DE1907199A1 - Piezoelectric ceramic material - Google Patents

Description

Applicant;

Nippon Electric Company Limited 7-15 "Shiba Gochorae, Minato-ku

Tokyo / Japan

Stuttgart, February 10, 1969 P 2188 88/89

Representative; Patent attorney Dipl.-Ing. Max Bunke

7 Stuttgart 1 Schloßstr. 73 B

Piezoelectric ceramic material

The invention relates to piezoelectric ceramic material having excellent piezoelectric properties *

The electromechanical coupling factor and the mechanical quality factor are important measures for the practical evaluation of the piezoelectric properties of piezoelectric material. The former is a measure of the efficiency in converting.-electrical vibrations into mechanical vibrations and in the inverse conversion of

0 0.9 8Q9 / U73

mechanical vibrations into electrical vibrations. The bigger the electromechanical coupling factor, the higher the conversion efficiency. The mechanical quality factor indicates the inverse ratio of the energy consumed by the material during energy conversion; the greater the mechanical quality factor, the lower the energy consumption.

One of the main areas of application for piezoelectric ceramic materials is the production of elements for ceramic filters. It is necessary in this case for the electromechanical coupling factor take the cheapest value from a wide range extending from an extremely high value to a very small value, and the mechanical quality factor must be as large as possible. These relationships are, for example, from R&V "Macario in an essay" design Data for Band-Pass Ladder Filter Employing Ceramic Resonators "outlined, that in the magazine ELECTRONIC ENGINEERING, Vol. 33, No. 3 (I96I) on pp. 171 to 177.

Another important field of application for piezoelectric ceramic material are the transducer elements of mechanical filters. In this case, both the electromechanical coupling factor and the mechanical quality factor should be as large as possible.

The German patent no (application P 17 71 I98.7) relates to one

Piezoelectric ceramic with the composition Pb (Sb. /_Z./_)O PbTiO -PbZrO. In the formula, Z stands for Nb or Ta. Ceramic materials of this type have a very high electromechanical coupling factor, but the mechanical quality factor is greatly reduced. Their possible uses are therefore limited. They are not suitable for the production of elements for ceramic filters and transducer elements for mechanical filters «

The invention is based on the object of creating a piezoelectric ceramic material which has both a high electromechanical coupling factor and a high mechanical quality factor.

Such a piezoelectric ceramic material having a high or in a electromechanical coupling factor and a

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I,

1307199

has a high mechanical quality factor, is said to be in various fields such as the manufacture of elements for ceramic filters and transducer elements for mechanical filters are applied where the properties mentioned are needed.

The invention relates to piezoelectric ceramic material, which essentially consists of a solid solution of the components Pb (Sb ^ / ■ & *

and PbZrO-, where Z is one of the elements niobium (Nb) and tantalum (Ta) represents, which is characterized in that 0.10 to 3.0 percent by weight of manganese oxide (HnO) are added and that up to 25 atomic percent lead (Pb) by at least one of the elements barium (Ba), strontium (Sr) and Calcium (Ca) are replaceable

Z is chosen for niobium (Nb), and the basic composition represented by the formula ^ Pb (SbW ₃ Nb _1/2) 0,) x jPbTiO_J £ ^ js PbZrO J is given in Figure 2E. + Σ + L · - 1 »00 molar proportions, the basic composition should be within a range determined by the following molar proportions

is: Z •
Σ 0.38 0.61 0.90 0.09 0.90 0.05 0, IfO 0.30 0.20. 0.70 £ and 2. determined x_ 0.01 0.01 0.05 0.30 0.10

Tantalum (Ta) is selected for Z and the basic composition is given by the formula (Pb (SbW ₂ Ta ₁ Z ₂ ) O Jx (PbTiO J £ [pbZrO J z, in which 2 £ + Σ ⁺ - ⁼ 1 »00 Molar proportions mean, the basic composition should be within a range defined by the following molar proportions

3C, £ ^and £. is determined:

0.01
0.01
0.05
0.30
0.30

0.05

Σ -. 0.55 0, Mf 0.09 0.90 0.05 0.90 0.05 0.65 O ₁ IfO 0.30 0.65 0.30. 009809 / 1A 7 3

The addition of hangan oxide (MnO) in the amount of 0.10 to 3 «0 percent by weight to the basic composition improves the mechanical quality factor without the electromechanical coupling factor decreasing appreciably. Thus, there is a piezoelectric ceramic material that is used for elements 'vpn ceramic filters and transducer elements are suitable for mechanical filters »

The excellent piezoelectric properties of the ceramic material according to the invention will emerge from the following description of examples for material according to the invention, which are given with reference to the drawings will.

1 and 3 are diagrams of the composition of the ternary system ^ covering the range of useful basic compositions of ceramic material according to the invention and show the particular basic compositions described by way of example; Fig. 1 relates to the case that for Z niobium (Nb), FIG. 2 for the case that tantalum (Ta) is selected for Z.

2 and * f show in graphical representation the dependence of the electromechanical coupling factor and the mechanical quality factor of ceramic material according to the invention on the content of manganese oxide; Fig. Relates to the case that for Z niobium (Nb), Fig. 2 to the case "where tantalum (Ta) is selected for Z. ·

Example Te.

Unless otherwise specified, were used as starting materials in powdered lead oxide (PbO), antimony-III-oxide (Sb ₃ O), niobium-V-oxide (Nb ₃ O) _t titanium dioxide _(Ti0?), Zirconia (ZrO) and manganese carbonate ( MnCO-) used to obtain three-component ceramic material Pb (Sb ₁ / -, Nb ₁ , _) 0, -PbTiO-PbZrO with manganese oxide (MnO) »These pulverized substances were weighed so that they were in the samples composed of them the basic composition with variable molar proportions 3C, ^ L ^{un <} * L · could occur, and that manganese oxide (MnO) could be added in the desired amounts of 0.00 to 3 ° percent by weight, as can be seen from Table 1. In order to arrive at ceramic material with the compositions shown in Table 3, barium carbonate (BaCO,),

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Strontium carbonate (SrCO) or calcium carbonate (CaCO) added. For the substances according to Table 3, u, atomic percent is lead (Pb) of the basic composition with the molar proportions χ. » Σ ^{un <} * L · replaced by barium (Ba), strontium (Sr) or calcium (Ca). This is indicated in the column headed "Me".

To obtain ceramic material of the three-component system Pb (Sb, / "Ta .. / _) 0, -PbTiO-PbZrO, with a content of manganese oxide (MnO), powdered lead oxide (PbO), antimony- were used as starting materials, unless otherwise stated. III oxide (Sb ₂ O), tantalum V oxide (Ta ₃ O), titanium dioxide ₂ zirconium dioxide (ZrO) and manganese carbonate (MnCO) are used.

In this case, too, the pulverized substances were weighed so that basic compositions with an additional agent (MnO), as shown in Table 2, could be formed. In order to arrive at the ceramic material with compositions according to table h , barium carbonate (BaCO.,), Strontium carbonate (SrCO.,) Or calcium carbonate (CaCO,) were added. According to table * f, ii atomic percent lead (Pb) is the basic composition of the components Pb (Sb, _Ta ₁ / _? ) 0, PbTiO and PbZrO with the molar proportions x. » ^ L ^unc * 2. replaced by a part Me (Ba, Sr or Ca). The antimony III oxide (Sb_O,), the manganese carbonate (MnCO.,) And the barium, strontium or calcium carbonate (BaCO ,, SrCO or CaCQ.) Were weighed as the calculation based on antimony -V oxide CSh ₃ O-), manganese oxide (MnO) and barium, strontium or calcium oxide (BaO, SrO or CaO) results.

The above pulverized materials were mixed with distilled water in a ball mill. The mixed powder was filtered, dried, crushed, presintered at 900 ° C. for one hour, and crushed again. Subsequently, the mixtures were pressed with a low Susatz of distilled water under a pressure of 00? Kg / om in discs of 20 mm diameter and sintered for one hour at a temperature of 1260 to I3OO ⁰ C in an atmosphere of lead oxide (PbO). The resulting ceramic disks were ground to a thickness of one millimeter on both surfaces and provided with a silver electrode on both surfaces. The samples according to Tables 1 and 3 were then subjected to a one-hour polarization treatment at 100 ° C and with the application of a direct current electric field

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of ^ O kV / cm piezoelectrically activated. For the samples according to Tables 2 and k with up to 20 mol percent of the component Pb (Sb./ ₂ ^Ta 1/2 ^ 3 ^be ~, the field strength was 50 kV / cm, and for samples according to Tables 2 and 4 with more than Room temperature prevailed for 20 mole percent of the component mentioned and the constant electric field was 50 kV / cm.

After 2 hours, the electromechanical coupling factor for radial vibrations (k) and the mechanical quality factor (Q) were measured to determine the piezoelectric activities. These piezoelectric properties were measured in accordance with the IRE standard circuit. The value k was determined using the resonance-antiresonance frequency method The dielectric constant (S ) * and the dielectric loss factor (tan O ) were also measured at a frequency of 1 kHz.

Tables 1 to k show the results. The samples are arranged in the tables according to their Pb (Sb ₁ / »Ζ., _) 0 content in the basic composition (Z stands for Nb or Ta). The samples with the same basic composition are sorted according to the increasing amount of the additional agent MnO. In FIGS. 1 and 3, the basic compositions according to Tables 1 and 2 are entered by dots.

Tables 1 and 2 show that the addition of 0.10 to 3 »0 percent by weight MnO to the basic composition Pb (Sb. / -Nb .., _) 0 -PbTiO, -

PbZrO- and Pb (Sb. / -, Ta " _/ _) 0- _z -PbTi0 -, - PbZr0, to an increased or in a 3 1/2 1/2 3 3 3

a wide range of values of k and a greatly increased value of g ^r

from Q leads. This addition creates an excellent material for the elements of ceramic filters ^ the transducer elements of mechanical filters and for other areas of application in which both a high or a wide range of factor k and a large factor Q are required. 2 and k show the relationship between the MnO content and exhibited piezoelectric properties (k and Q) for Samples Nos. 10 to 16 of Table 1 and Nos. 51 to 57 of Table 2, respectively, as typical examples · Man clearly recognizes from these two figures that the piezoelectric properties are excellent when the content of MnO is within the range of 0.10 to 5.0% by weight.

If the content is below 0.10 percent by weight, the addition

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from ENT there is only a slight improvement in the piezoelectric properties. If the content of MnO above 3.0 weight percent, then Q fills from considerably, and it is difficult to produce a uniform solid _solution} of the additional agent and the base composition and to perform the polarization treatment. Thus, the useful range for the MnO content is set to be 0.10 to 3.0 percent by weight.

It has also been found to have the best piezoelectric properties are available when the basic compositions of the formula

in which 3c + £ + z_ = 1.00 mean the molar fractions, 'and if for Z niobium (Nb) Cev / is within polygon A-B-C-D-E of Figure 1 of the drawings lie or - if tantalum (Ta) is selected for Z - within the polygon F-G-H-I-J-K of Figure 3 of the drawings. The mole fraction coordinates x. » £ and 2. for the corners of the polygons »are as follows:

3C Σ 0.38 A. 0.01 0.61 0.90 B. 0.01 0.09 0.90 C. 0.05 0.05 O, ifO D. 0.30 0.30 0.20 E. 0.10 0.70 0, Mf F. 0.01 0.55 0.90 G 0.01 0.09 0.90 H 0.05 0.05 0.65 I. 0.30 0.05 0.30 J 0.30 0, * K) 0.30 K 0.05 0.65

If the basic compositions are not within the designated areas these ceramic materials have only moderate or even unusable piezoelectric properties.

It can be seen from Tables 3 ^u * id ^ that excellent piezoelectric properties are also found in ceramic material in which part of the lead (Pb) of the basic composition is replaced with Ba, Sr or Ca. in the

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in general, at least one of the elements Ba, Sr and Ga can be up to 2 $ Replace the atomic percent of the lead (Pb) contained in the base composition. The result of the addition of MnO in terms of the piezoelectric The improvement achieved in properties is due to the presence

of manganese ions. Various methods are known for releasing manganese ions. For example, manganese ions can be introduced by using manganese oxide itself, such as MnO or MnO- or other manganese compounds such as MnCO-, which easily decomposes at elevated temperature and forms manganese oxide, as the starting material. If a manganese compound other than MnO is used, this should be done in the amount that is calculated on the basis of MnO. In the above examples, MnCO is mostly used instead of MnO, and in the examples according to Nos. 1 * f, 18 and * 25 of Table 1 and 7, 30, 55, 72 and 77 of Table 2, MnO _{3 was} used. '

It is clear that the starting materials to be used in the manufacture of ceramic material according to the invention are not limited to those used in the examples mentioned. For example, to form the desired compositions, instead of each starting material in the examples given, an oxide can be used which decomposes easily at elevated temperature, e.g. Pb-ZCh instead of PbO. Salts such as oxalates or carbonates, which easily break down into the corresponding oxides at elevated temperature, can also be used instead of the oxides used in the examples. Furthermore, instead of the oxides, hydroxides with the above-mentioned properties can be used, e.g. Nb (OHX instead of Nb ₂ Oj-. Furthermore, an excellent piezoelectric ceramic material with the listed example substances having the same properties can also be obtained by using the pulverized substance components' Pb (Sb ₁ ^ ₂ Nb ₁ y ₂₎ 0_ or Pb (Sb ₁ → ₃ Ta _1/2) 0_ _f PbTiO, and are provided PbZrO- and the powdered raw material for MnO in advance separated and used as starting materials for the subsequent mixture.

The commercially available substances niobium V oxide (Nb ₂ O ₅ ), tantalum V oxide (Ta ₂ O ₅ ) and zirconium dioxide (ZrO) usually contain a few percent tantalum V oxide (Ta ₃ O), niobium V oxide (Nb ₃ O) and hafnium dioxide (HfOg). The ceramic compositions according to the invention may contain small amounts of such oxides or elements as they occur in commercially available substances ". . _v , *

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Specified and described in more detail, the compositions were according to the invention, which have so far proved to be particularly favorable, "But it is clear that further modifications within the scope of the invention are _t even all ceramic compositions which are detected by the following claims ·

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Table 1

No. Mole fractions the reason
composition PbTiO PbZrO L. ,Additive
liches
agent
MnO ^k r 8th Sl e 1
tan σ PbCSb. i, Nb. / OQr
yd Λ / Ζ? Σ L Ge * %) (*) 8th «> ■■ 1.· X 0.30 0.40 0.00 9 170 530 3.5 2. 0.30 Il Il 0.10 5 390 490 1.2 4 3. Il Il Il 0.50 33 2270 420 1.1 4th It • 1 Il 3.00 33 650 380 3.1 5. * Il 0.30 0.60 0.00 36 215 655 3.6 β. 0.10 • 1 dd 0.10 34 330 800 1.1 7th Il ' Il Il 0.20 33 1370 310 0.8 8th. Il Il Il 0.50 34 3480 440 0.8 ' 9. Il It ■ I • 1.00 26th 3160 400 0.8 j 10. * Il 0.48 0.42 0.00 30th 150 1030 1
2.3 11. 0.10 Il It 0.10 41 300 680 1.2 12th Il It Il 0.20 48 850 660 0.8 13th Il Il Il 0.50 45 1920 900 1.0
j 14t * It Il It 1.0 35 1660 1070 1.5 15th It It It 2.0 7th 1040 890 1.8 16. Il ti Il 3.0 7th 710 760 2.0 17. * • I 0.70 0.20 0.00 8th 180 345 4.7 18th 0.10 Il ■ t 0.10 5 390 300 1.5
ι 19th Il It It 0.50 1580 280 1.3 20th ti 'Il Il 3.0 βίο 230 3.6 Il

ΟΟ9Ε09- / Κ73

No.

- 11 -

MnO

tan

21. · 22. 23, 24.

25. * 26th 27 28t * 29 30th 31.

32. * 33. 34. 35. 3Θ.

37. 38.

39. * 40. 41. 42. 43.

0.05

0.05

0.05

0.05

0.05

0.20

0.40

0.48

0.90 0.00 It 0.10 Il 0.50 Il 3.0 0.75 0.00 Il 0.10 Il 0.20 It 0.50 Il 1.0 Il 2.0 ti 3.0 0.55 0.00 Il 0.10 Il 0.20 • 1 0.50 Il 1.0 I · 2.0 ti 3.0 0.47 0.00 It 0.10 • 9 0.20 It 0.50 M. ».0

13th 360 390 4.2 11th 720 350 1.2 10 1750 330 1.1 5 760 320 3.5 28 300 460 3.7 24 480 400 0.8 24 910 410 1.0 24 2480 340 1.2 24 2980 340 1.1 22nd 2000 320 1.5 18th 1180 290 2.0 52 115 760 3.7 51 290 670 1.5 4Θ 860 540 1.0 45 2440 420 1.0 37 1580 350 2.3 31 1210 330 2.6 28 1000 310 3.0 57 100 1610 2.4 38 220 1170 1.1 42 580 1130 1.0 58 2200 1150 0.9 48 620 1130 1.3

0 0 9 8 | Q9 / «147 3

- 12 -

MnO Sqm

f.

tan (Γ

44. *

0.05

0.02

0.01

0.01

0.55

0.47

0.09

0.61

0.40

0.51

0.Θ0

0.38

0.00 41 120 6Θ0 2.2 0.10 23 340 630 0.9 0.20 25th ■ 1380 550 0.9 0.50 36 3560 620 0.8 1.0 28 1910 460 1.3 2.0 23 1180 390 1.9 3.0 21 860 340 2.2 0.00 81 85 1760 2.6 0.10 47 480 1120 1.1 0.20 54 1630 860 0.9 0.30 69 1660 790 0.9 0.50 58 800 740 1.2 1.0 48 640 500 1.8 2.0 42 450 460 2.1 3.0 41 310 410 2.5 0.00 15th 500 290 4.3 0.10 13th 810 260 1.1 0.50 12th 1830 230 1.1 3.0 β 880 220 \ ·> 0.00 25th 180 500 2.8 0.10 22nd 380 400 1.1 0.50 22nd 2360 350 1.0 3.0 18th 1120 200 2.9

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- 13 table

Hol components of the basic composition Zunp;

^PbZr0

additive k
r % E - tan liches (#) (%) agent 4th 420 260 2.9 MnO 6th 1200 230 1.3 (Weight #) 10 2650 210 1.6 0.00 5 1050 180 2.5 0.10 12th 235 380 3.1 0.50 14th 1180 310 1.3 3.0 15th 2460. 280 1.8 0.00 18th 2250 290 1.9 0.10 17th 2050 290 1.9 0.20 , 10 1200 430 4.0 0.50 9 650 610 4.3 1.0 8th 270 190 * 3.3 2.0 4th 990 170 1.6 3.0 6th 2130 150 1.3 0.00 3 860 140 2.2 0.10 12th 180 = 410 3.6 0.50 10 1050 360 1.4 3.0 15th 3450 340 1.1 0.00 15th 4070 300 1.1 0.10 .- 12th 3600 250 1.· 0.20 0.50 ^BC 1.0

16. * 17. 18. 19. 20. ·

0.30

0.30

0.30

0.20

0.05

0.30

0.40

0.20

0.65

0.40

0.30

0.60

009 8D9 / U7

- Hf -

No. χ ϊ ζ MnO kr Qm £ ten j "

21. * 0.20 0.40 0.40

22. "

24. ■ "" "

28. * Q.10 0.10 0.80

3Ot * "" ".

31. ""

33. * 0.10 0.43 0.47

35. "" ^H.

36. ^M ""

38. * 0.05 0.05 0.Θ0

39 "" "

40. ""

42. * 0.05 0.30 '0.65

43. "" µ

44. "" ^M.

0.00 20th 140 640 2.5 0.10 20th 500 470 1.8 0.20 23 1040 440 1.1 0.50 25th 23-0 510 1.2 1.0 24 1250 580 2.3 2.0 23 540 690 3.8 3.0 20th 340 800 4.9 0.00 14th 420 495 3.8 0.10 11th 980 470 2.0 0.20 12th 1300 400 1.2 0.50 10 5110 360 1.1 1.0 6th 2800 280 1.9 0.00 43 120 1180 3J0 0.10 25th 280 910 1.6 0.20 28 630 760 1.1 0.50 23 500 660 1.6 1.0 20th 420 600 2.8 0.00 10 290 405 4Λ 0.10 12th 440 380 2.2 0.50 15th 2030 310 1.2 3.0 9 970 280 3.5 0.00 37 140 690 4.0 0.10 32 400 490 1.8 0.20 32 1460 430 1.1 0.50 2 » 4100 300 1.1

tan

46. *

51. *

55t *

57.

58. *

64. * 65. 66. 67.

0.05

0.05

0.05

0.05

0.35

0.48

0.65

0.60

0.455 0.4Θ5

0.47

0.30

0.00 42 120 700 4.0 0.10 30th 480 570, 1.5 0.20 20th 1240 530 1.1 0.50 28 2660 410 0.9 1.0 16 2030 310 1.9 • 0.00 i'.on 61 90 1210 3.1 0.10 50 520 1020 1.6 0.20 55 780 930 1.1 0.30 60 2030 720 1.1 0.50 56 2850 530 1.1 1.0 52 1880 420 1.6 3.0 48 960 330 2.7 0.00 54 105 1550 2.8 0.10 49 260 1300 1.2 0.20 57 540 1200 1.2 0.50 60 600 1150 1.2 1.0 50 500 960 2.8 3.0 14th 200 850 5.0 0.00 27 235 435 2.1 0.10 25th 550 360 1.1 0.50 25th 1950 310 1.0 3.0 " 20th 620 270 2.0

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No. χ χ ζ ^Μη0 * r Qm £ tan <f

68. * 0.02 0.47 0.51

■ 69. "" "

71.. ^Μ "" 72 ** "" ^Μ

W 75. * 0.01 0.09 0.90

77t * "" ti

79. * 0.01 Ο.βδ 0.44

0.00 69 100 1410 2. 7th 0.10 41 460 1000 1. 2 0.20 56 '1060 970 i. 1 0.50 61 1600 890 1. 2 1.0 52 1300 * 80 1. 8th 2.0 44 780 730 2. θ 3.0 42 380 660 4th 8th 0.00 11th 410 270 4th β 0.10 10 960 220 2. 1 0.50 13th 2860 180 1. 1 3 * 0 11th 690 170 3. 8th 0.00 14th 210 490 2. 5 0.10 12th 430 470 1. β 0.50 14th 2560 370 1, 0 3.0 8th 410 330 2. 3

Note i The samples whose numbers are marked with an asterisk (*) Bind * are not within the scope of the invention. '

In the manufacture of those marked with a double star Samples were used as one of the starting materials manganese dioxide CMnO-) instead of manganese carbonate (MnCO-)

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ORIGINAL INSPECTED

Tabel Σ 0.50 a -17
3 mm MnO system ^k r • 90 from
PbTiO - PbZrO 0.48 Il 0.10 Pb ( \ VJCW 4 / QJ (SS) 480 ε tan (Γ Basic composition Il Il Il
I. 0.00 75 1210 W) No. 5 Il Il Il Me 0.10 46 380 2160 2.9 1 0.02 Il 0.51 It Ba 0.50 56 90 1260 1.1 2 Il 0.47 It ο, οέ Il 3.0 40 510 790 1.2 3 Il Il Il Il Il 0.00 79 I28O 500 2.5 4th Il Il Il Il Il 0.10 46 410 1770 2.6 VJl 0.02 Il 0.51 It * Ba 0.50 59 90 1150 1.0 6th Il 0.47 H 0.10 Il 3.0 41 460 960 1.3- 7th Il Il Il Il It 0.00 76 1190 450 2.5 8th Il Il Il ti It 0.10 45 450 240 2.5 9 0.02 It 0.51 It Ba 0.50 56 80 1250 1.1 10 It 0.47 Il 0.25 It 3.0 38 560 81Ο 1.3 11th It It Il Il It 0.00 30th 1690 530 2.0 12th ti Il It Il It 0.10 26th 680 4120 3.1 13th 0.02 Il 0.51 Il Ba 0.50 27 85 369Ο 1.5 14th Il 0.47 It 0.01 Il 3.0 13th 390 3210 1.8 15th Il Il Il ti Il 0.00 80 1210 296Ο 2.6 16 Il Il ti ti . Il 0.10 48 530 I79O 2.5 17th 0.02 Il 0.51 Il Sr 0.50 60 100 1200 '1.2 18th Il 0.47 It 0.10 It 3.0 " 40 430 78Ο 1.6 19th Il Il Il
Il Il It 0.00 55 _ 13_10
560 480 · 2.3 20th Il Il
Il Il
00 9 8 Il 0.10 35 1720 2.1 21 0.02 Sr P, 59
3.0.
U73 51
26th 1210 1.1 22nd Il Il 1 "76Ö *"
500
• 2.V 23
24 Il
It Il
Il
09 /

Continuation of table 3

System of Pb (Sb _{i / 2} Nb _1/2 ) O - PbTiO ₃ - PbZrO

Basic composition χ y Z U Me MnO ^k r ^ m G tan <f No. 0.02 0.47 0.51 0.01 Approx (Wt. ^) (Ji) (#> 25th ti Il It It It 0.00 78 90 1740 2.6 26th Il Il Il It Il 0.10 46 430 1210 1.1 27 Il Il Il It Il 0.50 61 1260 710 1.5 ^λ 28 0.02 0.46 0.52 0.05 Sr 3.0 37 58O 43O 2.5 29 Il Il Il It fl 0.00 79 85 2140 2.6 30th Il dd Il dd dd 0.10 48 390 I59O 1.3 31 Il Il It Ir H It 0.50 63 1060 I36O 1.6 32 0.02 0.45 0.53 0.05 Approx 3.0 40 490 810 2.5 33 Il Il Il It It 0.00 75 90 218O 2.7 34 It It dd It It 0.10 43 390 I56O 1.5 35 dd Il • 1 Il It 0.50 55 1310 - 1230 1.6 36 0.02 0.44 0.54 0.10 Sr 3.0 36 580 9OO 2.6 37 Il Il It. It Il 0.00 77 80 273O 2.7 38 It It It dd It 0.10 45 510 239O ¹ · 5. 39 It It ti dd ti 0.50 - 59 • 1220 I85O 1.5 40 0.02 0.42 0.56 0.10 Approx 3.0 38 540 1590 2.6 41 Il dd It Il Il 0.00 65 75 286O 2.9 42 Il Il Il ti Il 0.10 40 480 238O 1.2 43 Il It Il it Il 0.50 52 1230 I960 1.8 44 0.02 0.41 0.57 0.20 Sr 3.0 31 660 I58O 2.8 45 It It Il Il Il 0.00 62 70 4O3O 2.9 46 Il Il Il Il It 0.10 38 480 38IO 1.5 47 Il It Il It It 0.50 51 .1510 3VIO 1.9 48 'OO 9809 / 3.0 52 650 2990 2.8 1473 *

Table if

Sys'tera of Pb (Sb _1/2 Ta _1/2 ) 0 ₃ - PbTiO ₃ - PbZrO ₃

0.02 Basic composition ft 0.02 Me MnO ^k r Si £ tancf * No. Il Σ 0.51 Il Ba (Wt. % ) (S0 (si), ' 1 Il OM Il Il ti 0.00 66 100 1470 2.7 2 dd Il Il It It 0.10 IfO if 70 1050 * 1.1 3 0.02 Il It 0.10 ti 0.50 ■ 61 1580 9M) 1.2 if Il Il 0.51 It Ba 3.0 if2 if10 690 2.7 5 Il 0, if7 H Il It 0.00 62 85 1770 2.7 6th It Il H Il Il 0.10 38 if60 iif30 .1,2 7 " 0.02 It Il 0.25 Il ■ 0.50 56 1if80 1210 1.2 8th Il ti 0.51 ti Ba 3.0 35 if20 880, 2.5 9 Il 0, lf7 It Il ti 0.00 32 80 38ifO 3.8 10 ti It Il If Il 0.10 30th 550 ■ 3210 1.5 ' 11th 0.02 ti ti 0.01 dd 0.50 30th 1750 2880 1.9 12th 11th Il 0.51 It Sr 3.0 23 630 2530 " 2.9 13th It 0Λ7 ti Il It 0.00 69 100 1if30 2.7 Iif Il Il Il H Il 0.10 if2 if80 1OifO 1.2 15th 0.02 Il Il 0.01 dd 0.50 62 1660 800 1.3. 16 Il Il 0.51 ti Approx 3.0 ifO if 30 680 2.6 17th tr 0, If ₇ dd ti Il 0.00 67 95 1 if if O 2.7 18th Il Il dd It ti 0.10 IfO if90 1000 1.2 19th Il Il dd 0.50 61 1720 760 1.3 20th 11th 3.0 38 510 630 2 * 5

0 0 9809 / U73

Continuation table k

Basic composition Σ Z dd Pb (£ system <2 ^{) 0} 3 ' from , - PbZrO- did JC 0.46 0.52 0.05 > b, Ta
^D i / 2 ^ia 1 / ^k r - PbTiO ε (X) 0.02 ti ti dd Me MnO «) * m 2.8 No. It dd ti Il Sr (Weight *) 68 1620 1.2 21 Il Il Il Il Il , 0.00 if if 95 1230 1.5 22nd It 0.45 0.53 0.05 Il 0.10 62 510 860 2.6 23 0.02 Il dd ti Il 0.50 ifO 1710 660 2.9 2k it Il ti Il Approx 3.0 Sk > 90 1660 1.2 ■ 25th ti Il It ' Il ti 0.00 41 90 1310 1.8 26th Il O ₁ Mf .0.5 * 0.10 Il 0.10 60 if50. 1140 2.5 27 0.02 Il Il ti U 0.50 31 iif90 740 2.8 28 It Il It ti Sr 3.0 65 if OO 2010 1.2 29 It ti Il ti Il 0.00 40 90 1590 1.7 30th It 0.42 0.56 0.10 Il 0.10 62 500 1300 2.7 31 0.02 Il Il Il Il 0.50 . 32 1580 880 3.1 32 ti Il Il Il Approx 3.0 57 if 70 2050. 1.5 33 Il Il It Il ti 0.00 36 ' 80 1480 1.8 34 It 0, if1 0.57 0.20. It 0.10 5k 390 1290 2.8 35 0.02 Il It ti " Il 0.50 27 1660 930 3.3 ν 36 Il ti Il Il Sr 3.0 5k 520 - 3770 1.8 37 ti Il 11th ti Il 0.00 32 80 3250 2.0 38 Il dd 0.10 50 420 2890 3.0 39 dd 0.50 26th 1570 Ζ6θ6 IfO 3.0 460

009809 / U73

Claims (3)

Claims / 1.! Piezoelectric ceramic material, which consists essentially of a solid solution of the components Pb (Sb. .- Z,) O, PbTiO and PbZrO, where Z represents one of the elements niobium (Nb) and tantalum (Ta), characterized that 0.10 to 3.0 percent by weight of manganese oxide (MnO) is added and that up to 25 atomic percent of lead (Pb) can be replaced by at least one of the elements barium (Ba), strontium (Sr) and calcium (Ca) * 2. Piezoelectric ceramic material, which essentially consists of a basic composition of the formula consists in which x_ + £ + "L - ^» 00 mean the molar fractions and Z one of the elements Nb and Ta, characterized in that 0.10 to 3.0 percent by weight of manganese oxide (MnO) are added, up to 25 atomic percent Lead (Pb) can be replaced by at least one of the elements barium (Ba), strontium (Sr) and calcium (Ca) and that the composition in the diagram of this three-component system, if niobium (Nb) is selected for Z, is within an area with the corners ABCDE (Fig. 1), and within a surface with the corners FGHIJK, if Tantalum (Ta) is selected for Z · (Fig. 3), the corners being determined by the following mole fraction coordinates: 3C X 0.38 A. 0.01 0.61 0.90 B. 0.01 0.09 0.90 C. 0.05 0.05 0, IfO D. 0.30 · 0.30 0.20 E. 0.10 0.70 . oM F. 0.01 0.55 0.90 G 0.01 0.09 0.90 H 0.05 0.05 009809 / U73 I. 0.30 0.05 0.65 J 0.30 0, if0 0.30 K 0.05 0.65 0.30 3. Piezoelectric ceramic material according to claim 1 and 2, characterized by commercially available niobium V oxide (Nb ₃ O-), tantalum V oxide (Ta_0) and
Zirconium dioxide (ZrO), which contains a few percent tantalum V oxide (Ta ₃ O-), niobium V oxide (Nb ₂ O ₅ ) or hafnium dioxide (HfO-), as three of the starting materials. k. Use of ceramic material according to claims 1 to 3 for the production of components for ceramic filters and transducer elements for
mechanical filters. 009809> 1473