US2633543A - Bimorph element - Google Patents

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US2633543A
US2633543A US21842A US2184248A US2633543A US 2633543 A US2633543 A US 2633543A US 21842 A US21842 A US 21842A US 2184248 A US2184248 A US 2184248A US 2633543 A US2633543 A US 2633543A
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ceramic
sheet
conducting
barium titanate
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Glenn N Howatt
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GULTON Manufacturing CORP
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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
    • C04B35/462Shaped 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
    • C04B35/465Shaped 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 based on alkaline earth metal titanates
    • C04B35/468Shaped 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 based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682Shaped 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 based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • HELECTRICITY
    • H04ELECTRIC COMMUNICATION TECHNIQUE
    • H04RLOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00Piezoelectric transducers; Electrostrictive transducers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/42Piezoelectric device making

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  • the present invention relates to a bimorph element and method of making the same and, more in particular, to a bimorph barium titana-te transducer element.
  • the principal object of the present invention is the provision of an improved bimorph titanate ceramic element particularly adapted for use in a transducer.
  • an alkali earth metal titanate is first produced in the form of a thin sheet and this thin sheet is then partially reduced by heating the same to a relatively high temperature in a reducing atmosphere until the flat sheet becomes uniformly partially conducting.
  • the reduced sheet is then heated for a shorter period of tim in an oxidizing atmosphere to oxidize the exterior portions of the sheet and leave a conducting layer in the center thereof.
  • Fig. 2 is a similar view of the reduced ceramic
  • Fig, 3 is a perspective view of the oxidized ceramic with dotted lines indicating one manner of trimming the so reduced and oxidized element;
  • Fig. 4 is a perspective view showing the trimmed element and indicating the center conducting layer
  • Fig. 5 is a perspective view showing the complete transducer with the signal leads and the center charging lead attached thereto.
  • the barium titanate ceramic shown in Fig. l was then placed in a refractory porcelain plaque and reheated to a temperature of 1300 degrees C. in a hydrogen atmosphere for ten minutes.
  • the resulting partially reduced body. shown in 2 is much darker in color than the pure barium titanate starting material and has a much lower electrical resistance than the original material.
  • the resistance of the reduced material will be found to be of the order of ohms (the total resistance of the element shown in Fig. 2 measured from end to end is about 890 ohms), while the resistance of the original barium titanate ceramic unreduced is of the order of about lC- ohms.
  • Resistance measurements have not been accurately determinedand have been made and are referred to only for the purpose of explaining that the material definitely becomes conductive when subjected to the high temperature reducing treatment.
  • a piece of ten mil thickness will be found to be substantially uniformly reduced throughout its mass by ten minutes treatment at the temperature disclosed.
  • the partially reduced ceramic shown in Fig. 2 having first been permitted to cool, was then reheated at a temperature of 1000 degrees C. for a period of five inimites in an oxidizin atmosphere, suitably air. This treatment "re-oxidizes the surface portion of the sample but leaves a conductive strip or layer on the inside portion. By cutting the so partially re-oxidized element along the broken line A of Fig. 3, a strip 0.8"
  • Electrodes l2 were then applied to the opposite large area surfaces as shown in Fig. by painting a conductive silver paste thereon, taking care not to make a contact between either of such electrodes and the center blackish reduced conducting layer in the center. A spot of silver was then placed on one end of the body and a charging lead I3 secured thereto. Signal leads 5 were soldered to the electrodes l2. The element was then charged by means of a direct current potential of 200 volts, the charging lead 13 being connected to the positive pole of the two leads l4 connected to the negative pole. Charging was continued for six minutes. The signal leads were then connected to an electronic galvanometer and the element stressed between rubber pads. The particular sample showed that a voltage of approximately 0.4 volt was generated under these circumstances, thus showing that the element had piezoelectric properties and comprised an active transducer element.
  • the significant feature is the production of a conducting center layer by successive reducing and oxidizing procedures in which the re-oxidization is so limited as to extend only part way through the body of the reduced material.
  • the center conductive layer constitutes the center electrode and the signal electrodes are applied by conventional methods such as painting with conductive paint, sputtering, or the like.
  • the reduced material may be treated to apply the silver electrodes by spraying, dipping, painting, or the like, after which the element is dried and then sintered. If the sintering operation is carried out in an oxidizing atmosphere, it has the effect not only of bonding the silver to the ceramic but also of producing the oxidized surface layers in the same operation.
  • the material treated was barium titanate, but one may practice the invention using other alkali earth metal titanates or mixtures of the same as, for example, a desirable mixture of strontium and barium titanate.
  • barium titanate is much preferred for many purposes because of its relatively high Curie point.
  • the elements have been produced in various sizes and shapes and embodied in operable devices where they performed satisfactorily as transducer elements, as, for example, in phonograph pick-ups and the like.
  • the ceramic body is advantageously treated by the method described to reduce and then re-oxidize the same, other oxidation and reduction methods, or combinations thereof, may be employed.
  • the ceramic may be the cathode of an electrolytic cell during reduction and the anode during oxidation, as when the electrolyte comprises potassium perchlorate dissolved in sulfuric acid and maintained at 100 degrees C. during electrolysis.
  • a molten body of sodium or potassium nitrate may also be employed as the electrolyte.
  • Direct chemical treatment at temperatures below those employed in the hydrogen and oxygen reduction and oxidation, respectively, may be used.
  • One advantageous method is to reduce the ceramic in a hydrogen atmosphere and carry out the oxidation electrolytically so that the thickness of the fully oxidized layers may be more readily controlled.
  • the bimorph element of my invention is not limited to use as a transducer.
  • t may, for example, be a unit of a capacitor, and is extremely efiective because of the high dielectric constant of the fully oxidized layer. It has a dielectric constant of the order of 1200 to 1400, for example, for BaTiOz, as contrasted with a dielectric constant of 6 for aluminum oxide layers which are used in electrolytic condensers.
  • any portion of the surface not desired to be oxidized may be covered with a protective layer during the re-oxidation procedure.
  • the bimorph element of my invention When employing the bimorph element of my invention as a transducer it is desirable that it be an alkaline earth metal titanate, and barium titanate is particularly effective for this purpose.
  • the bimorph element When the bimorph element is a unit in a capacitor or rectifier, however, other metal titanates, including titanium dioxide and mixtures thereof with various titanates, may be used.
  • a bimcrph titanate which comprises forming a strip of ceramic of a class consisting of metal titanates, titanium dioxide, and mixtures thereof, treating the said strip to partiall reduce the ceramic body and decrease the electrical resistance thereof, and thereafter oxidizing only a portion of the strip to produce at least two layers having difierent electrical conductivity.
  • a bimorph titanate ceramic element of the character described which comprises heating a strip of the class consisting of titanium dioxide and metal titanate and mixtures thereof, at an elevated temperature in a chemically reducing atmosphere until substantially the entire sheet becomes electrically conducting and then heating the so reduced sheet in an oxidizing atmosphere to oxidize only the surface portion thereof, leaving a conducting unoxidized center portion.
  • the method of producing a barium titanate transducer which comprises forming a relatively thin fiat sheet of barium titanate ceramic, heating said sheet in a reducing atmosphere at an elevated temperature until substantially the entire body of the sheet becomes electrically conducting, heating the sheet in an oxidizing atmosphere to oxidize only the surface portion thereof, leaving a center layer of conducting material, cutting a transducer element from said sheet while at the same time exposing the conducting layer at at least one edge of said element, applying conducting electrodes to the opposite flat barium titanate layers to form signal electrodes, and charging the element by connecting the center conducting layer to one pole or" the charging source and the two signal electrodes to the opposite ole of the charging source.
  • a bimorph element comprising a single piece alkali earth metal titanate having exterior non-conducting layers and an intermediate electrically conducting layer comprising a partially chemically reduced alkali earth metal titanate.
  • a bimorph element comprising a relatively thin fiat sheet of barium titanate having a center layer sufficiently chemically reduced to be electrically conducting.
  • a bimorph element comprising a relatively thin flat sheet of barium titanate having a center layer sufliciently chemically reduced to be electrically conducting, and a pair of signal electrodes on opposite large area fiat surfaces of the barium titanate, the layers of barium titanate on opposite sides of the conducting layer being oppositely charged.
  • a bimorph element comprising a ceramic body of the class consisting of titanium dioxide and metal titanate in the form of at least two layers, at least one layer of which comprises a partially chemically reduced layer of the said ceramic.
  • a bimorph element comprising a single piece alkali earth metal titanate having exterior electrically non-conducting layers and an intermediate electrically conducting layer comprising a partially chemically reduced alkali earth metal titanate, said exterior layers on opposite sides of the conducting layer being oppositely electrically charged.
  • a bimorph element in the form of a relatively thin fiat sheet of a ceramic comprising barium titanate, said sheet having a central layer sufficiently chemically reduced to be electrically conducting, and a pair or signal electrodes on the opposite large area fiat surfaces of said sheet.
  • a bimorph element comprising a relatively thin flat sheet comprising barium titanate having a center layer sufficiently chemically reduced to be electrically conducting, the exterior layers on opposite sides of the conducting layer being oppositely electrically charged.
  • the method of producing a transducer which comprises forming a relatively thin flat sheet comprising barium titanate, heating said sheet in a reducing atmosphere at an elevated temperature until substantially the entire body of the sheet becomes electrically conducting, heating the sheet in an oxidizing atmosphere to oxidize only the surface portion thereof whereby to leave a center layer of conducting material, applying conducting electrodes to the opposite fiat surfaces of said sheet to form signal electrodes, and charging the resulting element by connecting the center conducting layer to one pole of the charging source and the two signal electrodes to the opposite pole of the charging source.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Description

C 4 6 5? wee ra 170 1- (0m 9 Age? IN VEN TOR.
Wm J
lvl 1 l I i G. N. HOWATT BIMORPH ELEMENT Filed April 19, 1948 March 31, 1953 Patented Mar. 31, 1953 BIMORPH ELEMENT Glenn N. Howatt, Metuchen, N. J., assignor to G-ulton Mfg. Corp, a corporation of New Jersey Application April 19, 1948, Serial No. 21,842
Claims.
The present invention relates to a bimorph element and method of making the same and, more in particular, to a bimorph barium titana-te transducer element.
It is known that if polygranular ceramics of the class comprising alkali earth metal titanates are subjected to an electro static charge they become active as piezoelectric elements. Barium titanate, particularly, has been used successfully as a transducer element. When so used, the element is supported in such a way as to be vibrated mechanically as by a phonograph needle and the alternating potential developed is picked up from signal electrodes carried on the large area fiat surfaces of a thin sheet of the ceramic body. Various expedients have been employed to avoid a cancelling-out efiect caused by the production of opposing stresses, and one such means comprises the use of two fiat ceramic bodies with opposite charges and so secured together as to vibrate as a single body.
The principal object of the present invention is the provision of an improved bimorph titanate ceramic element particularly adapted for use in a transducer.
In carrying out the invention, an alkali earth metal titanate is first produced in the form of a thin sheet and this thin sheet is then partially reduced by heating the same to a relatively high temperature in a reducing atmosphere until the flat sheet becomes uniformly partially conducting. The reduced sheet is then heated for a shorter period of tim in an oxidizing atmosphere to oxidize the exterior portions of the sheet and leave a conducting layer in the center thereof. By applying electrodes to the opposite large area surfaces and making an electric contact to the center conducting area the portions of the element on opposite sides of the conducting center area may be oppositely charged and vibration of the element so produced and so charged generates a voltage after the manner of conventional transducer elements. The details of the manner of carrying out the invention will be supplied hereinbelow in connection with the accompanying drawing where- Fig. 1 is an enlarged perspective view, partly broken away, showin the ceramic before reduction thereof;
Fig. 2 is a similar view of the reduced ceramic;
Fig, 3 is a perspective view of the oxidized ceramic with dotted lines indicating one manner of trimming the so reduced and oxidized element;
Fig. 4 is a perspective view showing the trimmed element and indicating the center conducting layer; and
Fig. 5 is a perspective view showing the complete transducer with the signal leads and the center charging lead attached thereto.
In carrying out the process and producing the element, desirable results have been obtained with barium titanate ceramic and the drawing is prepared to show the steps of the process. In accordance with the example indicated bythe drawing, a sheet of substantially pure barium titanate ceramic was first produced 1" long by K wide by 0.010" thick. This sheet, shown in Fig. l, was fabricated s1 liable thin sheet techniques such as disclosed in my copending application Serial No. 554,294, filed September 15, 1944:, now Fatent No. 2, i42,524= granted June 1, 1948, and the thin sheet fired to density in accordance with practices common in the art. The sheet so produced was of the type used for production of polygranular piezo crystals but generally of considerably greater dimension commonly used for such purpose.
The barium titanate ceramic shown in Fig. l was then placed in a refractory porcelain plaque and reheated to a temperature of 1300 degrees C. in a hydrogen atmosphere for ten minutes. The resulting partially reduced body. shown in 2, is much darker in color than the pure barium titanate starting material and has a much lower electrical resistance than the original material. In general, the resistance of the reduced material will be found to be of the order of ohms (the total resistance of the element shown in Fig. 2 measured from end to end is about 890 ohms), while the resistance of the original barium titanate ceramic unreduced is of the order of about lC- ohms. Resistance measurements have not been accurately determinedand have been made and are referred to only for the purpose of explaining that the material definitely becomes conductive when subjected to the high temperature reducing treatment. A piece of ten mil thickness will be found to be substantially uniformly reduced throughout its mass by ten minutes treatment at the temperature disclosed.
The partially reduced ceramic shown in Fig. 2, having first been permitted to cool, was then reheated at a temperature of 1000 degrees C. for a period of five inimites in an oxidizin atmosphere, suitably air. This treatment "re-oxidizes the surface portion of the sample but leaves a conductive strip or layer on the inside portion. By cutting the so partially re-oxidized element along the broken line A of Fig. 3, a strip 0.8"
long by 0.2" wide by 0.010 thick was produced, as shown in Fig. 4. By so trimming the material, the reduced center layer It is exposed around the edges leaving two outside layers l! of totally oxidized substantially pure barium titanate ceramic.
Electrodes l2 were then applied to the opposite large area surfaces as shown in Fig. by painting a conductive silver paste thereon, taking care not to make a contact between either of such electrodes and the center blackish reduced conducting layer in the center. A spot of silver was then placed on one end of the body and a charging lead I3 secured thereto. Signal leads 5 were soldered to the electrodes l2. The element was then charged by means of a direct current potential of 200 volts, the charging lead 13 being connected to the positive pole of the two leads l4 connected to the negative pole. Charging was continued for six minutes. The signal leads were then connected to an electronic galvanometer and the element stressed between rubber pads. The particular sample showed that a voltage of approximately 0.4 volt was generated under these circumstances, thus showing that the element had piezoelectric properties and comprised an active transducer element.
Those skilled in the art will understand that the features of the invention may be employed in various ways. The significant feature is the production of a conducting center layer by successive reducing and oxidizing procedures in which the re-oxidization is so limited as to extend only part way through the body of the reduced material. The center conductive layer constitutes the center electrode and the signal electrodes are applied by conventional methods such as painting with conductive paint, sputtering, or the like. Instead of partially reoxidizing the ceramic body and then applying the signal electrodes, the reduced material may be treated to apply the silver electrodes by spraying, dipping, painting, or the like, after which the element is dried and then sintered. If the sintering operation is carried out in an oxidizing atmosphere, it has the effect not only of bonding the silver to the ceramic but also of producing the oxidized surface layers in the same operation.
In the specific example given, the material treated was barium titanate, but one may practice the invention using other alkali earth metal titanates or mixtures of the same as, for example, a desirable mixture of strontium and barium titanate. Those skilled in the art will understand that barium titanate is much preferred for many purposes because of its relatively high Curie point. The elements have been produced in various sizes and shapes and embodied in operable devices where they performed satisfactorily as transducer elements, as, for example, in phonograph pick-ups and the like.
While the ceramic body is advantageously treated by the method described to reduce and then re-oxidize the same, other oxidation and reduction methods, or combinations thereof, may be employed. For example, the ceramic may be the cathode of an electrolytic cell during reduction and the anode during oxidation, as when the electrolyte comprises potassium perchlorate dissolved in sulfuric acid and maintained at 100 degrees C. during electrolysis. A molten body of sodium or potassium nitrate may also be employed as the electrolyte. Direct chemical treatment at temperatures below those employed in the hydrogen and oxygen reduction and oxidation, respectively, may be used. One advantageous method is to reduce the ceramic in a hydrogen atmosphere and carry out the oxidation electrolytically so that the thickness of the fully oxidized layers may be more readily controlled.
The use of a 200 volt charging potential for six minutes is, of course, illustrative, and is made possible because of the extreme thinness of the effective piezo layer. Usual times and charging voltages may be employed, depending on the results desired.
The bimorph element of my invention is not limited to use as a transducer. t may, for example, be a unit of a capacitor, and is extremely efiective because of the high dielectric constant of the fully oxidized layer. It has a dielectric constant of the order of 1200 to 1400, for example, for BaTiOz, as contrasted with a dielectric constant of 6 for aluminum oxide layers which are used in electrolytic condensers. When my process is used to produce a capacitor or like body, any portion of the surface not desired to be oxidized may be covered with a protective layer during the re-oxidation procedure.
When employing the bimorph element of my invention as a transducer it is desirable that it be an alkaline earth metal titanate, and barium titanate is particularly effective for this purpose. When the bimorph element is a unit in a capacitor or rectifier, however, other metal titanates, including titanium dioxide and mixtures thereof with various titanates, may be used.
What I claim as new and desire to protect by Letters Patent of the United States is:
1. The method of producing a bimcrph titanate which comprises forming a strip of ceramic of a class consisting of metal titanates, titanium dioxide, and mixtures thereof, treating the said strip to partiall reduce the ceramic body and decrease the electrical resistance thereof, and thereafter oxidizing only a portion of the strip to produce at least two layers having difierent electrical conductivity.
2. The method of producing a bimorph titanate ceramic element of the character described which comprises heating a strip of the class consisting of titanium dioxide and metal titanate and mixtures thereof, at an elevated temperature in a chemically reducing atmosphere until substantially the entire sheet becomes electrically conducting and then heating the so reduced sheet in an oxidizing atmosphere to oxidize only the surface portion thereof, leaving a conducting unoxidized center portion.
3. The method of producing an improved bimorph element of the character described which comprises heating a flat strip of barium titanate ceramic in a chemically reducing atmosphere until substantially the entire strip becomes electrically conducting, and then heating the so reduced strip in an oxidizing atmosphere to oxidize only substantially the surface portion thereof, leaving a center reduced conducting area.
4. The method defined in claim 2 wherein the temperature of the reducing treatment is of the order of 1250 degrees C. and in which both the time and temperature utilized in the oxidizing treatment are less than the time and tempera.- ture utilized in the reducing treatment.
5. The method of producing a barium titanate transducer which comprises forming a relatively thin fiat sheet of barium titanate ceramic, heating said sheet in a reducing atmosphere at an elevated temperature until substantially the entire body of the sheet becomes electrically conducting, heating the sheet in an oxidizing atmosphere to oxidize only the surface portion thereof, leaving a center layer of conducting material, cutting a transducer element from said sheet while at the same time exposing the conducting layer at at least one edge of said element, applying conducting electrodes to the opposite flat barium titanate layers to form signal electrodes, and charging the element by connecting the center conducting layer to one pole or" the charging source and the two signal electrodes to the opposite ole of the charging source.
6. A bimorph element comprising a single piece alkali earth metal titanate having exterior non-conducting layers and an intermediate electrically conducting layer comprising a partially chemically reduced alkali earth metal titanate.
7. A bimorph element comprising a relatively thin fiat sheet of barium titanate having a center layer sufficiently chemically reduced to be electrically conducting.
8. A bimorph element comprising a relatively thin flat sheet of barium titanate having a center layer sufliciently chemically reduced to be electrically conducting, and a pair of signal electrodes on opposite large area fiat surfaces of the barium titanate, the layers of barium titanate on opposite sides of the conducting layer being oppositely charged.
9. A bimorph element comprising a ceramic body of the class consisting of titanium dioxide and metal titanate in the form of at least two layers, at least one layer of which comprises a partially chemically reduced layer of the said ceramic.
10. The method of claim 1, which includes the step of oppositely electrically charging the exterior layers on opposite sides of the conducting layer.
11. The method of claim 3, which includes the steps of oppositely electrically charging the exterior layers on opposite sides of the conducting layer.
12. A bimorph element comprising a single piece alkali earth metal titanate having exterior electrically non-conducting layers and an intermediate electrically conducting layer comprising a partially chemically reduced alkali earth metal titanate, said exterior layers on opposite sides of the conducting layer being oppositely electrically charged.
13. A bimorph element, in the form of a relatively thin fiat sheet of a ceramic comprising barium titanate, said sheet having a central layer sufficiently chemically reduced to be electrically conducting, and a pair or signal electrodes on the opposite large area fiat surfaces of said sheet.
14. A bimorph element comprising a relatively thin flat sheet comprising barium titanate having a center layer sufficiently chemically reduced to be electrically conducting, the exterior layers on opposite sides of the conducting layer being oppositely electrically charged.
15. The method of producing a transducer which comprises forming a relatively thin flat sheet comprising barium titanate, heating said sheet in a reducing atmosphere at an elevated temperature until substantially the entire body of the sheet becomes electrically conducting, heating the sheet in an oxidizing atmosphere to oxidize only the surface portion thereof whereby to leave a center layer of conducting material, applying conducting electrodes to the opposite fiat surfaces of said sheet to form signal electrodes, and charging the resulting element by connecting the center conducting layer to one pole of the charging source and the two signal electrodes to the opposite pole of the charging source.
GLENN N. HOWATT.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,270,872 Goede et a1. Jan. 27, 1942 2,272,330 Schupp Feb. 10, 1942 2,272,331 Schupp Feb. 10, 1942 2,434,236 Verwey et a1. Jan. 6, 1948 2,477,596 Gravley Aug. 2, 1949 2,484,950 Jafie Oct. 17, 1949 2,486,560 Gray Nov. 1, 1949

Claims (1)

1. THE METHOD OF PRODUCING A BIMORPH TITANATE WHICH COMPRISES FORMING A STRIP OF CERAMIC OF A CLASS CONSISTING OF METAL TITANATES, TITANIUM DIOXIDE, AND MIXTURES THEREOF, TREATING THE SAID STRIP TO PARTIALLY REDUCE THE CERAMIC BODY AND DECREASE THE ELECTRICAL RESISTANCE THEREOF, AND THEREAFTER OXIDIZING ONLY A PORTION OF THE STRIP TO PRODUCE AT LEAST TWO LAYERS HAVING DIFFERENT ELECTRICAL CONDUCTIVITY.
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Cited By (55)

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US2768421A (en) * 1952-05-17 1956-10-30 Clevite Corp Method of making circuit connections to a transducer unit
US2782397A (en) * 1953-10-01 1957-02-19 Ibm Piezoelectric interrogation of ferroelectric condensers
US2793288A (en) * 1950-02-21 1957-05-21 Charles F Pulvari Apparatus for electrostatic recording and reproducing
US2796564A (en) * 1953-12-21 1957-06-18 Sylvania Electric Prod Electric circuit element
US2806189A (en) * 1953-07-03 1957-09-10 Sylvania Electric Prod Alkaline titanate rectifiers
US2821490A (en) * 1953-03-11 1958-01-28 Sylvania Electric Prod Titanate rectifiers
US2836776A (en) * 1955-05-07 1958-05-27 Nippon Electric Co Capacitor
US2841508A (en) * 1955-05-27 1958-07-01 Globe Union Inc Electrical circuit elements
US2841722A (en) * 1953-03-18 1958-07-01 Clevite Corp Bending-responsive electromechanical transducer device
US2851405A (en) * 1953-07-03 1958-09-09 Sylvania Electric Prod Titanate rectifiers
US2852448A (en) * 1955-09-01 1958-09-16 Sylvania Electric Prod Crystal rectifiers and method
US2893930A (en) * 1956-10-03 1959-07-07 Gen Lab Associates Inc Process of making a ceramic element usable in surface-gap igniters
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US3146980A (en) * 1962-09-14 1964-09-01 North American Aviation Inc Shock preventive mounting structure
US3157835A (en) * 1960-04-29 1964-11-17 Siemens Ag Ceramic blocking layer capacitor
US3160944A (en) * 1959-04-24 1964-12-15 Int Standard Electric Corp Electrical circuit elements
US3210607A (en) * 1961-09-07 1965-10-05 Texas Instruments Inc Ferroelectric capacitor apparatus
US3213338A (en) * 1962-04-11 1965-10-19 Lockheed Aircraft Corp Semiconductive diode of single-crystal rutile and method of making same
US3221228A (en) * 1961-09-15 1965-11-30 Cornell Dubilier Electric Ceramic capacitor and the method of making the same
US3237066A (en) * 1963-02-25 1966-02-22 Sprague Electric Co Capacitor with electrodes of metal coated particles
US3251918A (en) * 1961-06-14 1966-05-17 Du Pont Process for making a capacitor element for high temperature operation
US3289118A (en) * 1962-03-29 1966-11-29 Globe Union Inc Filter
US3321683A (en) * 1965-06-01 1967-05-23 Sprague Electric Co Electric circuit elements
US3419759A (en) * 1965-09-17 1968-12-31 Matsushita Electric Ind Co Ltd Capacitor comprising ferroelectric ceramic with oxidic silver electrodes and heterojunction barrier layer between electrodes and ceramic
US3419758A (en) * 1966-01-03 1968-12-31 Matsushita Electric Ind Co Ltd Ceramic capacitor comprising semiconductive barium titanate body and silver alloy electrodes containing minor amount of cu, ca or bi
US3421195A (en) * 1965-12-23 1969-01-14 Dale Electronics Capacitor and method of making same
US3434015A (en) * 1959-02-06 1969-03-18 Texas Instruments Inc Capacitor for miniature electronic circuits or the like
US3447217A (en) * 1964-02-05 1969-06-03 Hitachi Ltd Method of producing ceramic piezoelectric vibrator
US3484258A (en) * 1966-10-26 1969-12-16 Owens Illinois Inc Conductive glass-ceramic product having a high dielectric constant and method of making same
US3569795A (en) * 1969-05-29 1971-03-09 Us Army Voltage-variable, ferroelectric capacitor
US3677184A (en) * 1955-08-16 1972-07-18 Us Army Proximity fuzes
US3755723A (en) * 1968-02-26 1973-08-28 Du Pont Novel glasses, silver compositions and capacitors therefrom
US4106933A (en) * 1975-06-18 1978-08-15 Minnesota Mining And Manufacturing Company Piezoelectric method and medium for producing electrostatic charge patterns
US4360762A (en) * 1979-12-21 1982-11-23 Tdk Electronics Co., Ltd. Rapid starter switch for a fluorescent lamp
US4669160A (en) * 1984-12-21 1987-06-02 General Electric Company Method for prepolarizing and centering a piezoelectric ceramic switching device
US4670682A (en) * 1984-12-21 1987-06-02 General Electric Company Piezoelectric ceramic switching devices and systems and method of making the same
US4675960A (en) * 1985-12-30 1987-06-30 Motorola, Inc. Method of manufacturing an electrically variable piezoelectric hybrid capacitor
US4678957A (en) * 1986-06-24 1987-07-07 General Electric Company Piezoelectric ceramic switching devices and systems and methods of making the same
US4714848A (en) * 1987-03-02 1987-12-22 The United States Of America As Represented By The United States Department Of Energy Electrically induced mechanical precompression of ferroelectric plates
US4769570A (en) * 1986-04-07 1988-09-06 Toshiba Ceramics Co., Ltd. Piezo-electric device
US4862029A (en) * 1987-02-11 1989-08-29 Tosoh Corporation Actuator
USRE33568E (en) * 1984-12-21 1991-04-09 General Electric Company Piezoelectric ceramic switching devices and systems and methods of making the same
USRE33577E (en) * 1984-12-21 1991-04-23 General Electric Company Advanced piezoceramic power switching devices employing protective gastight enclosure and method of manufacture
USRE33587E (en) * 1984-12-21 1991-05-14 General Electric Company Method for (prepolarizing and centering) operating a piezoceramic power switching device
USRE33618E (en) * 1984-12-21 1991-06-25 General Electric Company Method for initially polarizing and centering a piezoelectric ceramic switching device
USRE33691E (en) * 1984-12-21 1991-09-17 General Electric Company Piezoelectric ceramic switching devices and systems and method of making the same
US5142186A (en) * 1991-08-05 1992-08-25 United States Of America As Represented By The Secretary Of The Air Force Single crystal domain driven bender actuator
US5233260A (en) * 1989-04-26 1993-08-03 Hitachi, Ltd. Stack-type piezoelectric element and process for production thereof
US5653537A (en) * 1995-03-17 1997-08-05 Ircon, Inc. Non-contacting infrared temperature thermometer detector apparatus
US5812270A (en) * 1997-09-17 1998-09-22 Ircon, Inc. Window contamination detector
US6452310B1 (en) * 2000-01-18 2002-09-17 Texas Instruments Incorporated Thin film resonator and method

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Cited By (57)

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US2909716A (en) * 1949-10-31 1959-10-20 Siemens Ag Semi conductor arrangement
US2793288A (en) * 1950-02-21 1957-05-21 Charles F Pulvari Apparatus for electrostatic recording and reproducing
US2768421A (en) * 1952-05-17 1956-10-30 Clevite Corp Method of making circuit connections to a transducer unit
US2821490A (en) * 1953-03-11 1958-01-28 Sylvania Electric Prod Titanate rectifiers
US2841722A (en) * 1953-03-18 1958-07-01 Clevite Corp Bending-responsive electromechanical transducer device
US2806189A (en) * 1953-07-03 1957-09-10 Sylvania Electric Prod Alkaline titanate rectifiers
US2851405A (en) * 1953-07-03 1958-09-09 Sylvania Electric Prod Titanate rectifiers
US2782397A (en) * 1953-10-01 1957-02-19 Ibm Piezoelectric interrogation of ferroelectric condensers
US2796564A (en) * 1953-12-21 1957-06-18 Sylvania Electric Prod Electric circuit element
US2836776A (en) * 1955-05-07 1958-05-27 Nippon Electric Co Capacitor
US2841508A (en) * 1955-05-27 1958-07-01 Globe Union Inc Electrical circuit elements
US3677184A (en) * 1955-08-16 1972-07-18 Us Army Proximity fuzes
US2852448A (en) * 1955-09-01 1958-09-16 Sylvania Electric Prod Crystal rectifiers and method
US2893930A (en) * 1956-10-03 1959-07-07 Gen Lab Associates Inc Process of making a ceramic element usable in surface-gap igniters
US2967282A (en) * 1957-09-30 1961-01-03 Gen Electric High temperature resistor
US3074804A (en) * 1957-11-29 1963-01-22 Nat Res Dev Intergranular barrier layer dielectric ceramic compositions and the method of production thereof
US3028248A (en) * 1958-11-28 1962-04-03 Nat Res Dev Dielectric ceramic compositions and the method of production thereof
US3434015A (en) * 1959-02-06 1969-03-18 Texas Instruments Inc Capacitor for miniature electronic circuits or the like
US3160944A (en) * 1959-04-24 1964-12-15 Int Standard Electric Corp Electrical circuit elements
US3157835A (en) * 1960-04-29 1964-11-17 Siemens Ag Ceramic blocking layer capacitor
DE1127478B (en) * 1960-08-23 1962-04-12 Siemens Ag Electrolytic capacitor and process for its manufacture
US3251918A (en) * 1961-06-14 1966-05-17 Du Pont Process for making a capacitor element for high temperature operation
US3210607A (en) * 1961-09-07 1965-10-05 Texas Instruments Inc Ferroelectric capacitor apparatus
US3221228A (en) * 1961-09-15 1965-11-30 Cornell Dubilier Electric Ceramic capacitor and the method of making the same
US3289118A (en) * 1962-03-29 1966-11-29 Globe Union Inc Filter
US3213338A (en) * 1962-04-11 1965-10-19 Lockheed Aircraft Corp Semiconductive diode of single-crystal rutile and method of making same
US3146980A (en) * 1962-09-14 1964-09-01 North American Aviation Inc Shock preventive mounting structure
US3237066A (en) * 1963-02-25 1966-02-22 Sprague Electric Co Capacitor with electrodes of metal coated particles
US3447217A (en) * 1964-02-05 1969-06-03 Hitachi Ltd Method of producing ceramic piezoelectric vibrator
US3321683A (en) * 1965-06-01 1967-05-23 Sprague Electric Co Electric circuit elements
US3419759A (en) * 1965-09-17 1968-12-31 Matsushita Electric Ind Co Ltd Capacitor comprising ferroelectric ceramic with oxidic silver electrodes and heterojunction barrier layer between electrodes and ceramic
US3421195A (en) * 1965-12-23 1969-01-14 Dale Electronics Capacitor and method of making same
US3419758A (en) * 1966-01-03 1968-12-31 Matsushita Electric Ind Co Ltd Ceramic capacitor comprising semiconductive barium titanate body and silver alloy electrodes containing minor amount of cu, ca or bi
US3484258A (en) * 1966-10-26 1969-12-16 Owens Illinois Inc Conductive glass-ceramic product having a high dielectric constant and method of making same
US3755723A (en) * 1968-02-26 1973-08-28 Du Pont Novel glasses, silver compositions and capacitors therefrom
US3569795A (en) * 1969-05-29 1971-03-09 Us Army Voltage-variable, ferroelectric capacitor
US4106933A (en) * 1975-06-18 1978-08-15 Minnesota Mining And Manufacturing Company Piezoelectric method and medium for producing electrostatic charge patterns
US4360762A (en) * 1979-12-21 1982-11-23 Tdk Electronics Co., Ltd. Rapid starter switch for a fluorescent lamp
USRE33618E (en) * 1984-12-21 1991-06-25 General Electric Company Method for initially polarizing and centering a piezoelectric ceramic switching device
USRE33691E (en) * 1984-12-21 1991-09-17 General Electric Company Piezoelectric ceramic switching devices and systems and method of making the same
US4670682A (en) * 1984-12-21 1987-06-02 General Electric Company Piezoelectric ceramic switching devices and systems and method of making the same
US4669160A (en) * 1984-12-21 1987-06-02 General Electric Company Method for prepolarizing and centering a piezoelectric ceramic switching device
USRE33587E (en) * 1984-12-21 1991-05-14 General Electric Company Method for (prepolarizing and centering) operating a piezoceramic power switching device
USRE33577E (en) * 1984-12-21 1991-04-23 General Electric Company Advanced piezoceramic power switching devices employing protective gastight enclosure and method of manufacture
USRE33568E (en) * 1984-12-21 1991-04-09 General Electric Company Piezoelectric ceramic switching devices and systems and methods of making the same
US4716331A (en) * 1985-12-30 1987-12-29 Motorola Inc. Electrically variable piezoelectric hybrid capacitor
US4675960A (en) * 1985-12-30 1987-06-30 Motorola, Inc. Method of manufacturing an electrically variable piezoelectric hybrid capacitor
US4862030A (en) * 1986-04-07 1989-08-29 Toshiba Ceramics Co., Ltd. Piezo-electric device
US4769570A (en) * 1986-04-07 1988-09-06 Toshiba Ceramics Co., Ltd. Piezo-electric device
US4678957A (en) * 1986-06-24 1987-07-07 General Electric Company Piezoelectric ceramic switching devices and systems and methods of making the same
US4862029A (en) * 1987-02-11 1989-08-29 Tosoh Corporation Actuator
US4714848A (en) * 1987-03-02 1987-12-22 The United States Of America As Represented By The United States Department Of Energy Electrically induced mechanical precompression of ferroelectric plates
US5233260A (en) * 1989-04-26 1993-08-03 Hitachi, Ltd. Stack-type piezoelectric element and process for production thereof
US5142186A (en) * 1991-08-05 1992-08-25 United States Of America As Represented By The Secretary Of The Air Force Single crystal domain driven bender actuator
US5653537A (en) * 1995-03-17 1997-08-05 Ircon, Inc. Non-contacting infrared temperature thermometer detector apparatus
US5812270A (en) * 1997-09-17 1998-09-22 Ircon, Inc. Window contamination detector
US6452310B1 (en) * 2000-01-18 2002-09-17 Texas Instruments Incorporated Thin film resonator and method

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