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DE909819C - Substances of high dielectric constant and process for their production - Google Patents

Substances of high dielectric constant and process for their production

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Publication number
DE909819C
DE909819C DEN3632A DEN0003632A DE909819C DE 909819 C DE909819 C DE 909819C DE N3632 A DEN3632 A DE N3632A DE N0003632 A DEN0003632 A DE N0003632A DE 909819 C DE909819 C DE 909819C
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ioo
temperature
substances
dielectric constant
high dielectric
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German (de)
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Eugene Wainer
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NAT LEAD CO
NL Industries Inc
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NAT LEAD CO
NL Industries Inc
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth titanates
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Description

Stoffe hoher Dielektrizitätskonstante und Verfahren zu ihrer Herstellung Die Erfindung bezieht sich auf keramische, dielektrische Stoffe und Verfahren zu ihrer Herstellung. Insbesondere betrifft die Erfindung solche Stoffe, die Verbindungen von Titanerde als vorherrschenden Bestandteil zusammen mit Verbindungen von Zinn enthalten.High dielectric constant substances and processes for their manufacture The invention relates to ceramic, dielectric materials and methods their manufacture. In particular, the invention relates to such substances, the compounds of titania as the predominant component along with compounds of tin contain.

In den USA.-Patenten z 42o 692 und 2 467 169 sind die vorteilhaften Eigenschaften von Bariumtitanat- und Strontiumtitanatmischungen beschrieben. Die vorliegende Erfindung bezieht sich auf eine andere Gruppe dieser Körper, deren Zweckmäßigkeit in ähnlicher Weise weitreichend ist, da diese Gruppe von keramischen Zusammensetzungen Eigenschaften aufweist, die sie als Kondensatoren im Rundfunk, Fernsehen und allgemein im Fernmeldewesen, als kapazitive Temperaturabgleichvorrichtungen in Empfängern und Fernmeldeanlagen zur Verhinderung von Störungen infolge durch Temperaturänderungen hervorgerufener Änderungen der Stromkreischarakteristiken geeignet machen. Die Dielektrizitätskonstanten einiger dieser Zusammensetzungen sind so hoch, daß ihre Verwendung in Niederfrequenzverteiler - und Fernmeldesystemen, beispielsweise 6o-Hz-Leitungen, durch kapazitive Kopplung zwischen einer Niederfrequenz-Hochspannungs-Ü'bertragungsleitung mit 2o bis 12o Hz und einer Fernmeldetelephonleitung möglich wird.The advantageous properties of barium titanate and strontium titanate mixtures are described in U.S. Patents No. 42o 692 and 2,467,169. The present invention relates to another group of these bodies, the usefulness of which is similarly far-reaching, since this group of ceramic compositions has properties that make them useful as capacitors in radio, television and telecommunications in general, as capacitive temperature balancing devices in receivers and telecommunications systems Make appropriate prevention of disturbances due to changes in circuit characteristics caused by changes in temperature. The dielectric constants of some of these compositions are so high that their use in low frequency distribution and communication systems, for example 60 Hz lines, is possible by capacitive coupling between a low frequency high voltage transmission line at 20 to 120 Hz and a telecommunication telephone line.

Darüber hinaus machen die sehr hohen Dielektrizitätskonstanten der keramischen Zusammensetzung nach der vorliegenden Erfindung diese Körper für die Verwendung als elektromechanische Vorrichtungen, beispielsweise zur Umwandlung von mechanischer Energie oder Bewegung in elektrische Energie oder umgekehrt geeignet, und zwar ähnlich in ihrer Wirkung wie piezoelektrische Kristalle. So sind die neuen erfindungsgemäßen Zusammensetzungen in der Piezoelektrizität, im Ultraschall, bei Kristall- oder Kondensatormikrophonen, Frequenzstabilisatoren, Lautsprechern, Schallaufnahmegeräten, Telephonen und allgemein bei Oszillatoren verwendbar. Die genannten Anwendungsmöglichkeiten betreffen insbesondere solche Körper, deren Dielektrizitätskonstanten bei Hochfrequenz über iooo liegen. In Kondensatormikrophonen werden sehr dünne Blättchen aus Stoffen hoher Dielektrizitätskonstante entweder in der Mitte oder an den Rändern starr eingeklemmt und als Schwingungsmembran verwendet. Die kleinen Änderungen der Lage oder Abmessungen des Dielektrikums infolge der Schwingung ergeben verhältnismäßig große Änderungen der Kapazität, durch die der Schall in elektrische Energie umgewandelt wird.In addition, the very high dielectric constants make the ceramic composition according to the present invention, these bodies for the Use as electromechanical devices, for example for converting mechanical energy or movement into electrical energy or vice versa suitable, similar in their effect to piezoelectric crystals. So are the new ones Compositions according to the invention in piezoelectricity, in ultrasound, at Crystal or condenser microphones, frequency stabilizers, loudspeakers, sound recording devices, Telephones and generally applicable to oscillators. The mentioned application possibilities relate in particular to those bodies whose dielectric constants are at high frequency lie over iooo. In condenser microphones, very thin sheets of material are made high dielectric constant either in the middle or rigidly clamped at the edges and used as a vibrating membrane. The small changes in location or dimensions of the dielectric as a result of the vibration result in relatively large changes the capacity by which the sound is converted into electrical energy.

Andere Glieder dieser Gruppe, besonders solche mit Dielektrizitätskonstanten über iooo, zeigen elektrische und mechanische Eigenschaften wie bei piezoelektrischen und pyroelektrischen Kristallen. So ergibt beispielsweise ein Stab aus diesem Material, der an einem Ende starr eingespannt ist und am anderen Ende frei schwingen kann, bei Schwingungen eine Potentialdifferenz von mehreren Volt zwischen den beiden Stabenden.Other members of this group, especially those with dielectric constants about iooo, show electrical and mechanical properties like piezoelectric ones and pyroelectric crystals. For example, a rod made of this material which is rigidly clamped at one end and can swing freely at the other end, In the case of vibrations, a potential difference of several volts between the two rod ends.

Die besondere Zweckmäßigkeit der Glieder dieser Gruppe als Kondensatoren zur Korrektion von Frequenzverschiebungen liegt nicht nur darin, daß man sowohl positive als auch negative Temperaturkoeffizienten in einem weiten Bereich erhalten kann, sondern auch darin, daß man die Möglichkeit hat, die Änderung des Temperaturkoeffizienten durch Wahl der richtigen Zusammensetzung zu regeln. Diese Eigenschaften ergeben zusammen mit einem extrem niedrig liegenden Leistungsfaktor in manchen Fällen einen hohen Grad von Zweckmäßigkeit für diese letztere Anwendungsart.The particular usefulness of the members of this group as capacitors to correct for frequency shifts is not only that one has both received positive as well as negative temperature coefficients in a wide range can, but also in the fact that it is possible to change the temperature coefficient to regulate by choosing the right composition. These properties result together with an extremely low power factor, in some cases one a high degree of convenience for this latter type of application.

Im allgemeinen bestehen die neuen Zusammensetzungen nach der vorliegenden Erfindung aus gebrannten Mischungen der Titanate und Stannate der Erdalkalimetalle. Allgemein können diese Mischungen aus einem oder mehreren Titanaten und einem oder mehreren Stannaten bestehen. Obwohl die Erdalkalimetallverbindungen nach der vorliegenden Erfindung allgemein Verwendung finden, sind die Stannate und Titanate von Barium, Strontium und Kalzium von besonderer Wichtigkeit. Im allgemeinen überschreitet der Gesamtstannatgehalt des keramischen Körpers nicht 5o°/0. Die allgemeinen Klassen von Zusammensetzungen nach der Erfindung sind in den Beispielen angegeben, Der besonders wirkungsvolle Effekt des Stannatzusatzes ist am deutlichsten im Fall des Zusatzes zu Bariumtitanat. Bei Hochfrequenz hat Bariumtitanat eine Dielektrizitätskonstante von i2oo bis 1300 und einen Temperaturkoeffizienten, der zwischen 2o und 15o° zuerst negativ, dann stark positiv und schließlich stark negativ ist. Dieses merkwürdige Verhalten läßt sich nicht nur durch Zusatz der Stannate beseitigen, sondern es werden Dielektrizitätskonstanten von wenigstens 13 ooo bei Hochfrequenz erzielt.In general, the novel compositions consist of the present invention Invention of calcined mixtures of the titanates and stannates of the alkaline earth metals. In general, these mixtures of one or more titanates and one or more consist of several stannates. Although the alkaline earth metal compounds according to the present Invention find general use are the stannates and titanates of barium, Strontium and calcium of particular importance. In general, the Total stannate content of the ceramic body not 50%. The general classes of compositions according to the invention are given in the examples, The particular the effective effect of the stannate addition is most evident in the case of the addition to barium titanate. At high frequency, barium titanate has a dielectric constant from i2oo to 1300 and a temperature coefficient that is between 2o and 15o ° first negative, then strongly positive, and finally strongly negative. This strange one Behavior can not only be eliminated by adding the stannates, it can become one Dielectric constants of at least 13,000 at high frequency achieved.

Nach der Erfindung werden die in der Tabelle angegebenen Bestandteile keramisch reagiert und dann gemahlen, so daß die gröbsten Teilchen durch ein 325-Maschen-Sieb hindurchgehen. Die getrockneten Pulver werden dann in den unten angegebenen Verhältnissen gemischt. Es werden annähernd io °/o Wasser hinzugegeben und vollständig gemischt. Das feuchte Pulver wird durch ein 2o-Maschen-Sieb gedrückt und zerkleinert. Das zerkleinerte Produkt wird dann in einem Gesenk unter einem Druck von o,8 bis 1,6 t/cm2 gepreßt und an Luft 24 Stunden getrocknet. Die zur Prüfung bestimmten Stücke hatten einen Durchmesser von etwa 2,5 cm und eine Decke von 2,5 mm. Die Stücke dieser Größe wurden dann mit annähernd 22o°/Std. bis zur Spitzentemperatur gebrannt, auf dieser Spitzentemperatur 3 Stunden gehalten und dann abgekühlt. Die Reifungstemperatur für alle unten angegebenen Körper liegt zwischen 1340 und 1370°. Nach dem Abkühlen werden die gegenüberliegenden Parallelflächen mit einer Silberpaste bestrichen, die zur Silberelektrode bei g15° aufgebrannt wird.According to the invention, the components indicated in the table Ceramic reacts and then ground so that the coarsest particles pass through a 325-mesh sieve go through. The dried powders are then used in the proportions given below mixed. Approximately 10% water is added and mixed completely. The moist powder is pressed through a 2o-mesh sieve and crushed. That The crushed product is then placed in a die under a pressure of 0.8 to 1.6 t / cm2 pressed and dried in air for 24 hours. The pieces intended for examination had a diameter of about 2.5 cm and a ceiling of 2.5 mm. The pieces of this The size was then approximately 220 ° / h. Burned to the peak temperature this peak temperature was held for 3 hours and then cooled. The ripening temperature for all the bodies given below is between 1340 and 1370 °. After cooling down the opposite parallel surfaces are coated with a silver paste, which is burned to the silver electrode at g15 °.

Die unten erhaltenen Werte wurden bei- i MHz auf einer Normalhochfrequenzbrücke bestimmt. Der spezifische Widerstand wurde in einem hochempfindlichen Widerstandskreis bestimmt, auf der Widerstände von i ooo ooo Megohm leicht hergestellt werden können. Zur Nullpunktanzeige diente ein Gasvanometer. Die iooo-Hz-Messungen wurden durch Verwendung einer Normalimpedanzbrücke erhalten, deren Zweige Widerstandskomponenten waren.The values obtained below were at -1 MHz on a standard high frequency bridge certainly. The resistivity was measured in a highly sensitive resistor circuit determined, on which resistances of i ooo ooo megohms can easily be made. A gas vanometer was used to display the zero point. The iooo Hz measurements were made by Using a normal impedance bridge obtained the branches of which are resistance components was.

Nach der Beschreibung des erfindungsgemäßen Verfahrens sollen in den folgenden Tabellen die verschiedenen Arten der Zusammensetzungen und die erhaltenen Werte angegeben werden.After the description of the method according to the invention, in the the following tables show the various types of compositions and those obtained Values are given.

Der besondere Vorteil solcher Zusammensetzungen als Kondensatormaterial für Überbrückungs- und Filterkondensatoren läßt sich aus den folgenden Zahlen entnehmen. So haben beispielsweise die heutigen Elektrolytkondensatoren bestenfalls Leistungsfaktoren zwischen 6 und 16 °/o, während die in der Tabelle angegebenen Werte unter 3 °/o liegen. Diese Stoffe lassen sich deshalb als Ersatz für Papier und Elektrolyte verwenden. Körper mit Leistungsfaktoren unter o,i °/o eignen sich als Ersatz für Glimmerkondensatoren. Die Möglichkeit der Änderung und Steuerung der Temperaturkoeffizienten, die es ermöglichen, die Zusammensetzungen als Kondensatoren zu verwenden, ist in den in Tabelle V und folgenden angegebenen Daten aufgezeigt. Diese Temperaturkoeffizienten wurden bei i MHz gemessen. Tabelle I Tabelle III CaTi03 Reihe BaTi03 Reihe i MHz i kHz i MHz i kHz Zus. CaTi08 elektri- Lei- elektri- Lei- Zus. BaTi08- e] Dtri- Lei- el gtri- Lei- Nr. Stannat zitäts- stungs- zitäts- stungs- Nr. Stannat zitäts- stungs- zitäts- stungs- faktor faktor Faktor faktor kon- kon kon- stante . °/o stante I °/a stante °io stante °/o i Z foo+I Ba Sn0g I62 0,010 171 1,3 I ioo+I Ba Sn03 1,525 0,82o 1,590 1,0 2 ioo+5 Ba Sn03 158 0,010 165 1,3 2 ioo+5 Ba Sn03 2,010 1,190 2,155 1,6 3 ioo+io Ba Sn 0, 148 o,oio 161 1,3 3 ioo+io Ba Sn 0, 3,580 2,730 3,970 1,4 4 8o+20 Ba Sn03 131 0,010 139 1,2 4 80+2o Ba Sn03 4,175 o,870 4,275 0,01 5 65-I-35 Ba Sn 03 142 0,015 149 1,3 5 65-I-35 Ba Sn 03 679 0,420 683 0,03 6 50+5o BaSn03 133 0,015 140 1,4 6 50-1-5o Ba Sn03 263 0,260 28o 2,8 7 Ioo+1 SrSn03 145 0,010 155 1,4 7 100+1 Sr Sn0, 1,65o 0,95o 1,730 I,I 8 ioo+5 Sr Sn03 133 0,010 148 1,4 8 ioo+5 Sr Sn03 2,300 1,500 2,470 1,8 9 ioo+io Sr Sn03 132 0,010 137 1,4 9 ioo+io Sr Sn03 4,300 o,980 4,78o 2,4 I0 80+2o Sr Sn03 107 0,010 123 1,4 i0 8o+20 Sr Sri03 1,720 0,320 1,735 0,01 I1 65+35 Sr Sn 03 77 0,010 86 1,7 11 65+35 Sr Sn 03 593 0230 605 0,o6 12 50+50 Sr Sn03 57 0,030 78 2,5 12 50+50 Sr Sn03 272 0,180 276 1,6 13 Ioo+i Ca Sn 03 150 0,010 157 . 1,4 13 100+1 Ca Sn 03 1,710 1,100 1,790 1,4 14 100+5 Ca Sn03 145 0,010 153 [ 1,3 14 100+5 CaSn03 2,680 2,000 2,840 1,8 15 ioo+io Ca Sn 03 132 0,010 142 1,4 15 IOO+IO Ca Sn 03 8,500 2,500 9,400 1,5 16 8o+20 Ca Sn03 103 0,010 117 1,4 16 8o+20 Ca Sn 03 1,420 I 0,320 1,445 0,02 17 65-I-35 Ca Sn03 76 o,oio 85 2,1 17 65+35 Ca Sn03 235 0,060 238 i,I. 18 50+50 Ca Sn03 61 o,oio 72 1,8 18 50+50 Ca Sn03 124 0,010 130 1,4 19 92+8 BaSn03 2,81o 2,620 3,290 2,0 20 88+12 Ba Sn03 6,575 2,720 7,06o 1,2 21 86+14 Ba Sn0., 9450 2,900 10,200 o,8 22 84+16 Ba Sn03 12,60o 2,200 13,100 0,4 23 82+18 BaSn03 7,550 Togo 7,250 0,1 Tabelle II Tabelle IV SrTi03-Reihe Komplexe Reihe i MHz r kHz i MHz i kHz . ele#ktri- I Lei- el#tri- Lei- Zus. SrTiO$- el nktri_ # Lei- el ktri- Lei- 7us Zusammensetzung Nr. Stannat _zitäts- stungs- zitäts stungs- \7r. zitäts- . stungs- zitäts- stungs- kon- Ifaktor kon- faktor kon- Faktor kon- Faktor stante °/o stante % stante °/o stante i ioo+i Ba Sn03 249 o,oio 26o i,i i 8o BaTiOs 2 ioo+5 Ba Sn0, 247 0,010 240 1,0 io BaSn03 ... 4,16o 0,95 3,510 0,01 3 ioo+io Ba Sn03 2i0 o,oio 22o 1,7 io SrSnO$ 4 80+2o Ba Sn03 233 0,010 237 1,2 2 7o BaTi03 5 65-h-35 Ba Sn03 155 0,040 163 1,9 2o BaSn03 ... 1,46o 0,38 1,415 0,01 6 50-1-5o Ba Sn 03 99 0,030 97 1,6 i0 Sr Sn 03 7 100+1 Sr Sn03 242 0,040 244 1,2 8 Ioo+5 Sr Sn03 227 o,060 238 1,2 3 7o BaTi03 j 9 IOo+io Sr Sn03 215 0,08o 217 1,2 i0 BaSnOg ... 2,I05 0,5o 1,805 I 0,02 io 8o-1-20 Sr Sn03 144 o,oio i49 1,7 2o SrSn03 ii 65-1--35 Sr Sn03 76 o,oio 84 2,0 4 7o BaTi03 12 50-1-50 Sr Sn0, 45 0,030 52 8,o 15 Ba Sn03 ... 1,475 03I 1450 0,10 13 100+ 1 Ca Sn 03 247 0,030 261 i, i 15 Sr Sn 03 14 100+5 Ca Sn03 237 0,040 244 1,1 5 85 BaTi03 15 ioo+io Ca Sn 03 2o8 0,020 214 i,i 5 Ba Sn 03 16 8o+20 Ca Sn0, 141 0,010 146 1,3 . 7,720 1,74 8,i00 0,50 17 65+35 Ca Sn 03 97 0,010 i08 2,6 5 Sr Sn 03 18 50+5o casn03 75 o,oio 85 i,6 5 Sr Ti03 J . Noch Tabelle IV r MHz r kHz Di- I Di- ! Zus. Zusammensetzung elektri- Lei- elektri- Lei- 5 Nr. zitäts- stungs- zitäts- stungs- kon- Jfaktor kon faktor stante I °,/o stante 6 7o BaTi03 To Ba Sn 03@ 10 SrSn0 1,350 0,23 1,320 0,2o 3 ' ' =o SrTi03 7 55 BaTi03 15 BaSn03 615 o,16 625 ' 1,30 15 Sr Sn 03 ... =5 SrTi 03 1 Tabelle V Temperatur-Kapazitätsdaten Temperatur Körper Nr. 3 Körper Nr. 9 I Körper Nr. r 5 o C Ca T103 CaTiOä CaTi03 Reihe Reihe Reihe K K K 20 ......... 148 137 132 30 ......... 148 137 132 40 ......... 148 136 131 50 .» ....... 147 136 131 6o ......... 146 135 130 70 ......... 146 134 129 8o ......... 145 134 I28 9o ......... 144 133 128 =oo ......... 143 132 127 IM ......... 141 131 126 120 ......... 140 129 125 1 30 ......... 139 128 124 140 ......... 138 127 123 1 50 ......... 137 126 122 Tabelle VI Temperatur-Kapazitätsdaten Temperatur Körper Nr. 3 Körper Nr. 9 Kö rperNr. 15 o C S: @i03 SrTi03 SrTi03- Reihe Reihe Reihe K K K 20 ......... 210 215 208 30 ......... 210 215 2o8 40 ......... 2O8 215 207 50 ......... 207 213 2o6 6o ......... 205 212 205 70 ......... 203 210 203 8o ......... 201 208 202 go ......... 198 2o6 199 j Too ......... 196 2o6 197 110 ......... 193 204 194 120 ......... 189 202 IgI 130 ......... 186 200 188 140 ......... 184 198 184 15 0 ......... 18o 196 182 Tabelle VII Temperatur-Kapazitätsdaten Körper Körper Körper Körper Temperatur Nr. 3 Nr. 9 Nr. 15 Nr. 5 ° C B&Ti03- BaTi03- BaTi0$- komplexe Reihe Reihe Reihe Reihe K K K K 20 ......... 3,580 4,300 8,500 7,720 30 ......... 3,78o 4,300 8,60o 7,500 40 ......... 4,020 4,270 8,940 7,400 50 ......... 4,330 4250 9.170 7,26o 6o ......... 4,780 4,180 9,48o 6,65o 70 ......... 5,350 4,120 9,I70 5,900 8o ......... 6,200 4,030 8,640 4,96o go ......... 6,8=o 3,94o 6,640 4,210 =OO ......... 7,220 3,900 5,46o 3,930 ==o ......... 8,=8o 3,80o q.,260 2,920 120 ......... 8,86o 3,540 3,530 2,380 130 ......... 8,950 3,120 2,830 1,940 =40 ........: 8,26o 2,640 2,290 I,600 150 ........ 7,520 2,210 2,000 1,470 Die Temperaturkoeffizienten der Zusammensetzungen nach den Tabellen V, VI und VII zeigen den Rahmen der möglichen Änderung. Während einzelne Zusammensetzungen den gewünschten Koeffizienten ergeben, ist eine unendliche Mannigfaltigkeit der Koeffizienten durch Parallelkombination von einem oder mehreren Körpern möglich.The particular advantage of such compositions as capacitor material for bypass and filter capacitors can be seen from the following figures. For example, today's electrolytic capacitors have power factors between 6 and 16% at best, while the values given in the table are below 3%. These substances can therefore be used as a substitute for paper and electrolytes. Bodies with power factors below o, i ° / o are suitable as a substitute for mica capacitors. The ability to vary and control the temperature coefficients that enable the compositions to be used as capacitors is shown in the data given in Table V and below. These temperature coefficients were measured at i MHz. Table I Table III CaTi03 series BaTi03 series i MHz i kHz i MHz i kHz Add. CaTi08 electric- Lei- electric- Lei- Add. BaTi08- e] Dtri- Lei- el gtri- Lei- No. Stannat zitäts- stzitts- factor factor factor factor con- con con- stante. ° / o stante I ° / a stante ° io stante ° / o i Z foo + I Ba Sn0g I62 0.010 171 1.3 I ioo + I Ba Sn03 1.525 0.82o 1.590 1.0 2 ioo + 5 Ba Sn03 158 0.010 165 1.3 2 ioo + 5 Ba Sn03 2.010 1.190 2.155 1.6 3 ioo + io Ba Sn 0, 148 o, oio 161 1.3 3 ioo + io Ba Sn 0, 3.580 2.730 3.970 1.4 4 8o + 20 Ba Sn03 131 0.010 139 1.2 4 80 + 2o Ba Sn03 4.175 o.870 4.275 0.01 5 65-I-35 Ba Sn 03 142 0.015 149 1.3 5 65-I-35 Ba Sn 0 3 679 0.420 683 0.03 6 50 + 5o BaSn03 133 0.015 140 1.4 6 50-1-5o Ba Sn03 263 0.260 28o 2.8 7 Ioo + 1 SrSn03 145 0.010 155 1.4 7 100 + 1 Sr Sn0, 1.65o 0.95o 1.730 I, I. 8 ioo + 5 Sr Sn03 133 0.010 148 1.4 8 ioo + 5 Sr Sn03 2.3 0 0 1.500 2.470 1.8 9 ioo + io Sr Sn03 132 0.010 137 1.4 9 ioo + io Sr Sn03 4.300 o, 980 4.78o 2.4 I0 80 + 2o Sr Sn03 107 0.010 123 1.4 i0 8o + 20 Sr Sri03 1.720 0.32 0 1.735 0.01 I 1 65 + 35 Sr Sn 03 77 0.010 86 1.7 11 65 + 35 Sr Sn 03 593 0230 605 0, o6 12 50 + 5 0 Sr Sn03 57 0.030 78 2.5 12 50 + 5 0 Sr Sn03 272 0.180 276 1.6 13 Ioo + i Ca Sn 03 15 0 0.010 157. 1.4 13 100 + 1 Ca Sn 03 1.710 1.100 1.790 1.4 14 100 + 5 Ca Sn03 145 0.010 153 [1.3 14 100 + 5 CaSn03 2.68 0 2.000 2.840 1.8 15 ioo + io Ca Sn 03 132 0.010 142 1.4 15 IOO + IO Ca Sn 03 8.500 2.500 9.400 1.5 16 8o + 20 Ca Sn03 1 0 3 0.010 117 1.4 16 8o + 20 Ca Sn 03 1.420 I 0.32 0 1.445 0.02 17 65-I-35 Ca Sn03 76 o, oio 85 2.1 17 65 + 35 Ca Sn03 235 0 , 060 238 i, I. 18 50 + 50 Ca Sn03 61 o, oio 72 1.8 18 50 + 5 0 Ca Sn03 124 0.010 13 0 1.4 19 92 + 8 BaSn03 2.81o 2.620 3.29 0 2.0 20 88 + 12 Ba Sn03 6.575 2.72 0 7.06o 1.2 21 86 + 14 Ba Sn0., 9450 2,900 10,200 o, 8 22 84 + 16 Ba Sn03 12.60o 2.200 13.100 0.4 23 82 + 18 BaSn03 7.55 0 Togo 7.25 0 0.1 Table II Table IV SrTi03 series Complex series i MHz r kHz i MHz i kHz . ele # ktri- I Lei- el # tri- Lei- Add. SrTiO $ - el nktri_ # Lei- el ktri- Lei- 7us composition No. Stannat _zitäts- zitätsstungs- \ 7r. citizen. performance con- I factor con- factor con- factor con- factor stante ° / o stante % stante ° / o stante i ioo + i Ba Sn03 249 o, oio 26o i, ii 8o BaTiOs 2 ioo + 5 Ba Sn0, 247 0,010 240 1, 0 ... io BaSn03 4,16o 0 95 3.510 0.01 3 ioo + io Ba Sn03 2i0 o, oio 22o 1.7 io SrSnO $ 4 80 + 2o Ba Sn03 233 0.010 237 1.2 2 7o BaTi03 5 65-h-35 Ba Sn03 155 0.040 163 1.9 2o BaSn03 ... 1.46o 0.38 1.415 0.01 6 50-1-5o Ba Sn 03 99 0.030 97 1.6 i0 Sr Sn 03 7 100 + 1 Sr Sn03 242 0.040 244 1.2 8 Ioo + 5 Sr Sn03 227 o, 060 238 1.2 3 7o BaTi03 j 9 IOo + io Sr Sn03 215 0.08o 217 1.2 i0 BaSnOg ... 2, I05 0.5o 1.805 I 0.02 io 8o-1-20 Sr Sn03 144 o, oio i49 1,7 2o SrSn03 ii 65-1--35 Sr Sn03 76 o, oio 84 2.0 4 7o BaTi03 12 50-1-5 0 Sr Sn0. 45 0.030 52 8, o 15 Ba Sn03 ... 1.475 03I 1450 0 , 10 13 100+ 1 Ca Sn 03 247 0.030 261 i, i 15 Sr Sn 03 14 100 + 5 Ca Sn03 237 0.040 244 1.1 5 85 BaTi03 15 ioo + io Ca Sn 03 2o8 0.020 214 i, i 5 Ba Sn 03 16 8o + 20 Ca Sn0, 141 0.010 146 1.3. 7.720 1.74 8, i00 0.50 17 65 + 35 Ca Sn 03 97 0.010 i08 2.6 5 Sr Sn 03 18 50 + 5o casn03 75 o, oio 85 i, 6 5 Sr Ti03 J. Table IV r MHz r kHz Di- I Di-! Additional composition of electrical line electrical line 5 no. sturdy con- j factor con factor stante I °, / o stante 6 7o BaTi03 To Ba Sn 03 @ 10 SrSn0 1 , 350 0.23 1.320 0.2o 3 '' = o SrTi03 7 55 BaTi03 15 BaSn03 615 o, 16 625 '1.30 15 Sr Sn 03 ... = 5 SrTi 03 1 Table V Temperature capacity data Temperature Body No. 3 Body No. 9 I Body No. r 5 o C Ca T103 CaTiOä CaTi03 Row row row KKK 20 ......... 148 137 132 30 ......... 148 137 132 40 ......... 148 136 131 50. " ....... 147 136 131 6o ......... 146 135 130 70 ......... 146 134 129 8o ......... 145 134 I28 9o ......... 144 133 128 = oo ......... 143 132 127 IM ......... 141 131 126 120 ......... 140 129 125 1 30 ......... 139 128 124 140 ......... 138 127 123 1 50 ......... 137 126 122 Table VI Temperature capacity data Temperature body no. 3 body no. 9 body no. 15th o CS : @ i03 SrTi03 SrTi03- Row row row KKK 20 ......... 210 215 208 30 ......... 210 215 2o8 40 ......... 2O8 215 207 50 ......... 207 213 2o6 6o ......... 205 212 205 7 0 ......... 2 0 3 210 203 8o ......... 201 208 202 go ......... 198 2o6 199 j Too ......... 196 2o6 197 110 ......... 193 204 194 120 ......... 189 202 IgI 130 ......... 186 200 188 140 ......... 184 1 98 184 15 0 ......... 18o 196 182 Table VII Temperature capacity data Body body body body Temperature No. 3 No. 9 No. 15 No. 5 ° C B & Ti03- BaTi03- BaTi0 $ - complex Row row row row KKKK 20 ......... 3.580 4.300 8.500 7.72 0 30 ......... 3.78o 4.300 8.60o 7.5 0 0 40 ......... 4.020 4.270 8.940 7.400 50 ......... 4.330 4250 9.170 7.26o 6o ......... 4 , 780 4.180 9.48o 6.65o 70 ......... 5,350 4,120 9, I70 5,900 8o ......... 6.20 0 4.030 8.640 4.96o go ......... 6.8 = o 3.94 o 6.640 4.210 = OO ......... 7.22 0 3.90 0 5.46o 3.930 == o ......... 8, = 8o 3.80o q., 260 2.920 120 ......... 8.86o 3.540 3.530 2.38 0 130 ......... 8.950 3.120 2.83 0 1.940 = 40 ........: 8.26o 2.640 2.290 I, 600 150 ........ 7.520 2.210 2.000 1.470 The temperature coefficients of the compositions according to Tables V, VI and VII show the scope of the possible change. While individual compositions result in the desired coefficients, an infinite variety of coefficients is possible through the parallel combination of one or more bodies.

Aus dem Vorhergehenden ergibt sich, daß nach der vorliegenden Erfindung Verbindungen erhalten werden, die in einem weiten Anwendungsbereich äußerst geeignet als Dielektrika sind. Die oben gegebenen Beispiele dienen nur zur Erläuterung der Erfindung, da sich für den Fachmann von selbst ergibt, daß weite Abweichungen von den besonderen Beispielen möglich sind.From the foregoing it can be seen that according to the present invention Compounds are obtained which are extremely suitable in a wide range of applications than dielectrics are. The examples given above are only intended to illustrate the Invention, since it is obvious to those skilled in the art that there are wide deviations from the particular examples are possible.

Claims (4)

PATENTANSPRÜCHE: I. Keramische Zusammensetzung, dadurch gekennzeichnet, daß sie die Titanate und Stannate der Erdalkalimetalle enthält. PATENT CLAIMS: I. Ceramic composition, characterized in that that it contains the titanates and stannates of the alkaline earth metals. 2. Keramische Zusammensetzung nach Anspruch I, dadurch gekennzeichnet, daß die Titanate in größerem Anteil. als die Stannate vorhanden sind. 2. Ceramic composition according to claim I, characterized in that the titanates in a larger proportion. as the stannates are present. 3. Keramische Zusammensetzung nach Anspruch I oder 2, dadurch gekennzeichnet, daß sie Bariumtitanat, Strontiumtitanat oder Kalziumtitanat enthält. 3. Ceramic composition according to claim I or 2, characterized in that it contains barium titanate, strontium titanate or calcium titanate contains. 4. Keramische Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Stannat Kalzium-, Barium-oder Strontiumstannat ist. Angezogene Druckschriften USA.-Patentschrift Nr. 2 277 734.4. Ceramic composition according to one of the preceding claims, characterized in that the stannate is calcium, barium or strontium stannate. Reference U.S. Patent No. 2,277,734.
DEN3632A 1943-06-11 1951-03-17 Substances of high dielectric constant and process for their production Expired DE909819C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1113407B (en) * 1956-05-30 1961-08-31 Plessey Co Ltd Process for the production of a ceramic, dielectric material
DE2659672A1 (en) * 1976-12-30 1978-07-13 Siemens Ag CAPACITOR DIELECTRIC WITH INNER BARRIER LAYERS AND PROCESS FOR ITS MANUFACTURING

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2277734A (en) * 1939-07-04 1942-03-31 Titanium Alloy Mfg Co Dielectric material and method of making the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2277734A (en) * 1939-07-04 1942-03-31 Titanium Alloy Mfg Co Dielectric material and method of making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1113407B (en) * 1956-05-30 1961-08-31 Plessey Co Ltd Process for the production of a ceramic, dielectric material
DE2659672A1 (en) * 1976-12-30 1978-07-13 Siemens Ag CAPACITOR DIELECTRIC WITH INNER BARRIER LAYERS AND PROCESS FOR ITS MANUFACTURING

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