DE1796226C3 - Method for stabilizing the temperature dependence of the frequency constants of piezoelectric ceramics - Google Patents

Method for stabilizing the temperature dependence of the frequency constants of piezoelectric ceramics

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Publication number
DE1796226C3
DE1796226C3 DE1796226A DE1796226A DE1796226C3 DE 1796226 C3 DE1796226 C3 DE 1796226C3 DE 1796226 A DE1796226 A DE 1796226A DE 1796226 A DE1796226 A DE 1796226A DE 1796226 C3 DE1796226 C3 DE 1796226C3
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temperature
ceramic
lead zirconate
dependence
ceramics
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DE1796226A
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DE1796226A1 (en
DE1796226B2 (en
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Helmut Dipl.-Chem. Dr. 8000 Muenchen Thomann
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Siemens AG
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Siemens AG
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46Shaped 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped 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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped 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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49Shaped 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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C04B35/491Shaped 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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/51Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on compounds of actinides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/02Electrets, i.e. having a permanently-polarised dielectric
    • H01G7/025Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric
    • H01G7/026Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric with ceramic dielectric
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/01Manufacture or treatment
    • H10N30/04Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00Piezoelectric or electrostrictive devices
    • H10N30/80Constructional details
    • H10N30/85Piezoelectric or electrostrictive active materials
    • H10N30/853Ceramic compositions

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
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  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Claims (5)

1 2 dem Zuschneiden, ^nach dem Aufbringen der Elek- Patentansprüche: troden und/öderväacii'der Polarisation des Materials noch für lange Zeir|uiäerL1 2 the cutting, ^ after the application of the electrical claims: troden and / öderväacii'der polarization of the material for a long time 1. Verfahren zur Beseitigung der zeitlichen Aufgabe der Erfindung ist es, Maßnahmen anzu-Ändening der Temperaturabhängigkeit der Fre- 5 geben, mit denen die langzeitliche Änderung der quenzkonstanten.piezoelektrischer Keramik, da- Temperaturabhängigkeit der Frequenzkonstante bedurch gekennzeichnet, daß der polari- seitigt werden kann bzw. durch die der darin versierte Keramikkörper nach dem letzten Bearbei- borgene Alterungseffekt wesentlich beschleunigt wertungsvorgang, bei dem eine Erwärmung auf 80° C den kann.1. Method for eliminating the temporal object of the invention is to change measures the temperature dependence of the Fre- 5 with which the long-term change in the quenzkonstanten.piezoelectric ceramic, because temperature dependence of the frequency constant characterized by the fact that the polar side can be turned off or by those who are well versed in it Ceramic body after the last processing - borrowed aging effect significantly accelerates the evaluation process, which can be heated to 80 ° C. und höher eintritt, mehrmalig aufeinanderfolgend 10 Diese Aufgabe wird durch ein Verfahren gelöst, einem Temperaturzyklus unterworfen wird, bei das erfindungsgemäß dadurch gekennzeichnet ist, dem er mit einer Geschwindigkeit von höchstens daß ein polarisierter Keramikkörper nach der letzten etwa 30° C/h bis auf eine vom Material abhän- Erwärmung auf Temperaturen höher als etwa 80° C gige Maximaltemperatur unterhalb der Curie- mehrmalig aufeinanderfolgend einem Temperatur-Temperatur erwärmt und wieder abgekühlt wird. 15 zyklus unterworfen wird, bei dem das Material mitand higher, several times in succession 10 This task is achieved by a method, is subjected to a temperature cycle, which is characterized according to the invention, which he with a speed of at most that a polarized ceramic body after the last approx. 30 ° C / h apart from a heating to temperatures higher than approx. 80 ° C, depending on the material gige maximum temperature below the Curie several times in succession a temperature-temperature is heated and cooled again. 15 cycle is subjected in which the material with 2. Verfahren nach Anspruch 1, dadurch ge- einer Geschwindigkeit von höchstens etwa 30° C/h kennzeichnet, daß 80° C als Maximaltemperatur bis auf eine vom Material abhängige Maximaltempegewähltwird. ratur unterhalb der Curietemperatur erwärmt und2. The method according to claim 1, characterized ge a speed of at most about 30 ° C / h indicates that 80 ° C is selected as the maximum temperature up to a maximum temperature dependent on the material. temperature below the Curie temperature and 3. Anwendung des Verfahrens nach Anspruch 1 wieder auf die vorgesehene Betriebstemperatur, vor- oder 2 auf eine Bleizirkonat-Titanat-Keramik mit 20 zugsweise die Zimmertemperatur, abgekühlt wird. einem Verhältnis Zirkonat zu Titanat im Bereich Diese Maximaltemperatur beträgt, insbesondere für der Phasengrenze rhomboedrisch zu tetragonal. Bleizirkonat-Titanat mit einem Verhältnis Zirkon zu3. Application of the method according to claim 1 again to the intended operating temperature, before or 2 is cooled on a lead zirconate titanate ceramic with 20 preferably room temperature. a ratio of zirconate to titanate in the range This maximum temperature is, in particular for the phase boundary rhombohedral to tetragonal. Lead zirconate titanate with a ratio of zircon to 4. Anwendung nach Anspruch 2 auf eine Titan im Bereich der Phasengrenze, etwa 80° C. In dotierte oder substituierte Bleizirkonat-Titanat- vielen Fällen genügt es bereits, den Temperatur-Keramik, as zyklus 3- bis 4mal ablaufen zu lassen. Bezüglich der4. Application according to claim 2 to a titanium in the region of the phase boundary, about 80 ° C. In doped or substituted lead zirconate titanate - in many cases it is sufficient to use the temperature ceramic, Let the cycle run 3 to 4 times. Regarding the 5. Anwendung nach Anspruch 4 auf mit einem angegebenen Geschwindigkeit ist zu sagen, daß bei oder mehreren der Elemente Neodym, Mangan, langsamerer Erwärmung oder Abkühlung etwa mit Eisen, Magnesium, Wolfram dotierte oder sub- 10 oder 20° C/h im allgemeinen noch mehr Erfolg stituierte Keramik. erzielt wird. Dabei ist aber zu bedenken, daß ein so5. Application according to claim 4 at a specified speed is to say that at or more of the elements neodymium, manganese, slower heating or cooling, for example with Iron, magnesium, tungsten doped or sub- 10 or 20 ° C / h in general even more successful established ceramics. is achieved. But it should be remembered that such a 30 langsam ablaufender Prozeß fertigungstechnisch häufig unerwünscht ist. Aus diesen Angaben kann30 slow process is often undesirable from a manufacturing point of view. From this information can sich der Fachmann im übrigen die für den jeweiligenthe person skilled in the rest of the for the respective Anwendungsfall günstigste Geschwindigkeit auswählen. Select the most favorable speed for use. Die Erfindung betrifft ein Verfahren zur Beseiti- 35 Zu der Erfindung führten die folgenden Ubergung der Zeitabhängigkeit des Temperaturverhaltens legungen: Den Untersuchungen nach zu schließen, der materialabhängigen Frequenzkonstanten piezo- dürfte die zeitliche Änderung der Temperaturabhänelektrischer Keramik. gigkeit der Frequenzkonstanten der piezoelektrischenThe invention relates to a method for eliminating the invention the time dependence of the temperature behavior: According to the investigations, of the material-dependent frequency constants piezo-electric should change the temperature over time Ceramics. ity of the frequency constants of the piezoelectric Es ist bekannt, piezoelektrische Keramik als elek- Keramik darauf beruhen, daß sich nach einem mit tromechanische Umsetzer in mechanischen Filtern 40 einer Erwärmung der Keramik verbundenen Bearbeifür die Elektronik zu verwenden. Bei dieser Verwen- tungsprozeß der thermodynamische Gleichgewichtsdung der Keramik spielt die Temperaturabhängigkeit zustand nur sehr langsam einstellt. Es liegen also der Frequenzkonstanten der mechanischen Schwin- praktisch eingefrorene Zustände vor, die nun durch gung der Keramik eine ganz wesentliche Rolle. Es das erfindungsgemäße Verfahren beschleunigt in ein sind viele Versuche angestellt worden, diese Tempe- 45 Gleichgewicht übergeführt werden. Wie sich gezeigt raturabhängigkeit möglichst klein zu machen. Ein hat, darf der erfindungsgemäße Temperaturzyklus Weg, der hierzu beschritten wurde, ist derjenige, ein bei Bleizirkonat-Titanat nur bis zu einer Temperatur homogenes Material aus mehreren Komponenten zu von etwa 80° C ausgedehnt werden. Temperaturen verwenden. Ein typischer Vertreter hierfür ist das wesentlich darüber, etwa über 100° C, bringen erfah-Bleizirkonat-Titanat mit in bestimmten Grenzen fest- 50 rungsgemäß eher Nachteile als Vorteile. Wesentlich gelegtem Verhältnis Titan zu Zirkon. Gegebenenfalls unter S0° C zu bleiben hat sich wenigstens im allsind einem solchen Material noch weitere Stoffe als gemeinen Fall wenig bewährt. Bei zu niedrigen End-Dotierung oder Substitution hinzugefügt. So wurde temperaturen mußten nämlich, um das gleiche Ergefunden, daß sich die Temperaturabhängigkeit der gebnis zu erreichen, wesentlich mehr Temperatur-Frequenzkonstanten bei Bleizirkonat-Titanat, insbe- 55 zyklen durchgeführt werden, als sie bei z. B. 80° C sondere bei Zusammensetzungen Zirkon zu Titan im Endtemperatur erforderlich waren. Als besonders Bereich der Phasengrenze zwischen rhomboedrischer wirkungsvoll erwies sich das erfindungsgemäße Ver- und tetragonaler Struktur besonders stark beein- fahren bei Materialien wie
flüssen läßt Vorteilhafterweise sind an dieser Phasen- pb Zf Q M TJ Q4f) Q + , t/§ N{J Q
It is known to use piezoelectric ceramics as elek ceramics based on the fact that machining for the electronics is associated with a heating of the ceramics after an electro-mechanical converter in mechanical filters 40. In this process of using the thermodynamic equilibrium of the ceramic, the temperature-dependent state only sets in very slowly. So there are the frequency constants of the mechanical vibration - practically frozen states, which now play a very important role due to the movement of the ceramic. The process according to the invention accelerates into a number of attempts have been made to convert this temperature equilibrium. As shown to make temperature dependence as small as possible. The temperature cycle according to the invention has one way of doing this, that is to extend a material consisting of several components that is homogeneous with lead zirconate titanate only up to a temperature of about 80 ° C. Use temperatures. A typical representative of this is that significantly above, about 100 ° C., experience lead zirconate titanate has disadvantages rather than advantages within certain limits. Substantial relationship between titanium and zirconium. If necessary, staying below S0 ° C has proven to be of little use, at least in general, for such a material as other substances than the common case. If the end doping or substitution is too low, added. In order to achieve the same result that the temperature dependence of the result was found, temperatures had to be carried out with significantly more temperature-frequency constants in the case of lead zirconate-titanate, in particular cycles, than they were in e.g. B. 80 ° C special in compositions zirconium to titanium in the final temperature were required. The tetragonal structure according to the invention has proven to be particularly effective in the area of the phase boundary between rhombohedral and tetragonal structures, particularly in the case of materials such as
Advantageously, at this phase, pb Zf QM TJ Q4f) Q + , t / § N {JQ
grenze auch besonders hohe Koppltingsfaktoren fest- 60 Pb Zr 0 51 Ti 0 49 O + 1 2 Vo MnO,limit also particularly high coupling factors fixed- 60 Pb Zr 0 51 Ti 0 49 O + 1 2 Vo MnO, zustellen Pb Zr o',49', Ti 0^51 O* + Ο,'5'vo Fe.,O.J,'deliver Pb Zr o ', 49', Ti 0 ^ 51 O * + Ο, '5'vo Fe., O.J,' Es wurde aber festgestellt daß die Temperatur- pb Zr 057> τ· 043 Q + 05 i/§ Fe-Q·However, it was found that the temperature pb Zr 057> τ · 043 Q + 05 i / § Fe - Q · abhängigkeit eines wie oben beschriebenen Materials pb Zr 0 45 Tj 0 40 (M 0075) Wo 0 dependence of a material as described above pb Zr 0 45 Tj 0 40 (M 0075) Wo 0 nicht zeitunabhängig ist, sondern daß sie sich nachis not time-independent, but that it is based on Vornahme eines Bearbeitungsvorganges, z. B. nach 65 Die Prozentangaben sind Gewichtsprozente.Carrying out a processing operation, e.g. B. after 65 The percentages are percentages by weight.
DE1796226A 1968-09-25 1968-09-25 Method for stabilizing the temperature dependence of the frequency constants of piezoelectric ceramics Expired - Lifetime DE1796226C3 (en)

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DE1796226A1 DE1796226A1 (en) 1972-04-27
DE1796226B2 DE1796226B2 (en) 1975-03-06
DE1796226C3 true DE1796226C3 (en) 1975-10-23

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JP3125624B2 (en) * 1995-04-21 2001-01-22 株式会社村田製作所 Piezoelectric ceramic

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