Abstract:
An improved lead calcium titanate piezoelectric sintered body is produced by sintering in air at 1000° C.-1200° C. a calcined mixture of oxides or oxide compounds in amounts adapted to form a composition of the formula Pb 1-x  Ca x  Ti 1-y  (Co 1/2  W 1/2 ) y  O 3  +0.005-0.02(A) where A is at least one of MnO, MnO 2 , NiO and Nb 2  O 3 , wherein x=0.3-0.4 and 0.04&lt;y≦0.06.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to new and improved piezoelectric sintered bodies of the lead calcium titanate type. 
     Articles by Y. Yamashita, K. Tokoyama et al, Japan. J. Appl. Phys. 20, Suppl. 20-4, 183 (1981), Y. Yamashita, S. Yoshida et al, Proc. FMA 4, Kyoto, Japan, 25 (1983) and S. Jyomura et al, J. Appl. Phys. 52, 4472 (1981) disclose sintered lead titanate piezoelectric ceramics exhibit characteristics making these useful for ceramic ultrasonic transducers. However, the piezoelectric ceramics disclosed in these references while showing properties that render these materials useful in some aspects exhibit other properties that make these materials less useful for use in ultrasonic transducers and for similar uses. 
     While the Yamashita et al 1981 article shows piezoelectric compositions exhibiting a relatively high thickness mode coupling (k t ) to planar mode coupling (k p ) ratio, it has been found that the piezoelectric constant (d 33 ) is not sufficiently high for some purposes. 
     It is highly desirable for many purposes that the piezoelectric constant d 33  be increased as far as possible while the ratio of k t  /k p  be maintained as high as possible. Additionally, it is also desired that the dielectric constant K be maintained as high as possible while the dissipation factor D be maintained as low as possible. 
     SUMMARY OF THE INVENTION 
     It is an object of this invention to provide a sintered lead titanate body which exhibits a high k t  /k p  ratio a high piezoelectric constant (d 33 ), a high dielectric constant (K) and a low dissipation factor (D). 
     According to one aspect of the invention, it has been found that a novel sintered lead calcium titanate of the formula Pb 1-x  Ca x  Ti 1-y  (Co 1/2  W 1/2 ) y  O 3  +0.005-0.02(A) where A is at least one of MnO, MnO 2 , NiO or Nb 2  O 3  and wherein x=0.3-0.4 and 0.04&lt;y≦0.06 exhibit an improved combination of a high piezoelectric constant d 33 , a high k t  /k p  coupling ratio, a low dissipation factor D and a high dielectric constant K. 
     According to another aspect of the invention, a new and novel method has been developed for producing the novel piezoelectric bodies of the invention. 
     In this method of the invention the novel piezoelectric bodies are produced by calcining a mixture of PbO, CaO, TiO, CO(OH) 2 , WO 3  and at least one of MnO, MnO 2 , NiO or Nb 2  O 3  the precursors of these materials and then sintering the resultant calcined mixture in an atmosphere consisting essentially of 10 to 20% of oxygen and 90-80% of nitrogen at a temperature of 1000° C.-1200° C. for a period of approximately 1-50 hours. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     In the drawing, 
     FIG. 1 is a graph showing the thickness coupling factor, the planar coupling factor, the dielectric constant, the piezoelectric constant and the dissipation factor as a function of the amounts of calcium present in the piezoelectric bodies; 
     FIG. 2 is a graph showing the thickness coupling factor, the planar coupling factor, the piezoelectric constant, the dielectric constant, and the dissipation factor as a function of the amount of cobalt and tungsten present in a piezoelectric body of the invention; 
     FIG. 3 shows the thickness coupling factor, the planar coupling factor, the dielectric constant, the piezoelectric constant and the dissipation factor as a function of the sintering time in producing the piezoelectric bodies of the invention; and 
     FIG. 4 is a graph showing the thickness coupling constant, the planar coupling constant and the dielectric constant as a function of the amount of calcium in the sintered piezoelectric body of the prior art; 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     While improved results are achieved with the piezoelectric bodies of the invention having calcium content of 30-40 at.%, it has been found that even more improved results are achieved when the content of calcium is within 34-36 at.% inclusive. 
     According to the novel method of the invention, the piezoelectric bodies may be prepared while calcining the ground mixture of the oxides PbO, CaO, TiO, CoO, WO 3  and at least one of MnO, MnO 2 , NiO and Nb 2  O 3  or of the precursors of these oxides such as the hydroxides, carbonates or acetates, all in amounts adapted to form piezoelectric bodies of the composition of the invention and sintering the resultant calcined mixture in an atmosphere consisting essentially of 10-20% of oxygen and 90-80% of nitrogen at a temperature of 1000° C.-1200° C. at a period of 1-50 hours. 
     Calcining is carried out preferably at a temperature of 925° C.-975° C. It has been found that the best results are achieved when the sintering is carried out in air at a temperature of 1100° C.-1150° C. for a period of 5 hours to 30 hours. 
     For a more complete understanding of the invention, operation of preferred embodiments of the invention will now be described in greater detail with reference to the following example. 
     EXAMPLE 
     Compositions of several variations of x and y in the formula 
     
         Pb.sub.1-x Ca.sub.x Ti.sub.1-y (Co.sub.1/2 W.sub.1/2).sub.y O.sub.3 +0.01MnO 
    
     were prepared from the raw materials: PbO, CaO or CaCO 3 , TiO 2 , Co(OH) 2 , WO 3  and MnO in the amounts as shown in the following Table 1. 
     
                       TABLE 1______________________________________Material weight forPb.sub.1-X Ca.sub.X Ti.sub.1-Y (Co.sub.1/2 W.sub.1/2).sub.Y O.sub.3 +0.01 MnO systemMaterial Weight for       X = 0.34  X = 0.34 X = 0.36                                 X = 0.381 Mole (g)  Y = 0.04  Y = 0.06 Y = 0.04                                 Y = 0.04______________________________________Raw MaterialsPbO (223.19)       147.3054  147.3054 142.8416                                 138.3778CaO (56.08) 19.0672   --       --     21.3104CaCO.sub.3 (100.0912)       --        34.0310  36.0328                                 --TiO.sub.2 (79.90)       76.7040   75.1060  76.7040                                 76.7040Co(OH).sub.2 (92.933)       1.8587    2.7880   1.8587 1.8587WO.sub.3 (231.85)       4.6370    6.9555   4.6370 4.6370MnO (70.938)       0.7094    0.7094   0.7094 0.70942% extra PbO       4.4638    4.4638   4.4638 4.4638EvaporationCO.sub.2 (44.0112)       --        -14.9638 -15.8440                                 --H.sub.2 O (18.0000)       -0.3600   -0.5400  -0.3600                                 -0.36002% extra PbO       -4.4638   -4.4638  -4.4638                                 -4.4638Composition 249.6016  251.3915 246.5795                                 242.9172Weight (g)______________________________________ 
    
     After being weighed, the mixtures of these raw materials were prepared by mixing in a plaster bottle with zirconic balls and alcohol. 
     The resultant mixtures were then ball milled for 24 hours, dried at 120° C., crushed and calcined in an aluminum crucible at 950° C. for 2 hours. 
     The resultant calcined lumps were then crushed and ground in a mortar, sieved to pass 50 mesh, and ground again with a few weight % of deionized water. The wet calcined mixture was then pressed at 1×10 8  N/m 2  (1000 Kg/cm 2 ) in a die of 1.905 cm in diameter into green discs. 
     The green discs were positioned between two platinum sheets to decrease Pb evaporation, and sintered in a covered crucible at 1100°-1120° C. for 1, 5 or 30 hours. 
     The sintered discs were lapped to a thickness of 0.9-1.3 mm. Both surfaces of the discs were then polished to a high brightness. 
     Gold electrodes were then provided on both surfaces of the discs by sputtering. 
     The gold-electroded discs were then poled in an oil bath at an elevated temperature in an electric field of 50 kV/cm for 5 minutes. 
     The dielectric constant K, the thickness coupling factor k t , the planar coupling factor k p , the dissipation factor D and the piezoelectric constant of d 33  were then determined for the resultant sintered discs. 
     The dielectric constant K, the coupling factors k t  and k p , the piezoelectric constant d 33  and the dissipation factor D as a function of x amounts of Ca for bodies of the system Pb 1-x  Ca x  Ti 0 .96 (Co 1/2  W 1/2 ) 0 .04 O 3  +0.01MnO are shown in the graph of FIG. 1. 
     These are also shown as a function of y amounts of (Co 1/2  W 1/2 ) for the bodies of the system. Pb 0 .66 Ca 0 .34 Ti 1-y  (Co 1/2  W 1/2 ) y  O 3  +0.01MnO in the graph of FIG. 2. 
     The effect of sintering time on these for bodies of the system Pb 0 .66 Ca 0 .34 Ti 0 .94 (Co 1/2  W 1/2 ) 0 .06 O 3  +0.01MnO are shown in the graph of FIG. 3. 
     Additionally the dielectric constant K, and the coupling factors k p  and k t  as a function of x amounts of Ca for bodies of the system Pb 1-x  Ca x  Ti 0 .96 (Co 1/2  W 1/2 ) 0 .04 O 3  +0.3wt% MnO+0.4wt%NiO as described in Yamashita and Yokoyama et al, 1981 are shown in the graph of FIG. 4. 
     As will be noted from a comparison of the graphs of FIGS. 1, 2 and 3 with the graph of FIG. 4, the sintered lead calcium titanate piezoelectric bodies of the invention exhibit significantly higher k t  /k p  ratios particularly when sintered from 5 to 30 hours. 
     The sintered lead calcium titanate piezoelectric bodies of the invention have the additional advantage of exhibiting a significantly higher piezoelectric constant.