by substituting a part of niobium by tantalum.
In this case, if a substitution rate X of tantalum with respect to niobium is not larger than 0.1, an effect of tantalum substitution does not appear so much. Moreover, if a value X is not smaller than 0.9, a Curie point of the piezoelectric porcelain decreases.
Further, if the value X is increased, a piezoelectric constant d.sub.31 of the piezoelectric porcelain is improved gradually. Particularly, if the value X is larger than 0.3, it is effective for an improvement of the piezoelectric constant d.sub.31. Moreover, it is confirmed that, if the value X is smaller than 0.8, a Curie point of the piezoelectric porcelain becomes higher gradually. On this case, it is preferred that the coefficients a, b and c and the value X satisfy the following in equations (5).about.(8);
25.ltoreq.a.ltoreq.43 (5)
35.ltoreq.b.ltoreq.43 (6)
14.ltoreq.c.ltoreq.40 (7)
0.3.ltoreq.X.ltoreq.0.8 (8).
Furthermore, from the view point mentioned above, it is further effective if the value X is larger than 0.4, and a piezoelectric constant d.sub.31 is most improved if the value X is near 0.6. However, if the value X is not larger than 0.7, a decrease of a Curie point becomes larger. Therefore, in this case, it is further preferred that the coefficients a, b and c and the value X satisfy the following conditions (9).about.(12);
30.ltoreq.a.ltoreq.42 (9)
37.ltoreq.b.ltoreq.40 (10)
18.ltoreq.c.ltoreq.33 (11)
0.4.ltoreq.X.ltoreq.0.6 (12).
Moreover, if up to 10 atomic % of Pb is substituted by one or more metal elements selected from a group of strontium, calcium and barium, it is possible to improve a piezoelectric constant d.sub.31 more. If a substitution rate of the metal elements is larger than 3 atomic %, a piezoelectric constant d.sub.31 is most improved. From this view point, it is further preferred if the substitution rate is larger than 4 atomic %. However, if the substitution rate is not smaller than 8 atomic %, a Curie point of a piezoelectric porcelain is decreased gradually. Therefore, it is preferred that the substitution rate is smaller than 8 atomic % and it is further preferred that the substitution rate is smaller than 7 atomic %.
In the second aspect of the invention, the present inventors find that, in a piezoelectric porcelain having a composition of Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 -Pb(Ni.sub.1/3 Ta.sub.2/3)O.sub.3 -PbTiO.sub.3 -PbZrO.sub.3, both of a piezoelectric constant d.sub.31 and a Curie point of the piezoelectric porcelain are improved by substituting a part of magnesium by nickel and by substituting a part of niobium by tantalum simultaneously.
In this case, if values X and Y satisfy Y-X.gtoreq.0.05, a Curie point of the piezoelectric porcelain is improved, and also the piezoelectric porcelain having a particularly large piezoelectric constant d.sub.31 can be obtained.
In this case, if the values X and Y become larger, a Curie point of the piezoelectric porcelain is decreased generally, and a piezoelectric constant d.sub.31 thereof is improved. In addition, a piezoelectric constant d.sub.31 becomes larger if the values X and Y are in a range of 0.3.about.0.9, and it becomes even larger if the values X and Y are in a range of 0.4.about.0.8. However, if the values X and Y are not smaller than 0.9, a Curie point is decreased abruptly. From the view point of a Curie point, it is preferred that the values X and Y are smaller than 0.8, and it is further preferred that the values of X and Y are smaller than 0.6.
Therefore, it is preferred that the coefficients a, b and c and the values X and Y satisfy the following in equations (27).about.(31);
25.ltoreq.a.ltoreq.43 (27)
35.ltoreq.b.ltoreq.43 (28)
14.ltoreq.c.ltoreq.40 (29)
0.3.ltoreq.X.ltoreq.0.8 (30)
0.3.ltoreq.Y.ltoreq.0.8 (31).
Moreover, it is further preferred that the coefficients a, b and c and the values X and Y satisfy the following in equations (32).about.(36);
30.ltoreq.a.ltoreq.42 (32)
37.ltoreq.b.ltoreq.40 (33)
18.ltoreq.c.ltoreq.33 (34)
0.4.ltoreq.X.ltoreq.0.6 (35)
0.4.ltoreq.Y.ltoreq.0.6 (36).
Further, it is necessary to set a difference between X and Y larger than 0.05. In this case, it is preferred to set the difference larger than 0.1 so as to increase a piezoelectric constant d.sub.31. Moreover, from the point of view of preventing a decrease of a Curie point, it is further preferred to set the difference smaller than 0.4.
Furthermore, if up to 10 atomic % of Pb is substituted by one or more elements selected from a group of strontium, calcium and barium, it is possible to improve a piezoelectric constant d.sub.31 more. If a substitution rate of the metal elements is larger than 3 atomic %, a piezoelectric constant d.sub.31 is most improved. From this point of view, it is further preferred if the substitution rate is larger than 4 atomic %. However, if the substitution rate is not smaller than 8 atomic %, a Curie point of a piezoelectric porcelain is decreased gradually. Therefore, it is preferred that the substitution rate is smaller than 8 atomic % and it is further preferred that the substitution rate is smaller than 7 atomic %.
In the third aspect of the invention, the present inventors find that, in a piezoelectric porcelain having a composition of Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 -Pb(Ni.sub.1/3 Ta.sub.2/3)O.sub.3 -pbTiO.sub.3 -PbZrO.sub.3, both of a piezoelectric constant d.sub.31 and a Curie point of the piezoelectric porcelain are improved by substituting a part of magnesium by nickel and by substituting a part of niobium by tantalum simultaneously.
In this case, if values X and Y satisfy X-Y.gtoreq.0.05, a Curie point of the piezoelectric porcelain is improved, and also the piezoelectric porcelain having a particularly large piezoelectric constant d.sub.31 can be obtained.
In this case, if the values X and Y become larger, a Curie point of the piezoelectric porcelain is decreased generally, and a piezoelectric constant d.sub.31 thereof is improved. In addition, a piezoelectric constant d.sub.31 becomes larger if the values X and Y are in a range of 0.3.about.0.9, and it becomes even larger if the values X and Y are in a range of 0.4.about.0.8. However, if the values X and Y are not smaller than 0.9, a Curie point is decreased abruptly. From the view point of a Curie point, it is preferred that the values X and Y are smaller than 0.8, and it is further preferred that the values of X and Y are smaller than 0.6.
Therefore, it is preferred that the coefficients a, b and c and the values X and Y satisfy the following conditions (47).about.(51);
25.ltoreq.a.ltoreq.43 (47)
35.ltoreq.b.ltoreq.43 (48)
14.ltoreq.c.ltoreq.40 (49)
0.3.ltoreq.X.ltoreq.0.8 (50)
0.3.ltoreq.Y.ltoreq.0.8 (51).
Moreover, it is further preferred that the coefficients a, b and c and the values X and Y satisfy the following conditions (52).about.(56);
30.ltoreq.a.ltoreq.42 (52)
37.ltoreq.b.ltoreq.40 (53)
18.ltoreq.c.ltoreq.33 (54)
0.4.ltoreq.X.ltoreq.0.6 (55)
0.4.ltoreq.Y.ltoreq.0.6 (56).
Further, it is necessary to set a difference between X and Y larger than 0.05. In this case, it is preferred to set the difference larger than 0.1 so as to increase a piezoelectric constant d.sub.31. Moreover, from the point of view of preventing a decrease of a Curie point, it is further preferred to set the difference smaller than 0.4.
Furthermore, if up to 10 atomic % of Pb is substituted by one or more elements selected from a group of strontium, calcium and barium, it is possible to improve a piezoelectric constant d.sub.31 more. If a substitution rate of the metal elements is larger than 3 atomic %, a piezoelectric constant d.sub.31 is most improved. From this point of view, it is further preferred if the substitution rate is larger than 4 atomic %. However, if the substitution rate is not smaller than 8 atomic %, a Curie point of a piezoelectric porcelain is decreased gradually. Therefore, it is preferred that the substitution rate is smaller than 8 atomic % and it is further preferred that the substitution rate is smaller than 7 atomic %.

BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing a relation between a substitution rate X of tantalum with respect to niobium and a piezoelectric constant d.sub.31 and a Curie point of a piezoelectric porcelain according to a first aspect of the invention in a piezoelectric porcelain of three component series having a composition of PbTiO.sub.3 -PbZrO.sub.3 -Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 ;
FIG. 2 is a graph illustrating a relation between a substitution rate Y and a piezoelectric constant d.sub.31 and a Curie point of a piezoelectric porcelain according to a second aspect of the invention under such a condition that coefficients a, b and c are set in a range within the scope of the second aspect of the invention and also a substitution rate Y is varied from 0.0 to 1.0 while a substitute rate X is constant at 0.1;
FIG. 3 is a graph depicting a relation between a substitution rate X and a piezoelectric constant d.sub.31 and a Curie point of a piezoelectric porcelain according to a third aspect of the invention under such a condition that coefficients a, b and c are set in a range within the scope of the third aspect of the invention and a substitution rate X is varied from 0.5 to 1.0 while a substitution rate Y is constant at 0.4; and
FIG. 4 is a graph showing a relation between the substitution X and a piezoelectric constant d.sub.31 and a Curie point of the piezoelectric porcelain according to the third aspect of the invention under such a condition that the coefficients a, b and c are set in a range within the scope of the third aspect of the invention and the substitution rate X is varied from 0.2 to 1.0 while a substitution rate Y is constant at 0.2.

DESCRIPTION OF THE PREFERRED EMBODIMENTS
A method of producing piezoelectric porcelains according to the invention is not limited particularly. However, the following producing method is preferred. At first, raw materials of metal compound, preferably oxides, hydroxides or carbonates of metal elements are mixed in a ball mill or the like to obtain mixed powders having a composition within the scope of the invention. Then, the thus obtained mixed powders are calcined in the atmosphere at a temperature of 900.degree. C..about.1100.degree. C. to obtain a calcined body. The calcined body is crushed in the ball mill or the like and the crushed powders are pressed to obtain a formed body. Then, the thus obtained formed body is sintered at a temperature of 1200.degree. C..about.1300.degree. C. to obtain a sintered body. The thus obtained sintered body is worked to obtain a specimen having a predetermined dimension and a predetermined shape. Finally, electrodes are arranged on the specimen and the specimen with the electrodes is subjected to a poling for a piezoelectric porcelain. Of course, other producing methods can be applied freely in the present invention.
Hereinafter, experiments according to a first aspect of the invention will be explained.
EXPERIMENT 1
Raw material powders of PbO, MgO, Nb.sub.2 O.sub.5, Ta.sub.2 O.sub.5, TiO.sub.2, ZrO.sub.2 were mixed in a ball mill for 24 hours to obtain mixed powders having compositions shown in a Table 1. The thus obtained mixed powders were calcined in the atmosphere at 1000.degree. C. for 2 hours to obtain a calcined body. The thus obtained calcined body was crushed in the ball mill for 48 hours to obtain crushed powders. Then, the crushed powders were formed under a pressure of about 400 kg/cm.sup.2 by means of a press machine to obtain a formed body having a diameter of 20 mm and a thickness of 5 mm. The thus obtained formed body was sintered at a temperature of 1200.degree. C..about.1300.degree. C. for 2 hours to obtain a sintered body.
The thus obtained sintered body was worked to obtain a plate-like specimen having dimensions of 12 mm (length).times.3 mm (width).times.1 mm (thickness). Then, silver electrodes were arranged on the planes of the specimen, and the specimen with the silver electrodes was subjected to a poling in such a manner that a DC voltage of 2 kV/mm was applied to the specimen in a silicone oil having a temperature of 80.degree. C. With respect to the respective specimens after a poling, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 1 as well as coefficients a, b and c and a substitution rate X in a Pb[Mg.sub.1/3 (Nb.sub.1-X Ta.sub.X).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, wherein the coefficients a, b and c were mol % and a sum of the coefficients a, b and c was 100. In sample Nos. 1.about.17 in the Table 1, a substitution rate X of tantalum was varied while coefficients a, b and c were set in a range within the scope of the first aspect of the invention.
TABLE 1______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________1 15 40 45 0 136 312 Comparative example2 15 40 45 0.6 264 264 Present invention3 15 35 50 0 107 284 Comparative example4 15 35 50 0.6 240 236 Present invention5 25 40 35 0 179 270 Comparative example6 25 40 35 0.3 255 246 Present invention7 25 40 35 0.7 293 214 Present invention8 37.5 37.5 25 0 208 243 Comparative example9 37.5 37.5 25 0.1 275 235 Present invention10 37.5 37.5 25 0.4 336 211 Present invention11 37.5 30 32.5 1.0 182 142 Comparative example12 45 45 10 0 176 231 Comparative example13 45 45 10 0.4 255 199 Present invention14 45 32 23 0 194 213 Comparative example15 45 32 23 0.3 250 189 Present invention16 40 32 28 0 172 224 Comparative example17 40 32 28 0.4 252 192 Present invention______________________________________
By comparing the differences between the sample Nos. 1 and 2, between the sample Nos. 3 and 4, between the sample No. 5 and the sample Nos. 6 and 7, between the sample No. 8 and the sample Nos. 9 and 10, between the sample Nos. 12 and 13, between the sample Nos. 14 and 15 and between the sample Nos. 16 and 17, it is understood that a piezoelectric constant d.sub.31 is improved by substituting a part of niobium by tantalum. Moreover, as shown in the sample No. 11, if the substitution rate X was 1.0, it is understood that a piezoelectric constant d.sub.31 is decreased and a Curie point is also decreased extraordinarily.
EXPERIMENT 2
In the same manner as experiment 1, specimens according to sample Nos. 18.about.33 in a Table 2 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 2.
TABLE 2______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________18 10 45 45 0.4 215 294 Comparative example19 15 40 45 0.6 264 264 Present invention20 15 35 50 0.6 240 236 Present invention21 20 30 50 0.4 200 224 Comparative example22 25 25 50 0.8 210 234 Comparative example23 25 40 35 0.3 255 246 Present invention24 25 40 35 0.7 293 214 Present invention25 37.5 37.5 25 0.1 275 235 Present invention26 27.5 37.5 25 0.4 336 211 Present invention27 37.5 30 32.5 1.0 182 142 Comparative example28 45 45 10 0.4 255 199 Present invention29 50 32.5 17.5 0.4 254 163 Comparative example30 50 32.5 17.5 0.1 202 187 Comparative example31 55 40 5 0.4 214 159 Comparative example32 45 32 23 0.3 250 189 Present invention33 40 32 28 0.4 252 192 Present invention______________________________________
By comparing the a difference between the sample Nos. 18 and 19 in Table 2, it is understood that the sample No. 19 having a substitution rate X of 0.6 has an improved piezoelectric constant d.sub.31. by comparing the sample Nos. 20 and 21, it is understood that a piezoelectric constant d.sub.31 is decreased extraordinarily if the coefficient b is not larger than 32. The same result is also shown in the sample No. 22. In the sample Nos. 23.about.26, both of a piezoelectric constant d.sub.31 and a Curie point were preferred. However, in the sample No. 27, since the substitution rate X is 1.0, a piezoelectric constant d.sub.31 is decreased extraordinarily and a Curie point is also decreased.
By comparing sample Nos. 28 and 29, it is understood that a Curie point is decreased extraordinarily if the substitution rate X is not smaller than 45. Moreover, in the sample No. 30, since the substitution rate X is not smaller than 45, a Curie point is decreased extraordinarily and a piezoelectric constant d.sub.31 is decreased as compared with the sample No. 29 in response to a decrease of the substitution rate X. In the sample No. 31, since the coefficient a is increased to 55 and the coefficient c is not larger than 10, a Curie point is particularly decreased. In the sample Nos. 32 and 33, both of a piezoelectric constant d.sub.31 and a Curie point are preferred.
EXPERIMENT 3
In the same manner as experiment 1, according to sample Nos. 34.about.44 in Table 3 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results were shown in Table 3. In this experiment 3, the substitution rate X of tantalum was varied from 0 to 1.0 gradually while the coefficients a, b and c were maintained constant. From the results shown in the previous experiments, it was understand that the coefficients a, b and c in the Table 3 were substantially most suitable values. Moreover, the results of this experiment 3 were shown in FIG. 1, which showed a relation between the substitution rate X and a piezoelectric constant d.sub.31 or a Curie point.
TABLE 3______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________34 37.5 37.5 25 0 208 243 Comparative example35 37.5 37.5 25 0.1 275 235 Present invention36 37.5 37.5 25 0.2 305 227 Present invention37 37.5 37.5 25 0.3 322 219 Present invention38 37.5 37.5 25 0.4 336 211 Present invention39 37.5 37.5 25 0.5 344 203 Present invention40 37.5 37.5 25 0.6 351 195 Present invention41 37.5 37.5 25 0.7 342 187 Present invention42 37.5 37.5 25 0.8 330 179 Present invention43 37.5 37.5 25 0.9 312 171 Present invention44 37.5 37.5 25 1.0 285 163 Comparative example______________________________________
From the results shown in the Table 3, it is understood that a piezoelectric constant d.sub.31 is improved if the substitution rate X is larger than 0.1 and it is further improved if the substitution rate X is in a range of 0.3.about.0.8, more preferably 0.4.about.0.7. However, if the substitution rate X is not smaller than 0.7, a Curie point is particularly decreased. Therefore, it is preferred that the substitution rate X is smaller than 0.6. Moreover, in the case that the substitution rate X is 1.0 (i.e., all the niobium is substituted by tantalum), a piezoelectric constant d.sub.31 is decreased and also a Curie point is decreased to a range under 170.degree. C. as shown in the sample No. 44.
EXPERIMENT 4
In the manner as experiment 1, specimens according to sample Nos. 45.about.54 in Table 4 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 4. In this experiment 4, SrCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Sr.
TABLE 4______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________45 10 40 50 0.6 263 204 Comparative example46 20 40 40 0.4 299 192 Present invention47 25 50 25 0.4 242 206 Comparative example48 25 30 45 0.5 237 142 Comparative example49 37.5 47.5 15 0.6 273 153 Comparative example50 37.5 37.5 25 0.0 272 183 Comparative example51 37.5 37.5 25 0.3 325 159 Present invention52 37.5 37.5 25 1.0 302 103 Comparative example53 37.5 30 32.5 0.4 245 130 Comparative example54 50 35 15 0.4 291 110 Comparative example______________________________________
From results shown in the Table 4, if the substitution rate X of tantalum is set in a range of 0.1.about.0.9 under such a condition that the coefficients a, b and c are maintained constantly as shown in the Table 4, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 5
In the same manner as experiment 4, specimens according to sample Nos. 55.about.64 in Table 5 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point measured. The measuring results are shown in Table 5. In this experiment 5, CoCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Ca.
TABLE 5______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________55 10 40 50 0.6 270 194 Comparative example56 20 40 40 0.4 306 182 Present invention57 25 50 25 0.4 248 196 Comparative example58 25 30 45 0.5 243 132 Comparative example59 37.5 47.5 15 0.6 280 143 Comparative example60 37.5 37.5 25 0.0 279 173 Comparative example61 37.5 37.5 25 0.3 332 149 Present invention62 37.5 37.5 25 1.0 309 93 Comparative example63 37.5 30 32.5 0.4 252 120 Comparative example64 50 35 15 0.4 298 100 Comparative example______________________________________
From the results shown in Table 5, if the substitution rate X of tantalum is set in a range of 0.1.about.0.9 under such a condition that the coefficients a, b and c are maintained constant as shown in Table 5, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 6
In the same manner as experiment 4, specimens according to sample Nos. 65.about.74 in Table 6 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in the Table 6. In this experiment 6, BaCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Ba.
TABLE 6______________________________________ CurieComposition Piezoelectric pointSample a b c X constant d.sub.31 (.degree.C.) Remarks______________________________________65 10 40 50 0.6 262 209 Comparative example66 20 40 40 0.4 297 197 Present invention67 25 50 25 0.4 241 211 Comparative example68 25 30 45 0.5 236 147 Comparative example69 37.5 47.5 15 0.6 272 158 Comparative example70 37.5 37.5 25 0.0 270 188 Comparative example71 37.5 37.5 25 0.3 323 164 Present invention72 37.5 37.5 25 1.0 300 108 Comparative example73 37.5 30 32.5 0.4 244 135 Comparative example74 50 35 15 0.4 290 115 Comparative example______________________________________
From the results shown in Table 6, if the substitution rate X of tantalum is set in a range of 0.1.about.0.9 under such a condition that the coefficients a, b and c are maintained constant as shown in the Table 6, it is possible to improve both a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 7
In the previous experiments, use was made of oxide powders as raw material powders. In this experiment 7, use was made of hydroxide powders or carbonate powders of metal elements rather than oxide powders, and specimens were prepared in the same manner as the previous experiments. With respect to the specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. As a result, the specimens according to this experiment 7 have substantially the same piezoelectric constant d.sub.31 and a Curie point as those of the previous experiments.
As mentioned above, according to the first aspect of the invention, since a part of niobium in the piezoelectric porcelain having a composition of PbTiO.sub.3 -PbZrO.sub.3 -Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3 is substituted by tantalum, a piezoelectric constant d.sub.31 can be improved extraordinarily.
Hereinafter, experiments according to a second aspect of the invention will be explained.
EXPERIMENT 8
Raw material powders of PbO, MgO, NiO, Nb.sub.2 O.sub.5, Ta.sub.2 O.sub.5, TiO.sub.2, ZrO.sub.2 were mixed in a ball mill for 24 hours to obtain mixed powders having compositions shown in Table 7. The thus obtained mixed powders were calcined in the atmosphere at 1000.degree. C. for 2 hours to obtain a calcined body. The thus obtained calcined body was crushed in the ball mill for 48 hours to obtain crushed powders. Then, the crushed powders were formed under a pressure of about 400 kg/cm.sup.2 by means of a press machine to obtain a formed body having a diameter of 20 mm and a thickness of 5 mm. The thus obtained formed body was sintered at a temperature of 1200.degree. C..about.1300.degree. C. for 2 hours to obtain a sintered body.
The thus obtained sintered body was worked to obtain a plate-like specimen having a dimensions of 12 mm (length).times.3 mm (width).times.1 mm (thickness). Then, silver electrodes were arranged on the planes of the specimen, and the specimen with the silver electrodes was subjected to a poling in such a manner that a DC voltage of 2 kV/mm was applied to the specimen in a silicone oil having a temperature of 80.degree. C. With respect to the respective specimens after a poling, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 7 as well as coefficients a, b and c and substitution rates X and Y in aPb[Mg.sub.1-X Ni.sub.X).sub.1/3 (Nb.sub.1-Y Ta.sub.Y).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, wherein the coefficients a, b and c were mol % and a sum of the coefficients a, b and c was 100. In sample Nos. 101.about.118 in Table 7, substitution rates X and Y and the coefficients a, b and c were varied respectively.
TABLE 7______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________101 10 45 45 0.2 0.4 217 284 Comparative example102 15 40 45 0.3 0.7 260 241 Present invention103 15 35 50 0 0.5 202 244 Comparative example104 15 35 50 0.4 0.6 251 216 Present invention105 20 30 50 0.6 0.9 206 154 Comparative example106 25 25 50 0.1 0.1 163 285 Comparative example107 25 40 35 0.3 0.7 310 199 Present invention108 25 40 35 0.5 0.8 301 181 Present invention109 37.5 37.5 25 0.5 1.0 304 138 Comparative example110 37.5 37.5 25 0.2 0.5 345 193 Present invention111 37.5 37.5 25 0.4 0.6 366 175 Present invention112 37.5 30 32.5 0.9 1.0 168 97 Comparative example113 45 45 10 0.3 0.4 268 184 Present invention114 50 32.5 17.5 0.3 0.4 266 148 Comparative example115 50 32.5 17.5 0.1 0.9 240 118 Comparative example116 55 40 5 0.4 0.8 217 107 Comparative example117 45 32 23 0.2 0.4 273 171 Present invention118 40 32 28 0.3 0.4 266 177 Present invention______________________________________
If the sample Nos. 102, 103 and 104 are compared, it is understood that a piezoelectric constant d.sub.31 is decreased extraordinarily in the sample No. 103 in which the substitution rate X is 0 i.e. no nickel exists. In the sample No. 105 in which the coefficient b is out of the scope of the second aspect of the invention, it is understood that a piezoelectric constant d.sub.31 is decreased and a Curie point is also decreased. If the sample Nos. 106, 107 and 108 are compared, it is understood that a piezoelectric constant d.sub.31 is decreased extraordinarily in the sample No. 106 in which the substitution rates X and Y are identical, but, in the sample Nos. 107 and 108 in which the coefficients a, b and c are same as those of the sample No. 106, a piezoelectric constant d.sub.31 is larger than 300 pm/V. If the sample No. 109, 110, 111 and 112 are compared, it is understood that a Curie point is decreased extraordinarily in the sample No. 109 and thus the sample No. 109 has a problem for an actual use. In the sample No. 110 and 111, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are improved. In the sample No. 112 in which no niobium exists, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased extraordinarily.
In the sample No. 113, it is understood that a piezoelectric constant d.sub.31 is increased. In the sample Nos. 114, 115 and 116, it is understood that the coefficient a is larger than 50, but a Curie point is decreased extraordinarily. In the sample No. 117 and 118 having similar composition as that of the sample Nos. 114.about.116, both of a piezoelectric constant d.sub.31 and a Curie point are increased extraordinarily.
EXPERIMENT 9
In the same manner as the experiment 8, specimens according to sample Nos. 119.about.132 in Table 8 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results were shown in Table 8. In the experiment 9, the substitution rates X and Y were varied while the coefficients a, b and c were maintained constant within the scope of the second aspect of the invention.
TABLE 8______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________119 15 40 45 0.3 0.8 245 223 Present invention120 15 40 45 0.8 0.8 225 208 Comparative example121 15 35 50 0.2 0.6 247 226 Present invention122 15 35 50 0.2 0.2 188 258 Comparative example123 25 40 35 0.3 0.7 310 199 Present invention124 25 40 35 0.7 0.7 303 179 Comparative example125 37.5 37.5 25 0.1 0.9 299 166 Present invention126 37.5 37.5 25 0.8 0.8 308 139 Comparative example127 45 45 10 0.3 0.4 268 184 Present invention128 45 45 10 0.7 0.7 269 140 Comparative example129 45 32 23 0.1 0.6 296 160 Present invention130 45 32 23 0.6 0.6 300 135 Comparative example131 40 32 28 0.2 0.6 289 166 Present invention132 40 32 28 0.6 0.6 294 146 Comparative example______________________________________
If the sample Nos. 119 and 120 are compared, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are increased in the sample No. 119 in which the substitution rate Y is larger than the substitution rate X. If the sample Nos. 121 and 122 are compared, it is understood that a piezoelectric constant d.sub.31 is increased extraordinarily in the sample No. 121 in which a substitution rate Y of tantalum is larger than that of the sample No. 122. If the sample Nos. 123 and 124 are compared, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are improved largely in the sample No. 123 in which the substitution rate Y is larger than the substitution rate X. If the sample Nos. 127 and 128 are compared, it is understood that a Curie point is improved in the sample No. 127 according to the second aspect of the invention. If the sample Nos. 129 and 130 are compared, it is understood that a Curie point is decreased to a region under 150.degree. C. in the sample No. 130. If the sample Nos. 131 and 132 are compared, it is understood that a Curie point is decreased to a region under 150.degree. C. in the sample No. 132.
EXPERIMENT 10
In the same manner as experiment 8, specimens according to sample Nos. 133.about.144 in Table 9 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 9. In the experiment 9, the coefficients a, b and c were varied while the substitution rate X was maintained at 0.2 and the substitution rate Y was maintained at 0.4.
TABLE 9______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________133 10 40 50 0.2 0.4 222 270 Comparative example134 15 40 45 0.2 0.4 243 270 Present invention135 20 30 50 0.2 0.4 211 214 Comparative example136 25 25 50 0.2 0.4 225 256 Comparative example137 25 40 35 0.2 0.4 290 228 Present invention138 37.5 37.5 25 0.2 0.4 328 201 Present invention139 37.5 30 32.5 0.2 0.4 228 180 Comparative example140 45 45 10 0.2 0.4 265 189 Present invention141 50 32.5 17.5 0.2 0.4 263 153 Comparative example142 55 40 5 0.2 0.4 219 149 Comparative example143 45 32 23 0.2 0.4 273 171 Present invention144 40 32 28 0.2 0.4 262 182 Present invention______________________________________
If the sample Nos. 135, 136 and 137 are compared, it is understood that piezoelectric constants d.sub.31 of the sample Nos. 135 and 136, in which the coefficient b is not larger than 32, are decreased extraordinarily as compared with the sample No. 137. If the sample Nos. 138 and 139 are compared, it is understood that a piezoelectric constant d.sub.31 of the sample No. 139, in which the coefficient b is not larger than 32, is decreased extraordinarily. If the sample Nos. 140.about.144 are compared, it is understood that a Curie point of the sample No. 141, in which the coefficient a is larger than 45, is decreased largely as compared with that of the sample No. 140, 143 and 144 according to the second aspect of the invention. In the sample No. 142, in which the coefficient a is larger than 45 and the coefficient c is not larger than 10, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased extraordinarily.
EXPERIMENT 11
In the same manner as experiment 8, specimens according to sample Nos. 145.about.155 in Table 10 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 10. In the experiment 11, the substitution rate Y was varied while the coefficients a, b and c were maintained constantly within the scope of the second aspect of the invention and the substitution rate X is maintained at 0.1. Moreover, a relation between the substitution rate Y and a piezoelectric constant d.sub.31 or a Curie point is shown in FIG. 2.
TABLE 10______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________145 37.5 37.5 25 0.1 0 221 238 Comparative example146 37.5 37.5 25 0.1 0.1 235 230 Comparative example147 37.5 37.5 25 0.1 0.2 307 222 Present invention148 37.5 37.5 25 0.1 0.3 323 214 Present invention149 37.5 37.5 25 0.1 0.4 340 206 Present invention150 37.5 37.5 25 0.1 0.5 348 198 Present invention151 37.5 37.5 25 0.1 0.6 356 190 Present invention152 37.5 37.5 25 0.1 0.7 345 182 Present invention153 37.5 37.5 25 0.1 0.8 333 174 Present invention154 37.5 37.5 25 0.1 0.9 317 166 Present invention155 37.5 37.5 25 0.1 1.0 268 158 Comparative example______________________________________
From the results shown in the Table 10, it is understood that, in the samples having the substitution rate Y of 0.2.about.0.9, a piezoelectric constant d.sub.31 is increased largely to a level of more than 300 pm/V and also a Curie point is increased to a level more than 166.degree. C. In the sample No. 145 in which the substitution rate Y is 0, it is understood that a piezoelectric constant d.sub.31 is decreased. Moreover, in the sample No. 155 in which the substitution rate Y is 1.0, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased largely. In the case that the substitution rate Y=0.1 (i.e. the substitution rate X is equal to the substitution rate Y), it is understood that a piezoelectric constant d.sub.31 is decreased. Moreover, it is understood that a piezoelectric constant d.sub.31 can be made more than 320 pm/V if the substitution rate Y is in a range of 0.3.about.0.8 and also it can be made more than 340 pm/V if the substitution rate Y is in a range of 0.4.about.0.7. Moreover, it is understood that, in order to obtain a Curie point greater than 190.degree. C., it is necessary to limit the substitution rate Y to be smaller than 0.6.
EXPERIMENT 12
In the same manner as experiment 11, specimens according to sample Nos. 156.about.166 in Table 11 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 11. In this experiment 12, CoCO.sub.3 raw material powders were added in the mixed powders ad 5 atomic % of Pb was substituted by Ca.
TABLE 11______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________156 10 40 50 0.6 0.8 249 148 Comparative example157 20 40 40 0.4 0.6 343 146 Present invention158 20 40 40 0.4 1.0 286 114 Comparative example159 25 50 25 0.4 0.6 275 160 Comparative example160 25 30 45 0.1 0.8 230 103 Comparative example161 37.5 47.5 15 0.4 0.6 280 123 Comparative example162 37.5 37.5 25 0.0 0.3 332 149 Comparative example163 37.5 37.5 25 0.2 0.4 355 131 Present invention164 37.5 37.5 25 0.7 0.7 354 82 Comparative example165 37.5 30 32.5 0.4 0.6 273 84 Comparative example166 50 35 15 0.3 0.7 310 61 Comparative example______________________________________
From the results shown in Table 11, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the second aspect of the invention while the coefficients a, b and c are also within the scope of the second aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 13
In the same manner as the experiment 11, specimens according to sample Nos. 167.about.177 in a Table 12 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results were shown in Table 12. In this experiment 13, SrCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Sr.
TABLE 12______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________167 10 40 50 0.6 0.8 243 158 Comparative example168 20 40 40 0.4 0.6 335 156 Present invention169 20 40 40 0.4 1.0 279 124 Comparative example170 25 50 25 0.4 0.6 268 170 Comparative example171 25 30 45 0.1 0.8 224 113 Comparative example172 37.5 47.5 15 0.4 0.6 273 133 Comparative example173 37.5 37.5 25 0.0 0.3 325 159 Comparative example174 37.5 37.5 25 0.2 0.4 347 141 Present invention175 37.5 37.5 25 0.7 0.7 347 92 Comparative example176 37.5 30 32.5 0.4 0.6 266 94 Comparative example177 50 35 15 0.3 0.7 303 71 Comparative example______________________________________
From the results shown in the Table 12, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the second aspect of the invention while the coefficients a, b and c are also within the scope of the second aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 14
In the same manner as experiment 11, specimens according to sample Nos. 178.about.188 in Table 13 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 13. In this experiment 14, BaCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Ba.
TABLE 13______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________178 10 40 50 0.6 0.8 242 163 Comparative example179 20 40 40 0.4 0.6 334 161 Present invention180 20 40 40 0.4 1.0 278 129 Comparative example181 25 50 25 0.4 0.6 267 175 Comparative example182 25 30 45 0.1 0.8 223 118 Comparative example183 37.5 47.5 15 0.4 0.6 273 138 Comparative example184 37.5 37.5 25 0.0 0.3 323 164 Comparative example185 37.5 37.5 25 0.2 0.5 359 138 Present invention186 37.5 37.5 25 0.7 0.7 346 97 Comparative example187 37.5 30 32.5 0.4 0.6 265 99 Comparative example188 50 35 15 0.3 0.7 302 76 Comparative example______________________________________
From the results shown in the Table 13, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the second aspect of the invention while the coefficients a, b and c are also within the scope of the second aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 15
In the previous experiments, use was made of oxide powders as raw material powders. In this experiment 15, use was made of hydroxide powders or carbonate powders of metal elements rather than oxide powders, and specimens were prepared in the same manner as the previous experiments. With respect to the specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. As a result, the specimens according to this experiment 15 have substantially same piezoelectric constant d.sub.31 and a Curie point as those of the previous experiments.
As mentioned above, according to the second aspect of the invention, a piezoelectric constant d.sub.31 and a Curie point can be improved extraordinarily.
Hereinafter, experiments according to a third aspect of the invention will be explained.
EXPERIMENT 16
Raw material powders of PbO, MgO, NiO, Nb.sub.2 O.sub.5, Ta.sub.2 O.sub.5, TiO.sub.2, ZrO.sub.2 were mixed in a ball mill for 24 hours to obtain mixed powders having compositions shown in Table 14. The thus obtained mixed powders were calcined in the atmosphere at 1000.degree. C. for 2 hours to obtain a calcined body. The thus obtained calcined body was crushed in the ball mill for 48 hours to obtain crushed powders. Then, the crushed powders were formed under a pressure of about 400 kg/cm.sup.2 by means of a press machine to obtain a formed body having a diameter of 20 mm and a thickness of 5 mm. The thus obtained formed body was sintered at a temperature of 1200.degree. C..about.1300.degree. C. for 2 hours to obtain a sintered body.
The thus obtained sintered body was worked to obtain a plate-like specimen having a dimensions of 12 mm (length).times.3 mm (width).times.1 mm (thickness). Then, silver electrodes were arranged on the planes of the specimen, and the specimen with the silver electrodes was subjected to a poling in such a manner that a DC voltage of 2 kV/mm was applied to the specimen in a silicone oil having a temperature of 80.degree. C. With respect to the respective specimens after a poling, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 14 as well as coefficients a, b and c and substitution rates X and Y in aPb[Mg.sub.1-X Ni.sub.X).sub.1/3 (Nb.sub.1-Y Ta.sub.Y).sub.2/3 ]O.sub.3 -bPbTiO.sub.3 -cPbZrO.sub.3, wherein the coefficients a, b and c were mol % and a sum of the coefficients a, b and c was 100. In sample Nos. 201.about.218 in the Table 14, substitution rates X and Y and coefficients a, b and c were varied respectively.
TABLE 14______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________201 10 45 45 0.6 0.2 216 280 Comparative example202 15 40 45 0.6 0.5 269 242 Present invention203 15 35 50 0.5 0 156 259 Comparative example204 15 35 50 0.6 0.5 243 214 Present invention205 20 30 50 0.6 0.3 211 202 Comparative example206 25 25 50 0.2 0.2 192 272 Comparative example207 25 40 35 0.7 0.3 278 211 Present invention208 25 40 35 0.4 0.2 268 234 Present invention209 37.5 37.5 25 1.0 0.5 294 153 Comparative example210 37.5 37.5 25 0.8 0.2 283 187 Present invention211 37.5 37.5 25 0.4 0.2 303 207 Present invention212 38 30 33 1.0 0.5 193 132 Comparative example213 45 45 10 0.4 0.3 258 187 Present invention214 50 33 18 0.4 0.3 256 151 Comparative example215 50 33 18 0.8 0.2 220 139 Comparative example216 55 40 5 0.8 0.4 194 119 Comparative example217 45 32 23 0.4 0.2 253 177 Present invention218 40 32 28 0.5 0.2 246 183 Present invention______________________________________
In the sample No. 201, it is understood that the coefficient a is decreased and thus a piezoelectric constant d.sub.31 is decreased. If the sample Nos. 202, 203 and 204 are compared, it is understood that a piezoelectric constant d.sub.31 is decreased extraordinarily in the sample No. 203 in which the substitution rate Y is 0 (i.e. no tantalum exists tantalum). In the sample No. 205 in which the coefficient b is out of the scope of the third aspect of the invention, it is understood that a piezoelectric constant d.sub.31 is decreased. If the sample Nos. 206, 207 and 208 are compared, it is understood that a piezoelectric constant d.sub.31 is decreased extraordinarily in the sample No. 206 in which the substitution rates X and Y are identical, but, in the sample Nos. 207 and 208 in which the coefficients a, b and c are same as those of the sample No. 206, a piezoelectric constant d.sub.31 is improved. If the sample Nos. 209, 210, 211 and 212 are compared, it is understood that a Curie point is decreased extraordinarily in the sample No. 209 in which the substitution rate X is 1.0 (i.e., no magnesium) exists and thus the sample No. 209 has a problem for an actual use. In the sample Nos. 210 and 211, it is understood that a piezoelectric constant d.sub.31 is improved extraordinarily. In the sample No. 212 in which no magnesium exists, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased extraordinarily.
If the sample Nos. 213, 214 and 215 are compared, it is understood that a Curie point is decreased in the sample Nos. 214 and 215 wherein the coefficient a is larger than 45. Moreover, if the sample Nos. 216, 217 and 218 are compared, it is understood that a Curie point is decreased in the sample No. 216 wherein the coefficient a is larger than 45 and the coefficient c is not larger than 10.
EXPERIMENT 17
As is the same as the experiment 16, specimens according to sample Nos. 219.about.232 in Table 15 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 15. In the experiment 17, the substitution rates X and Y were varied while the coefficients a, b and c were maintained constant within the scope of the third aspect of the invention.
TABLE 15______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________219 15 40 45 0.7 0.5 255 237 Present invention220 15 40 45 0.8 0.8 225 208 Comparative example221 15 35 50 0.6 0.5 243 214 Present invention222 15 35 50 0.7 0.7 227 193 Comparative example223 25 40 35 0.8 0.3 262 206 Present invention224 25 40 35 0.8 0.8 273 166 Comparative example225 37.5 37.5 25 0.7 0.2 299 192 Present invention226 37.5 37.5 25 0.7 0.7 339 152 Comparative example227 45 45 10 0.7 0.3 249 172 Present invention228 45 45 10 0.7 0.7 269 140 Comparative example229 45 32 23 0.5 0.2 256 172 Present invention230 45 32 23 0.5 0.5 290 148 Comparative example231 40 32 28 0.6 0.3 261 170 Present invention232 40 32 28 0.7 0.7 267 133 Comparative example______________________________________
If the sample Nos. 219 and 220 are compared, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are increased in the sample No. 219 in which the substitution rate X is larger than the substitution rate Y. If the sample Nos. 221 and 222 are compared, it is understood that a piezoelectric constant d.sub.31 and a Curie point are increased in the sample No. 121 in which the substitution rate X is larger than the substitution rate Y. If the sample Nos. 223 and 224 are compared, it is understood that a Curie point is largely decreased in the sample No. 224 in which the substitution rate X is equal to the substitution rate Y. If the sample Nos. 225 and 226 are compared, it is understood that a Curie point is largely decreased to a level of about 150.degree. C. in the sample No. 226 in which the substitution rate X is equal to the substitution rate Y and thus the sample No. 226 has a problem for actual use.
If the sample Nos. 227 and 228 are compared, it is understood that a Curie point is largely decreased to a level under 150.degree. C. in the sample No. 228 in which the substitution rate X is equal to the substitution rate Y and thus the sample No. 228 has a problem for an actual use. If the sample Nos. 229 and 230 are compared, it is understood that a Curie point is largely decreased in the sample No. 230 in which the substitution rate X is equal to the substitution rate Y. If the sample Nos. 231 and 232 are compared, it is understood that a Curie point is decreased to a region under 150.degree. C. in the sample No. 232.
EXPERIMENT 18
As is the same as the experiment 16, specimens according to sample Nos. 233.about.242 in Table 16 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 16. In the experiment 16, the coefficients a, b and c were varied while the substitution rate X was maintained at 0.5 and the substitution rate Y is was maintained at 0.3.
TABLE 16______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________233 15 40 45 0.5 0.3 242 263 Present invention234 20 30 50 0.5 0.3 209 207 Comparative example235 25 25 50 0.5 0.3 223 249 Comparative example236 25 40 35 0.5 0.3 290 221 Present invention237 37.5 37.5 25 0.5 0.3 327 194 Present invention238 37.5 30 32.5 0.5 0.3 224 173 Comparative example239 45 45 10 0.5 0.3 261 182 Present invention240 50 33 18 0.5 0.3 258 146 Comparative example241 55 40 5 0.5 0.3 211 142 Comparative example242 40 32 28 0.5 0.3 259 175 Present invention______________________________________
If the sample Nos. 233 and 234 are compared, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased in the sample No. 234 in which the coefficient b is not larger than 32. If the sample Nos. 235 and 236 are compared, it is understood that a piezoelectric constant d.sub.31 is largely decreased in the sample No. 235 in which the coefficient b is 25. If the sample Nos. 237, 238 and 239 are compared, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are decreased in the sample No. 238 in which the coefficient b is not larger than 32. If the sample Nos. 240, 241 and 242 are compared, it is understood that a Curie point is largely decreased as compared with that of the sample No. 242 in the sample No. 240 in which the coefficient a is larger than 45. Moreover, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are extraordinarily decreased as compared with that of the sample No. 242 in the sample No. 241 in which the coefficient a is larger than 45 and the coefficient c is smaller than 10.
EXPERIMENT 19
As is the same as the experiment 16, specimens according to sample Nos. 243.about.248 in a Table 17 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results were shown in the Table 17. In the experiment 19, the substitution rate X was varied in a range of 0.5.about.1.0 while the coefficients a, b and c were maintained constant within the scope of the third aspect of the invention and the substitution rate Y is maintained at 0.4. Moreover, a relation between the substitution rate X and a piezoelectric constant d.sub.31 or a Curie point is shown in FIG. 3.
TABLE 17______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________243 37.5 37.5 25 0.5 0.4 312 186 Present invention244 37.5 37.5 25 0.6 0.4 316 181 Present invention245 37.5 37.5 25 0.7 0.4 306 176 Present invention246 37.5 37.5 25 0.8 0.4 294 171 Present invention247 37.5 37.5 25 0.9 0.4 383 166 Present invention248 37.5 37.5 25 1.0 0.4 250 161 Comparative example______________________________________
From the results shown in Table 17, it is understood that a Curie point is extraordinarily decreased to a level of smaller than 170.degree. C. if the substitution rate X is 1.0 Moreover, it is understood that a piezoelectric constant d.sub.31 is largely improved if the substitution rate X is smaller than 0.9. Further, it is understood that piezoelectric constant d.sub.31 is more largely improved to a level larger than 300 pm/V if the substitution rate X is smaller than 0.7. Furthermore, it is understood that a piezoelectric constant d.sub.31 becomes larger than 310 pm/V if the substitution rate X is 0.5 or 0.6.
EXPERIMENT 20
In the same manner as experiment 16, specimens according to sample Nos. 249.about.257 in Table 18 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in the Table 18. In the experiment 20, substitution rate X was varied in a range of 0.2.about.1.0 while the coefficients a, b and c were maintained constant within the scope of the third aspect of the invention and the substitution rate Y is maintained at 0.2. Moreover, a relation between the substitution rate X and a piezoelectric constant d.sub.31 or a Curie point is shown in FIG. 4.
TABLE 18______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________249 37.5 37.5 25 0.2 0.2 263 217 Comparative example250 37.5 37.5 25 0.3 0.2 299 212 Present invention251 37.5 37.5 25 0.4 0.2 309 207 Present invention252 37.5 37.5 25 0.5 0.2 312 202 Present invention253 37.5 37.5 25 0.6 0.2 316 197 Present invention254 37.5 37.5 25 0.7 0.2 306 192 Present invention255 37.5 37.5 25 0.8 0.2 294 187 Present invention256 37.5 37.5 25 0.9 0.2 283 182 Present invention257 37.5 37.5 25 1.0 0.2 250 177 Comparative example______________________________________
From the results shown in Table 18, it is understood that a Curie point is extraordinarily decreased if the substitution rate X is 1.0. Moreover, it is understood that a piezoelectric constant d.sub.31 is largely improved if the substitution rate X is smaller than 0.9. Further, it is understood that a piezoelectric constant d.sub.31 is largely decreased in the sample No. 249 in which the substitution rate X is equal to the substitution rate Y. Moreover, it is understood that both of a piezoelectric constant d.sub.31 and a Curie point are largely improved in the sample Nos. 250.about.256 in which the substitution rate X is larger than the substitution rate Y. Particularly, it is understood that a piezoelectric constant d.sub.31 is more largely improved to a level larger than 300 pm/V if the substitution rate X is in a range of 0.4.about.0.7. Moreover, it is understood that a piezoelectric constant d.sub.31 becomes larger than 310 pm/V if the substitution rate X is 0.5 or 0.6.
EXPERIMENT 21
In the same manner as experiment 16, specimens according to sample Nos. 258.about.268 in a Table 19 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results were shown in the Table 19. In this experiment 21, SrCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Sr.
TABLE 19______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________258 10 40 50 0.8 0.6 237 164 Comparative example259 20 40 40 0.6 0.4 315 162 Present invention260 20 40 40 1.0 0.4 256 142 Comparative example261 25 50 25 0.6 0.4 249 176 Comparative example262 25 30 45 0.8 0.1 177 134 Comparative example263 37.5 47.5 15 0.6 0.4 254 139 Comparative example264 37.5 37.5 25 0.2 0.0 286 173 Comparative example265 37.5 37.5 25 0.4 0.2 326 147 Present invention266 37.5 37.5 25 0.7 0.7 347 92 Comparative example267 37.5 30 32.5 0.6 0.4 247 100 Comparative example268 50 35 15 0.7 0.3 270 83 Comparative example______________________________________
From the results shown in Table 19, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the third aspect of the invention while the coefficients a, b and c are also within the scope of the third aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 22
As is the same as the experiment 16, specimens according to sample Nos. 269.about.279 in Table 20 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 20. In this experiment 22, CoCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Ca.
TABLE 20______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________269 10 40 50 0.8 0.6 244 154 Comparative example270 20 40 40 0.6 0.4 322 152 Present invention271 20 40 40 1.0 0.4 263 132 Comparative example272 25 50 25 0.6 0.4 256 166 Comparative example273 25 30 45 0.8 0.1 183 124 Comparative example274 37.5 47.5 15 0.6 0.4 261 129 Comparative example275 37.5 37.5 25 0.2 0.0 293 163 Comparative example276 37.5 37.5 25 0.4 0.2 333 137 Present invention277 37.5 37.5 25 0.7 0.7 354 82 Comparative example278 37.5 30 32.5 0.6 0.4 254 90 Comparative example279 50 35 15 0.7 0.3 277 73 Comparative example______________________________________
From the results shown in the Table 20, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the third aspect of the invention while the coefficients a, b and c are also within the scope of the third aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 23
In the same manner as experiment 16, specimens according to sample Nos. 280.about.290 in Table 21 were prepared. With respect to the thus prepared specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. The measuring results are shown in Table 21. In this experiment 23, BaCO.sub.3 raw material powders were added in the mixed powders and 5 atomic % of Pb was substituted by Ba.
TABLE 21______________________________________ CurieSam- Composition Piezoelectric pointple a b c X Y constant d.sub.31 (.degree.C.) Remarks______________________________________280 10 40 50 0.8 0.6 236 169 Comparative example281 20 40 40 0.6 0.4 313 167 Present invention282 20 40 40 1.0 0.4 255 147 Comparative example283 25 50 25 0.6 0.4 248 181 Comparative example284 25 30 45 0.8 0.1 176 139 Comparative example285 37.5 47.5 15 0.6 0.4 253 144 Comparative example286 37.5 37.5 25 0.2 0.0 285 178 Comparative example287 37.5 37.5 25 0.4 0.2 324 152 Present invention288 37.5 37.5 25 0.7 0.7 346 97 Comparative example289 37.5 30 32.5 0.6 0.4 246 105 Comparative example290 50 35 15 0.7 0.3 269 88 Comparative example______________________________________
From the results shown in the Table 21, if the substitution rate X of nickel with respect to magnesium and the substitution rate Y of tantalum with respect to niobium are within the scope of the third aspect of the invention while the coefficients a, b and c are also within the scope of the third aspect of the invention, it is possible to improve both of a piezoelectric constant d.sub.31 and a Curie point.
EXPERIMENT 24
In the previous experiments, use was made of oxide powders as raw material powders. In this experiment 24, use was made of hydroxide powders or carbonate powders of metal elements rather than oxide powders, and specimens were prepared in the same manner as the previous experiments. With respect to the specimens, a piezoelectric constant d.sub.31 and a Curie point were measured. As a result, the specimens according to this experiment 24 have substantially same piezoelectric constant d.sub.31 and a Curie point as those of the previous experiments.
As mentioned above, according to the third aspect of the invention, a piezoelectric constant d.sub.31 and a Curie point can be improved extraordinarily.

Number	Date	Country
7-033467	Feb 1995	JPX
7-033468	Feb 1995	JPX
7-042967	Mar 1995	JPX

Number	Name	Date
4940681	Ushida et al.	Jul 1990
5275988	Mori et al.	Jan 1994
5500142	Ushida et al.	Mar 1996
5525562	Kagata et al.	Jun 1996
5527481	Otsu et al.	Jun 1996

Number	Date	Country
3011521	Jan 1988	JPX
3011522	Jan 1988	JPX
3011523	Jan 1988	JPX
3-40964	Feb 1991	JPX

Piezoelectric porcelain

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