USRE24191E - Piezoelectric transducers using lead - Google Patents

Piezoelectric transducers using lead Download PDF

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USRE24191E
USRE24191E US58440856E USRE24191E US RE24191 E USRE24191 E US RE24191E US 58440856 E US58440856 E US 58440856E US RE24191 E USRE24191 E US RE24191E
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lead
transducers
piezoelectric
ceramic
titanate
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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
    • C04B35/50Shaped 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
    • C04B35/01Shaped 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
    • C04B35/51Shaped 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
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L41/00Piezo-electric devices in general; Electrostrictive devices in general; Magnetostrictive devices in general; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L41/16Selection of materials
    • H01L41/18Selection of materials for piezo-electric or electrostrictive devices, e.g. bulk piezo-electric crystals
    • H01L41/187Ceramic compositions, i.e. synthetic inorganic polycrystalline compounds incl. epitaxial, quasi-crystalline materials

Description

my 31, 1956 Re. 24,191

B. JA'F F E PIEZOELECTRIC TRANSDUCERS USING LEAD TITANATE AND LEAD ZIRCONATE Original Filed March 24. 1954 2 6172/0 coa ting I JSzYver Casi/1'7 INVENTOR. Bernard: J'affe ATTORNEYS,

PIEZOELECTRIC TRANSDUCERS USING LEAD 7 TITANATE AND LEAD ZIRCONATE Bernard Jaife, South Euclid, Ohio, assignor to the United States of America as represented by the Secretary of the Army Original No. 2,708,244, dated May10, 1955, Serial No. 418,487, March 24, 1954. Application for reisue May 11, 1956, Serial No. 584,408

(Granted under Title 35, U. S. Code (1952), see. 266) 4 Claims. (Cl. 310-8.0)

Matter enclosed in heavy brackets II] appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

The invention described herein may be manufactured and used by or for the Government for governmental purment and reproduction of sound, noise, shock, and vibration, has increased greatly in recent years. Measurement of noise, shock, and vibration have come to play a par ticularly important part in the development of military and industrial equipment, as well as of civilian consumer goods. Both crystal and ceramic types of transducers have been widely used. 1

Crystal transducers are expensive, as they must be formed by lapidary techniques from perfect single crystals. Many of the commonly used ones-Rochelle salt, for instance-are water soluble, and others dehydrate easily.

The newer ceramic. transducers, principally those using barium titanate, are more economical, more rugged, and capable of operation at somewhat higher temperatures, as compared with many popular crystal transducers. However, barium titanate transducers have a Curie point of only about 120 C. and lose their piezoelectric properties as they approach this temperature, so that such transducers are worthless for many applications. Furthermore, at C. and 90 C. barium titanate undergoes polymorphic transformations, and 'at these temperatures the dielectric and piezoelectric constants go through maxima. These maxima make barium titanate transducers unsuitable for certain applications where fiat or uniformly-varying output over a wide temperature range is desired.

I have now discovered that certain solid solutions of lead titan-ate and lead zirconate will provide ceramic piezoelectric transducers having a number of advantages over previous transducers. In particular, my transducers will operate at substantially higher temperatures than barium titanate transducers, and my transducers give a more uniform response over a wider temperature range.

A principal object of my invention is to provide a piezoelectric transducer that is rugged, low in cost, readily producible from readily available raw materials, insoluble in water, relatively uniform in characteristics over a wide temperature range, and capable of operation at elevated temperatures.

Other objects, aspects, uses, and advantages of the invention will become apparent from the following description and from the drawing.

The drawing shows a cross section of a piezoelectric transducer according to the invention.

Referring to the drawing, reference numeral 1 designates an electrically polarized ceramic body consisting of a solid solution of lead titanate (PbTiOa) and lead zirconate (PbzrOa). A preferred proportion of lead titanate in this solution is of the order of 45 mole percent. Silver electrodes 2 and 3 are coated on two opposite faces of the ceramic body. Wire leads 4 and 5 are attached to silver electrodes 2 and 3 respectively by means of solder 6. When the ceramic is subjected to shock, vibration, or other mechanical stress, an electrical output is generated that can be taken from wire leads 4 and 5. Conversely,

as with other piezoelectric transducers, application of electrical voltage to electrodes 2 and 3 will result in mechanical deformation of the ceramic body.

My transducers are fabricated by techniques similar to those used in the fabrication of other ceramic transducers- Lead oxide (PbO), zirconium dioxide (ZrOz), and titanium dioxide (TiOa) are mixed and pressed together in the form of discs or other suitable shapes and then heattreated. The heat treatment converts these raw materials to lead titanate and lead zirconate. Good results have been obtained when this heat-treatment is performed in an enclosed space with an additional source of lead oxide vapor, as suggested by S. Roberts (Iour. Am. Ceram. Soc. 33 (2), 63 (1950)). It has been found satisfactory to raise the temperature of the specimens at a rate of 4.5 C. per minute until a temperature of 1220 C. is reached, to hold them at this temperature for 30 minutes, and then to allow them to cool naturally. The disc surfaces may then be coated with silver paste and fired to form adherent silver electrodes. Finally, the silvered discs are polarized at room temperature; D. C. field strengths of the order of to volts per mil applied for time durations of the order of 1 hour are satisfactory.

I have prepared and'investigated transducer lements composed of solid solutions of lead titanate and lead zirconate in various proportions. I have found that those containing between 10 and 60 mole percent of lead titanate retain appreciable piezoelectric activity after re-' moval of the polarizing field. The following table shows, for a number of compositions, the radial (disc) coupling coefficient that was measured at room temperature 3 days after polarization for 1 hour or more at 150 volts per mil:

TABLE 1 Composition Radial coupling coat. (1:) PbZIO PbTiO;

Mole Mole percent percent It will be noted from the table that the piezoelectric properties of these solid-solution ceramics become very strong in the vicinity of the rhombohedral-tetragonal phase boundary reported by G. Shirane and K. Suzuki (Jour. Phys. Soc. Japan 7 (3), 333 (1952)); the composition having 45 mole percent lead titanate marks the limit of the rhombohedral field. Individual specimens of this composition have shown values of radial coupling coefiicient of as high as 0.40. Specimens of this composition show only a slight decrease of coupling coeflicient when heated to 200 C.; above this temperature the decrease is more rapid. Tests indicate that transducers of this composition are probably suitable for intermittent service at temperatures up to 200 C. or possibly higher.

Limited experiments show that the piezoelectric re- Reiuued July 31, 1956 l spouse persists from Dry-Ice (solid Q02) temperature (80 C.) and'probably lower, up to the Curie point (about 350 C. for the limiting rhombohedral composition containing about 55 mole percent lead zirconate and 45 mole percent lead titanate). There do not seem to be any crystalline inversions in this temperature range that would cause irregularities in the properties with varying temperature; The radial coupling coefiicient and resonance frequency change only very slight between -80 C. and room temperature.

The'following properties were found for the preferred composition at room temperature, before polarization:

TABLE 2 omposition:

PbZrOa 55 mole percent. PbTiO.-i 45 mole percent.

Density of ceramic 7.1)(10 kilogramsi'cuhic meter. Theoretical crystal density 7.!J8X10 kilograms/cubic meter. Dielectric constant at 1 n1c 585 Pissipation factor at 1 mr After polarization of this preferred composition at 150 volts per mil for 1 hour, the following properties wer found at room temperature: I

TABLE 3 Young's modulus. 7.5 l newton'/square meter. Dielectric constant at 50 kc. (trce). 500.

. V. 1.2 percent.

It has been found that the tetragonal compositions nearest the phase boundary, which contain slightly more than 45 mole percent PbTiOs, have equally high values of the radial coupling coefficient at room temperature. These tetragonal compositions, however, show a more severe decrease when the temperature of the specimen is raised. The addition of still more PbTiO: or PbZrOa, removing the composition further from the rhombohedraltetragonal phase boundary in one direction or the other, causes a lowering of the piezoelectric activity.

It may be pointed out that the two major advantages of my transducers over barium titanate transducers higher-temperature operation. and more uniform characteristics over a wider temperature range-are attained without sacrifice of other important features. My transducers are rugged and durable, insoluble in Water, high in piezoelectric activity, low in cost, and readily producible from raw materials that are readily available in large quantities.

In addition to use for sensing sound and vibration, my transducers can be used in various other applications requiring materials having piezoelectric properties. In particular. these transducers offer practical possibilities as piezoelectric filters. If desired, their piezoelectric properties would permit their use for frequency control in oscillator circuits, althoughtheir frequency stability would not be as high as that of conventional quartz crystals. When I speak of piezoelectric transducers I intend to in clude piezoelectric. filters, piezoelectric frequency control devices, and other devices dependent for their operation on the piezoelectric properties of a material.

It will be apparent that the embodiments shown are only exemplary and that various modifications can be made in construction'and arrangement within the scope of theirtvention as defined in the appended claims.

I claim as my invention: 7

l. A piezoelectric transducer comprising, in combination; a pair of electrodes; and, interposed between said electrodes. a ceramic element consisting of a solid solution of lead titanate and lead zirconate, the proportion of lead titanate in said solution being within the range 10 to 95 mole percent and the remainder being lead zirconatc.

I 2. A piezoelectric transducer comprising, in combina tion; a pair ofelectrodes; and, interposed between said electrodes, :1 ceramic element consisting of an electrically polarized solid solution of lead titanate and lead zir conate, the proportion of lead titanate in said solid solution being within the range 10 to mole percent and the remainder being lead zirconat'e.

3. A piezoelectric transducer comprising, in combination; a pair of electrodes; and, interposed between said electrodes, a ceramic element consisting of an electrically polarized solid solution of lead titanate and lead zirconate, the proportion of lead titanate in said solution being substantially the maximum that will yield a ceramic composed of rhombohedral crystals at room temperature, said proportion being nominally 45 mole percent.

4. A piezoelectric transducer comprising, in combination; a pair of electrodes; and, interposed between said electrodes. a ceramic element consisting of an electrically polarized solid solution of lead titanate and lead zirconate, the proportion of lead titanate in said solid solution being between 42 and 47 mole percent and the remainder being lead zirconate.

Wainer June 18, 1946 Roberts Feb. 13, 1951

US58440856 1954-03-24 1956-05-11 Piezoelectric transducers using lead Expired USRE24191E (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3112414A (en) * 1961-03-15 1963-11-26 Gen Telephone & Elect Acoustic transformer
US3191108A (en) * 1962-10-03 1965-06-22 Cts Corp Electrical capacitor and method of making the same
US3194765A (en) * 1965-07-13 Cadmium substituted lead zirconate titanate compositions
US3287692A (en) * 1963-02-13 1966-11-22 Raytheon Co Bender type electroacoustical apparatus
US5315203A (en) * 1992-04-07 1994-05-24 Mcdonnell Douglas Corporation Apparatus for passive damping of a structure

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117094A (en) * 1964-01-07 Lead titanate zirconate ceramic composition
US2911370A (en) * 1959-11-03 Time after polarization
US2906710A (en) * 1959-09-29 Ferroelectric ceramic composition
US2892107A (en) * 1953-12-21 1959-06-23 Clevite Corp Cellular ceramic electromechanical transducers
US2894317A (en) * 1954-06-07 1959-07-14 Spence T Marks Method for constructing a barium titanate blast velocity gauge
US2928163A (en) * 1955-08-11 1960-03-15 Clevite Corp Polarization of titanate ceramics
US2849404A (en) * 1956-04-13 1958-08-26 Jaffe Bernard Morphotropic piezoelectric ceramics
US2892955A (en) * 1956-10-10 1959-06-30 Gulton Ind Inc Ceramic transducers
US2915407A (en) * 1957-03-11 1959-12-01 Gulton Ind Inc Ceramic electrical bodies
US2960411A (en) * 1958-08-25 1960-11-15 Clevite Corp Dielectric ceramic compositions
US3006857A (en) * 1959-04-13 1961-10-31 Clevite Corp Ferroelectric ceramic composition
US3283044A (en) * 1962-12-26 1966-11-01 Arthur E Brown Method of firing ceramics
US3303133A (en) * 1964-02-06 1967-02-07 Honeywell Inc Process for producing dense ceramic of lead zirconate-titanate
GB1104383A (en) * 1964-05-30 1968-02-28 Matsushita Electric Ind Co Ltd Piezoelectric ceramic resonator devices
US3495996A (en) * 1966-05-13 1970-02-17 Ibm Ceramic composition,improved electronic devices employing same,and method of fabrication
US3533755A (en) * 1967-03-27 1970-10-13 Bell Telephone Labor Inc Radiation resistant lithium tantalate and method of producing same
US3517093A (en) * 1967-06-28 1970-06-23 Us Navy Method for producing lead zirconate-titanate transducer materials by slip casting
US4056654A (en) * 1975-07-24 1977-11-01 Kkf Corporation Coating compositions, processes for depositing the same, and articles resulting therefrom
US4279751A (en) * 1979-03-16 1981-07-21 Fishgal Semyon I Hydraulic system
NL7903964A (en) * 1979-05-21 1980-11-25 Philips Nv Pieezo electric body for an electromechanical conformation element.
EP0048536A3 (en) * 1980-09-18 1982-10-20 Matsushita Electric Industrial Co., Ltd. Sintered body of lead titanate and method of manufacturing same
US4961252A (en) * 1989-12-08 1990-10-09 Iowa State University Research Foundation, Inc. Means and method for nonuniform poling of piezoelectric transducers
BR9812150A (en) * 1997-09-05 2000-07-18 Ceramtec Ag High-capacity piezoelectric ceramics
US7132723B2 (en) * 2002-11-14 2006-11-07 Raytheon Company Micro electro-mechanical system device with piezoelectric thin film actuator
WO2010022158A2 (en) 2008-08-19 2010-02-25 The Johns Hopkins University Piezoelectric polymer fibers
US9362481B2 (en) 2012-03-05 2016-06-07 The Johns Hopkins University Continuous piezoelectric film including polar polymer fibers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2541833A (en) * 1951-02-13 Ceramic dielectrics and method
US2402517A (en) * 1943-11-02 1946-06-18 Titanium Alloy Mfg Co High dielectric material and method of making same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194765A (en) * 1965-07-13 Cadmium substituted lead zirconate titanate compositions
US3112414A (en) * 1961-03-15 1963-11-26 Gen Telephone & Elect Acoustic transformer
US3191108A (en) * 1962-10-03 1965-06-22 Cts Corp Electrical capacitor and method of making the same
US3287692A (en) * 1963-02-13 1966-11-22 Raytheon Co Bender type electroacoustical apparatus
US5315203A (en) * 1992-04-07 1994-05-24 Mcdonnell Douglas Corporation Apparatus for passive damping of a structure

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DE1105920B (en) 1961-05-04

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