DE2835861A1 - CERAMIC, DIELECTRIC MATERIAL FOR TEMPERATURE COMPENSATION PURPOSES - Google Patents

Description

B LU M BAG H WESER BERGEN. CHANDLER ZWiRNER. DEER . BREHM

PATENT LAWYERS IN MUNICH AND WIESBADEN i Q 3 Q Q Q!

Patentconsull Radeckestrasse 43 8000 Munich 60 Telephone (089) 883603/883604 Telex 05-212313 Telegrams Palenlconsull Patentconsull Sonnenberger SlraEe 43 6200 Wiesbaden Telelon (06121) 562943/561998 Telex 04-186237 Telegrams Patentconsult

KABUSHIKI KAISHA SWA SBIKOSHA

3-4, 4-chome, Ginza,

Chuo-ku, Tokyo, Japan

T4KAGI KOGYO KABUSHIKI KAISHA
5-5, 3-chome, Owa, Suwa-shi,
Nagano-ken, Japan

Ceramic, dielectric material for temperature compensation =

purposes

Description:

This invention "relates to a ceramic dielectric material for temperature compensation purposes, which has a high dielectric constant, a small temperature coefficient and more a small dielectric loss factor (tan J ") having.

Munich: R. Kramer Dipl.-Ing. · W. Weser Dipl.-Phys. Dr. rer. nat. · P. Hirsch Dipl.-Ing. . H. P. Brehm Oipl.-Chem. Dr. phil. nat. Wiesbaden: P. G. Blumbach Dipl.-Ing. . P. Bergen Dipl.-Ing. Dr. jur. . G. Zwirner Dipl.-Ing. Dipl.-W.-Ing.

909810/0740

Known materials of this type are obtained by adding BaO, CaO, SrO _5, ZrO ₂ , MgO and the like to TiO ₃ . The disadvantage of the known materials is that the temperature coefficient also increases with an increase in the dielectric constant. On the other hand v / ground materials required ₉ d: .e a high dielectric constant with a small temperature coefficient having "Furthermore, an increase in the dielectric Verlusxfaktors (tan J *) occur when the temperature coefficient is reduced. CaTiO ^ has a dielectric constant of 160 and a temperature coefficient of -1600 ppm / ° C; in the same way, SrTiO-, has a dielectric constant of 56O and. a temperature coefficient of -4500 ppm / C. An improvement can be achieved if Bi ₂ O or BipO ^ and TiO _{2 together are} added, which leads to a decrease in the temperature coefficient. In this case too, however, materials which have satisfactory values for both the dielectric constant and the temperature coefficient are not obtained

The object of this invention is to provide ₅ materials of the type mentioned _B which have a value of more than 500 for the dielectric constant, a value of less than 2500 ppm / ° C for the temperature coefficient and superior sintering conditions «

The inventive solutions to this task? are materials the composition specified in claims 1, 2 or 3

909810/0740

■ ■. " ⁵ ~ 283586T

Advantageous developments of these materials according to the invention result from the subclaims.

According to a facial trace of the present invention, a material is thus provided which consists of a base material (= 100 parts by weight) BaTiO ₃ -Ba (Na. .. V ₃ μ) ° 3 and 0.1 to 5 parts by weight Consists of SiO _3; In an alternative embodiment, this material can additionally contain 0.1 to 3 parts by weight of a material composed of one, two or more of the following components, namely MnO ₃ , Bi ₃ O ₃ , A1 ₂ ° 3 ' ^Fe 2 ° 3' ^Ti0 2 ' ^Sn0 2' ^Cu0 " ¹ ^ ^CcO '

According to another aspect of the invention, the material can consist of a basic mass (= 100 parts by weight) of BaTiO ₅ -Ba (Na ₁ /, Ta, /.) 0, and 0.1 to 5 parts by weight of SiO ₃ ; According to an alternative embodiment, this material can additionally contain 0.1 to 3 parts by weight of a "material made up of one, two or more of the following components, namely MnO ₂ , Bi ₃ O ₅ , Al ₃ O ₅ , Fe ₂ G ₅₁ TiO ₂ , SnO ₂ , CuO and GoO.

According to a further aspect, the material according to the invention consists of a basic mass (= 100 parts by weight) of 40 to 85 mol% BaTlO _{5, the} remainder GaTiO ₅ and 1 to 10 parts by weight Ba (Na ₁ Z (V ₅ Zj) O ₅ according to an alternative embodiment, this material 0.1 to 3 parts by weight, in addition a matter is from one, two or contain more of the following components, namely, SiO _2, MnO _2, TiO _2, Al ₃ O _5, Bi ₂ O ₅ , Fe ₂ O ₅₁ CuO and GoO.

Ji) HiJ If) / OVAO

The following examples serve to explain the invention in detail without restricting it »

Example 1:

BaCO ,, Na ₂ CO ^ and VpOc (in commercially available quality) are in a molar ratio of 8: 1; 3 mixed together; the mixture is treated in the form of a slurry in a ball mill (capacity 1 l) for 24 hours; The treated mixture is then dried and then for 2 hours at "Ί50 to" ^or ~~ ", .u-nalcined. Thereafter, the compound .. / aJ-x / λ) ⁰ - * ^m ^ Per ovskit structure is obtained.

To produce BaTiO-, BaCO ,, and TiO ₂ are mixed with one another in a molar ratio of 1: 1, and the mixture obtained is treated in the same way in a ball mill; after drying, it is pre-calcined ^{at 1150 to 125O 0 C for 2 hours.}

The BaTiO obtained in this way and Ba (Na. /J./,) 0-, and one or more of the following oxides SiO ₂ ,, MnO ₂ , BipO *, ALpO Pe ₂ O- ,, TiO ₂ , S11O2 »CuO and CoO are mixed with one another in the proportions given in Table 1 below, and the mixture obtained is treated in the form of a slurry in a ball mill for 20 hours.

It is then dried, mixed with polyvinyl alcohol and di.or.es Ma tec LaI to «in«? circular pleading with a diameter

) 0: J I) I Π / ü 7 k Ü

knife of 10 mm and a height of 2 mm pressed; thereupon becomes this compact under the conditions given below sintered.

When firing, silver is applied to the ceramic logs and the supply lines are attached to it. The dielectric constant, the dielectric loss factor (tan C ^) and the temperature coefficient of these sintered ceramic materials are then determined by known methods5 the measurements were made at a frequency of 1 kHz; the dielectric constant and the dielectric loss factor (tan (P) vrarden determined at 20 ⁰ C; the results obtained are shown in Table 2 below.

909810/0740

Composition of the dielectric material

Sample BaIDiCU Ba (Na ^_1/1 SiO MnO _{0 9 9} Bi O, Al ₉ O, Fe ₉ O, TiO _{9 9} SnO CuO CoO

Mol-? £ Mol-? 6 wt. Wt. Wt. Wt. Wt. Wt. Wt. Wt. % * -% -% -% <- % -% -% -% -%

1 90 10 0.05 O ₅ 05 O ₉ 05 O ₃ 5 Op 3 o _s 05 O, 5 2 ₉ 5 0.3 5 1.0 4th 2 80 20th 1 * 5 1, 5 1.5 3 70 30th 5.5 3 ₉ 1 3p1 2 _pp O ₉ 5 O ₉ 2 4th 60 40 0p5 5 50 50 0.5 0.5 O ₈ 5 O ₉ 3 1* O O ₉ 5 O ₉ 6th 60 40 O ₉ 5 7th 60 40 O ₉ 5 O ₉ 5 O ₀ 5 O ₉ 3 1. O 1. O O ₉ 8th 60 40 0.5 9 70 30th 0.5 O ₉ 05 5 I ₈ O 1" O 10 70 30th 0.5 11 70 30th 0.5 0.5 5 12th 60 40 O ₅ 5 13th 60 40 0 _s 5 1.0 14th 60 40 0.5 If 60 40 0.5 16 70 30th 0.5 17th 60 40 0.5 η 0 18th 60 40 0.5 19th 70 30th 0.5 20th 70 30th 0.5 21st 60 40 22nd 60 40 ■ 23 70. 30th 24 70 30th 25th 70 • 30

These inputs refer to the Gex ^ icht of the basic mass from (BaTiO ₅ + Ba (CTa ₁ ^ Vj ^ Oj) - 100 % .

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2:

Sintering conditions and electrical properties of the samples

according to Tab. 1

No. Sintering dielectric dielectric Temperature-

constant loss factor coefficient (tan J *) (ppni / ° C)

1 3h at 135O ⁰ G 1500 0.7 + 2000 2 3h at 1380 ⁰ C 1200 0.5 + 1300 3 3h at 1400 ⁰ C 850 0.2 + 950 4th 3h at 145O ⁰ C 650 0.4 + 550 5 3h at 1450 ⁰ C 450 0.8 - 1500 6th 3h at 1420 ⁰ C 550 0.45 + 500 7th 3h at 1400 ⁰ C 500 0.1 + 430 8th 3h at 13SO ⁰ G 430 1.35 + 380 9 3h at 1380 ⁰ C 750 0.1 + 870 10 3h at 1380 ⁰ C 670 0.1 ■ f 800 11 3h at 138O ⁰ C 540 2.1 + 720 12th 3h at 1420 ⁰ C 550 0.1 + 460 13th 3h at 1420 ⁰ C 500 0.15 + 400 14th 3h at 142O ⁰ C 430 1.4 + 340 15th 3h at 1420 ⁰ C 500 0.15 + 400 16 3h at 1380 ⁰ C 640 0.2 + 500 17th 3h at 142O ⁰ C 500 0.3 + 380 18th 3h at 1420 ⁰ C 520 0.35 + 400 19th 3h at 1380 ⁰ C 450 2.2 + ■ "350 20th 3h at 1380 ⁰ C 600 0.05 + 500 21st 3h at 1420 ⁰ C 580 3.5 + 480 22nd 3h at 1420 ⁰ C 580 0.05 + 42o 23 3h at 138O ⁰ C 480 0.15 {- 560 24 3h at 1380 ⁰ C 460 4.5 + 540 25th 3h at 1380 ⁰ C 430 0.2f + 480

90 9 8 I ü / 0740

As can be seen from samples 1 to 5 of Table 2, with an increase in the Ba (Na ./. T, /.) O ₇ content, the dielectric constant, the dielectric loss factor (tan (P ) and the temperature coefficient decrease The minimum value for the loss factor (tan cT) is obtained for an AnMLmL 30 mol% Ba (Wa ₁ , .Y-? / a) 0-z ; a minimum value for the temperature coefficient is obtained for a proportion of 40 mol % Ba (Fa ₁ , .V - / *) £> ■ * obtained.

If the composition BaTiO, -Ba (] Ta .. / Λ-ζ / a) ^ 'a is present, large values for the loss factor (tanir) are obtained »W .: ^; ö .jet ¹ ■ (■ ueü samples 6 to 8 can be seen, the dielectric constant can be adjusted accordingly and the loss factor (tany) reduced by adding small amounts of SiO "to the base material. However, if the SiOp proportion is 5 wt .- / o exceeds the base mass, then the value for the dielectric loss factor (tan (P ) increases again.

Furthermore, it can be seen from samples 9 to 25 that the sintering conditions are improved by small proportions of other oxides and the fourth for the dielectric loss factor (tan </ ^) is reduced; furthermore, the mechanical strength of the ceramic material is increased by adding these oxides. If, however, the proportion of the added oxides exceeds a total of 3% by weight of the base material (= 100% by weight ) , the sub-conditions deteriorate and the dielectric constant decreases again.

909810/07 / »0

2B35861

The individual samples represent special versions of the invention, ceramic material. The samples obtained after dry blending show similar properties. Example 2:

BaCO ₅ , Na ₂ CCU and Ia ₂ Oc (in commercially available quality) are mixed with one another in a molar ratio of 8: 1: 5; the mixture is treated in the form of a slurry in a ball mill (capacity 1: 1) for 24 hours; the treated mixture is then dried and then pre-calcined ^{at 1150 to 1250 ° C. for 2 hours.} Then the compound Ba (Naw.üa, /.) With a perovskite structure is obtained.

To produce BaUiO, BaCO ₅ and TiOp are mixed with one another in a molar ratio of 1: 1, and the mixture obtained is treated in the same way in a ball mill; after drying, it is pre-calcined ^{at 1150 to 1250 ° C. for 2 hours.}

The BaTiO obtained in this way and Ba (Na .. / Λ & -Ζ / a) ® * ^s0 " such as one or more of the following oxides SiO ₂ , MnOg, Bi ₂ O ,, AlpO ₅ , Pe ₂ O ₅ , TiO ₂ , SnOp, CuO and CoO are mixed with one another in the proportions given in Table 3 below, and the mixture obtained in the form of a slurry is treated in a ball mill for 20 hours.

9098 10/0740

It is then dried, mixed with polyvinyl alcohol and this material is pressed into a circular disk with a diameter of 10 mm and a height of 2 mm; thereupon this compact is sintered under the conditions given below

During firing, silver is applied to the ceramic disc and the supply lines are attached to it. The dielectric constant, the dielectric loss factor (tan ν ) and the temperature coefficient of these sintered ceramic materials are then determined using known methods, the measurements were made at a frequency of 1 kHz 5 the dielectric constant and the dielectric loss factor (tan (F ) were determined at 20 ⁰ C ^ the results obtained are listed in the following table 4,

909810/0740

BaTiO ₅ 1-3 3. b e Mol% ^r 4 ^Si0 2 MnO ₂ 11 dielectric • 0.3 5 2 3 2835861 0.8 0.5 0.3 0.3 0.8 0, Mol% composition Weight Weight of Gev /. Materials 0.5 0, 5 -% * 3 ^A1 2 °: -tf sample 90 V 10 Bi ₂ O Weight TiO ₂ SnO ₂ CuO GoO 90 20th Ge ν /. -% 0.3 Weight weight weight weight 80 30th -% -% -% -% ~% __ 1 70 40 2 60 50 3 50 20th 1.0 4th 80 20th 0.08 5 80 20th 1.5 6th 80 30th 5.2 7th 70 30th 0.5 8th 70 30th 0.5 0.05 9 70 40 0.5 1.5 10 60 40 0.5 3.1 11 60 40 0.5 12th 60 20th 0.5 13th 80 20th 0.5 0.05 14th 80 20th 0.5 1.5 0.05 15th 80 20th 0.5 0.8 3.1 16 80 20th 0.5 17th 80 20th 0.5 0.01 18th 80 30th 0.5 1.5 1.0 0.8 19th 70 30th 0.5 0.5 20th 70 30th 0.5 0.5 21st 70 30th 0.5 1.5 22nd 70 0.5 0.5 23 24 25th 0.3

These figures relate to the weight of the matrix of (BaTiO ι- ₅ Ba (tia, _{l / 4} Ta _5/4) 0 ₃₎ = 100%.

9 0 9 0 1 0/0 7 A 0

Tabel

Sintering conditions and electrical properties of the samples adhere

according to tab.

No sintering

Dielectric constant dielect.
Loss factor
(tancA)

Temperature coefficient (ppm / ° C)

10
11
12th
13th
14th
15th
16

19th
20th
21
22nd
23
24
25th

3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at

3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at
3h at

1400 ⁰ C
1420 ⁰ C
1440 ⁰ C
148O ⁰ C
1500 ⁰ C
1520 ⁰ C
1420 ⁰ C
1380 ° Π

13 SO ⁰ C
138O ⁰ C
138O ⁰ C
138O ⁰ C
138O ⁰ C
1380 ⁰ C
138O ⁰ C
138O ⁰ C
136O ⁰ C
136O ⁰ C
136O ⁰ C
• f340 ° C
136O ⁰ C
138O ⁰ C
136O ⁰ C
136O ⁰ C

1400 1100 850 600 350 280 840 650 450 580 420 360 350 220 160 650 620 410 630 610 570 500 460 390 430 0.6

0.6

0.5

0 _s 5

0.2

0.3

0.5

0.4

2.0

0.5

O ₃ 3

0.2

0.2

0.3

1.75

0.3

0.35

0.25

0.2

0.35

0.55
0.45
1.35
0.55

+3000 + 1500

800 600 450 200 800 480 320

+ 550

470 310 300

+ 210

120 480 430 310 470 420 380 550 320 270 470

909810/0740

As can be seen from Table 4 with reference to Samples 1 to 6, with an increase in the Ba (Na ₁ /, Ta, /,) 0, content, the dielectric constant, the dielectric loss factor (tan (/ *) and The dielectric dissipation factor (tan c / ) has a minimum value of 4OMoI- ^ Ba (Na ₁ / iTa ^ /.) O ^; in the same way the temperature coefficient has a minimum value for a Ba ( Na ₁ / ^ Ta) O ₅ content of 55 mol%.

If the basic mass consists of BaTiO ^ -Ba (Na ₁ /.Ta·,/,)O^, large values are obtained for the dielectric loss factor (tan J *). ! However, as from the sample 7 is visible to 9, which can be adjusted according to dielectric constant and the dielectric loss factor (tan ν) lowered, the matrix provided that (= 100 percent by _e -%) 0 ₅ 1 wt .-% or more of SiO ₂ can be added. However, where the SiOP additional 5 wt .-% exceeds "then occurs again an increase in the dielectric loss factor (tan (P); therefore, the addition of siop is limited to a level of from 0.1 to 5 wt .-% of the base composition .

As can further be seen from samples 10 to 25 _s to _s 1 wt .-% or more, the sintering conditions are improved and the dielectric loss factor (tan c /?) Reduced v / ground by an addition of the other oxides in a proportion of 0 | furthermore, the corresponding ceramic materials have an increased strength. If, however, the addition of these other oxides exceeds a total of 3% by weight (based on the base mass = 100 (sew%),

909810/0740

In turn, deterioration of the sintering conditions occurs and the dielectric constant decreases. That's why the stake these other oxides are limited to 0.1 to 3 wt%.

The samples in this example represent special? Embodiments of the ceramic material according to the invention. The dry Mixing obtained samples show similar properties «Example 35

Commercially available starting materials are used for the production of these ceramic materials. In particular, for the production of BaTiO, the starting materials BaCO, and TiOp are mixed together in equal molar quantities. For the production of CaTiO, the starting materials CaCO and TiOp are mixed together in equal molar amounts mixed; finally, the starting materials for the production of Ba (NaW-V ₅ Z ^) O ₅

BaCO, j Na ₀ CO, and V ₀ Or- in the molar ratio 8: 1 ι 3 with each other 0 2 ρ 2 p

mixed; Each of these mixtures is pre-calcined for 2 hours at 1100 to 125O ⁰ C and after appropriate comminution gives the respective compounds ,,

These materials are then mixed with one another in the proportions given in Table 5 below, and the resulting Treated mixtures in the form of a slurry in a urethane-lined ball mill; then v / ird dried and then an aqueous solution of polyvinyl alcohol serving as a binding agent was added

909810/0740

is formed into circular disks with a diameter γοη 10 mm and a height of 2 mm and pressed under a pressure of 1 Ms 2 t / cm; it is then sintered under the sintering conditions given in Table 6 below. The ceramic disks obtained are fired with a Pd-Ag paste in order to produce electrical connections; then the dielectric constant, the dielectric loss factor (tan tr) and the temperature coefficient are determined; the measurements are made at a frequency of 1 kHz; the dielectric constant and the dissipation factor are determined at 20 ⁰ G; the largest fourths of the temperature coefficient occur in the range from -20 to +80 C, since no linear changes in the dielectric constant occur in this temperature range; the results obtained are listed in Table 6 below,

9 0 3810/0740

! table 5
Composition of the dielectric material

Sample BaTiO, OaTiO, Ba (Ka SnO ₀ SiO ₀ MhO ₀ TiO ₀ Al ₀ O, Bi ₀ O, Pe ₀ O, CuO GoO J j γ ZZZZZ ο Z 3 2 3

3/4> ° 3

Mole-96 mole-a weight weight weight weight weight weight weight weight weight weight weight weight weight weight

1 35 65 0.8 0.05. 0.05 0.03 0 , 5 0.03 0.02 0.5 0.3 0.3 0.2 0.2 0.2 2 40 60 0.8 3 60 40 - 4th 85 15th 3 1.0 0.2 0.3 5 90 10 9 0.5 1 , 0 0.5 0.2 6th 60 40 9 0.2 1 , 0 7th 80 20th 9 1.5 1.0 0 , 05 0.5 8th 60 40 11 0.5 1.0 1.0 9 85 ID 11 1.0 0 , 5 0.2 10 40 60 5 0.3 0.03 0.5 11 65 35 5 1.0 0.3 0.5 12th 90 10 5 0.2 O ₉ 5 13th 60 40 5 1.0 14th 80 20th 5 15th 60 40 5 16 60 40 5 17th 60 40 5 18th 60 40 5 19th 60 40 5 ZO 60 40 5 60 40 5 22nd 60 40 5 > 3 80 20th > 4 80 20th VJl 80 20th 16 80 20th Ϊ7 80 20th

Read data refer to the weight of the basic weight of BaTiO, l · GaTiO,) = 100 %.

ÖÜ9810 / 0740

Sintering "at 1320 ⁰ C according to Tab. 5 dielect « temperature hey 135O ⁰ C Yerl factor
(tan cf) coefficient
(ppm / ^Ö C) No. 3h "at 135O ⁰ C Dielectrics 0.5 2050 3h "at 135O ⁰ C constant 0.6 2480 1 3h "at 135O ⁰ C 460 0.6 3200 2 3h "at 135O ° C 510 0.6 4800 3 3h hey 135O ⁰ C 870 0.7 6200 4th 3h at 135O ⁰ C 2200 0.6 3200 5 3h at 135O ⁰ C 2700 0.6 4500 6th 3h at 135O ⁰ C . 860 0.5 1800 7th 3h at 135O ⁰ C 1900 0.5 2050 8th 3h at 135O ⁰ C 550 0.5 1200 9 3h at 135O ⁰ C 670 0.5 1800 10 3h at 135O ⁰ C 320 0.5 2600 11 3h at 135O ⁰ C 590 5.8 1700 12th 3h at 135O ° C 7BO 5.2 1900 13th 3h at 135O ⁰ C 530 0.6 1700 14th 3h at 135O ⁰ C 650 0.5 1750 15th 3h at 135O ⁰ C 540 0.6 1700 16 3h at 135O ⁰ C 550 0.3 900 17th 3h at 132O ⁰ C 550 0.3 950 18th 3h at 132O ⁰ C 500 0.3 1050 19th 3h at 132O ⁰ C 510 5.9 1200 20th 3h at 135O ⁰ C 520 • 6.2 1150 21st 3h at 135O ⁰ C 220 6.6 1300 22nd 3h at 135O ⁰ C 230 0.5 1250 23 3h at 135O ⁰ C 210 0.2 1300 24 3h 630 0.2 1200 25th 3h 600 0.2 1200 26th 580 27 590

909810/0740

Samples 1 to 5 of Table 5 consist only of the basic mass, that is to say in this case of the components BaTiO and CaTiO _7:; As can be seen from Table 6, Samples 1 and 2 have satisfactory values for the dielectric constant and the temperature coefficient; on the other hand, the mechanical strength is not entirely satisfactory and difficulties arise in manufacture

Samples 6 to 14 contain, in addition to the basic mass, Ba (Na. // V ₅ 1.) 0-, in the specified proportions. As can be seen from the samples 6 and 7, occurs at the low levels of only 0.8 part by weight 9o Ba (Na. / Λ-ζ / λ) * ® (based on the basic mass = 100 wt .-? O) no significant effect on; On the other hand, samples 13 and I4 with a Ba (Na. /? '^) content of more than 10% by weight exhibit deteriorated sintering conditions, and the loss factor (tan c /) increases again.

The proportion of Ba (Na. / Λ-ζ / λ) 0-z is therefore kept between 1 and 10 % by weight. The other samples 15 to 27 concern the addition of some oxides. Samples 15 »16, 17 and 24 have no noticeable effects because the addition is less than 0.1% by weight; On the other hand, samples 21, 22 and 23 with an addition of more than 3% by weight have deteriorated sintering conditions and an increase in the decomposition factor (tan tf * ), at the same time the reaction with a zirconium dioxide layer is facilitated. For this reason, the proportion of these oxides should be a total of 0.1 to 3% by weight of the basic mass of BaTiO and CaTiO.

909810/0740

The samples of this example represent specific embodiments of the inventive ceramic material. The dry Mixing obtained samples show similar properties.

The inventive, ceramic, dielectric material has high mechanical strength and superior abrasion resistance on; therefore this material can be processed under normal working conditions and represents a highly suitable one dielectric material for miniaturized components, such as for the miniaturized trimming capacitor one Timepiece with quartz crystal.

90 9 810/0740

Claims (6)

BLUMBACH ■ MEADOWS ι FjnRG'iN - KRAiVIER ZVVIRNER. HiRSGH - BREHM _{ft n} . ^ 8 3 b 8 β I. PATENT LAWYERS IN MUNICH AND WIESBADEN * '" Patontconsult RadeckostraBe 43 8000 Munich 60 Telephone (039) 883605/83360 + Telex 05-212313 Telegrams Paleniconsult Patentconsult Sonnenberger Straße 43 6200 Wiesbaden Telephone (06121) 562943/561998 Telex 04-186237 Telegrams Patoniconsult KABUSHIIQ KAISHA SlMA SEIKOSHA 3-4, 4-chome, Ginza,, 78/8750 Chuo-ku, Tokyo, Japan QIAKAGI KOGYO KABUSHIKI KAISHA 3-5, 3-chonie, Owa, Suv / a-shi, Nagano-ken, Japan Ceramic, dielectric material for temperature compensation zv ^"r corner Patent claims: v1. Ceramic, dielectric material for temperature compensation corners, consisting essentially of a solid solution of 50 to 99 MoI- ^ BaTiO ₅₁ remainder Ba (Na ₁ Z ₄ 2. Ceramic, dielectric material for temperature compensation purposes, . ■ consisting essentially of a solid solution of 50 to Munich: R. Kramer Dipl.-Ing. · W. Weser Dipl.-Phys. Dr. rer. nal. · P. Hirsch Dipl.-Ing. . H. P. Brehm Dipl.-Chem. Dr. phil. nat. Wiesbaden: P.G. Blumbach Dipl.-Ing. · P.Bergen Dipl.-Ing. Dr. jur. · G. Zwirner Dipl.-Ing. Dipl.-W.-Ing. 9 0 9 8 10/0740 MoI-SO BaTiO ₅ , remainder Ba (Na ₁ /, Ta -, / J 3. Ceramic, dielectric material for temperature coniperization purposes, consisting essentially of 100 parts by weight of a mixture of 40 to 85 mol% BaTiO ₅ , the remainder CaTiO ₅ ; and 1 to 10 parts by weight of Ba (Na ₁ /.V ₇ / ^) O- ,. 4. Material according to claim 1 characterized geke is used to mark, that the material contains in addition to the Grundnuasse (= 100 parts by weight) 0.1 to 5 wt. "Parts SiO _2. 5. Material according to claim 1 or 2, characterized irekenny.oic'nne I that the material in addition to the base material (= 100 parts by weight) 0.1 to 5 parts by weight of _{SiO 2} ; and 0.1 to 3 parts by weight of MnO ₂ , Bi ₂ O ₅ , Al ₃ O ₅ , Fe ₂ O ₅ , TiO ₂ , SnO ₂ , CuO and / or CoO. 6. Material according to claim 3 _f, characterized in that the material additionally 0.1 to 3 parts by weight of SnOp, SiO ₂ , MnO ₂ , iO ₂ , Al ₂ O ₅ , Bi ₂ O ₅ , Pe ₂ O ₅ , CuO and / or CoO. 90981 0/0740