US3359470A - Method of piezoelectrically activating ferroelectric materials - Google Patents

Method of piezoelectrically activating ferroelectric materials Download PDF

Info

Publication number
US3359470A
US3359470A US478572A US47857265A US3359470A US 3359470 A US3359470 A US 3359470A US 478572 A US478572 A US 478572A US 47857265 A US47857265 A US 47857265A US 3359470 A US3359470 A US 3359470A
Authority
US
United States
Prior art keywords
electric field
poling
intensity
app
same
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US478572A
Other languages
English (en)
Inventor
Takahashi Masao
Tsubouchi Norio
Ohno Tomeji
Yamauchi Fumio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEC Corp
Original Assignee
Nippon Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Co Ltd filed Critical Nippon Electric Co Ltd
Application granted granted Critical
Publication of US3359470A publication Critical patent/US3359470A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
    • H01G2/08—Cooling arrangements; Heating arrangements; Ventilating arrangements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/51—Shaped 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
    • H01G7/025—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric
    • H01G7/026—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric with ceramic dielectric
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
    • H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/42—Piezoelectric device making

Definitions

  • This invention relates to poling processes for ferroelectric materials.
  • FIG. 1 is a graph illustrating dependence of the electromechanical coupling factor in the radial mode (k1.) on the lapse of time of a ferroelectric material whose comp'osition can vbe expressed as:
  • FIGS. 2a, 2b and 2c show hysteresis curves as viewed on a cathode-ray tube screen, of several specimens at room temperature of a ferroelectric ceramic which can be expressed as:
  • FIG. 2d shows a hysteresis curve produced on a cathode-ray tube screen when a specimen having the same composition was subjected to a maximum AC voltage of 5 kv./mm. at 100 C. for 10 minutes after a time elapse of 24 hours at the conclusion of thermal depolarization.
  • FIGS. 3a, 3b and 3c show hysteresis curves produced on a tube screen, of several specimens at room temperature of a ferroelectric material which can be expressed as:
  • FIG. 3d shows such ahysteresis curve when a specimen having the same composition was subjected to a maximum A.C. voltage of 5 kv./mm. at 100 C. after a time elapse of three hours at the conclusion of thermal depolarization.
  • ferroelectric materials in general exhibit the characteristics of both ferroelectricity and piezoelectricity.
  • Displacement type ferr'oelectric materials such as are represented by barium titanate (BaTiO3) and lead titanate zirconate Pb(Zr-Ti)03 manifest no piezoelectricity even if a pair of electrodes are installed on the opposite surfaces of a specimen regardless of whether they are ceramic materials produced by sintering in terms of solid phase reaction or single crystal materials produced by melting in terms of liquid phase reaction. The reason is due to the fact that the internal structure of such material is divided ferroelectrically into what may be called ferroelectric domains.
  • piezoelectricity possessed by one domain has a direct bearing on the direction of the spontaneous polarization axis and the spontaneous polarization of all domains spatially distributed at random within la displacement type ferroelectric material even if a pair of electrodes are simply installed without applyi-ng la high DC electric field. Therefore, if 'a domain is elongated in proportion t'o the intensity of an externally applied electric eld, another domain whose spontaneous polarization is in the opposite sense to that domain must be contracted by the same amount, with the result that no overall piezoelectricity is exhibited. In order that the piezoelectricity characteristic may be exhibited, the spontaneous polarization of these domains should be reoriented in one common direction. Furthermore, if the spontaneous polarization of all domains is reoriented in one direction, the greatest piezoelectric effect would be manifested by any given specimen.
  • a common means for effecting the reorientation is to apply a high intensity DC electric eld to a ferroelectric material for a considerably long time interval to reorient the direction of spontaneous polarization of each domain in what is commonly called the easy axial direction of each domain which is the closest to the direction of the applied DC electric iield.
  • Such process is known as poling All piezoelectric materials, however, do not belong to the crystallographic cubic structure, and accordingly in certain materials a stress is created during reorient'ation. In poling, therefore, the spontaneous polarization of each domain must be reoriented approximately in the electric field direction against this stress, with the result that it takes 'a long time to effect the reorientati'on. Consequently, two requirements must be met in order to impart the largest possible piezoelectric characteristic to a ferroelectric material, i.e., poling by the application of a sufliciently high intensity DC electric field, and for a long time interval.
  • the present inventors have conducted many experimental tests to obtain a comparison of piezoelectricity attainable by poling at high temperatures with that at room temperature.
  • the electromechanical coupling factor in the radial mode (kr) was adopted as a measure of the assessment of piezoelectricity yas has been the common practice.
  • the larger the value of piezoelectricity the larger became the value of kr.
  • Table 1 shows the experimental result obtained in this manner.
  • NoTE.-Propeller in the remarks column denotes a propeller type hysteresis loop depicted on the CRT screen.
  • FIG. 1 illustrates our experimental Iresult with a lead titanate zirconate lbase ceramic material consisting of a 52 mole percent lead zirconate, 48 mole percent lead titanate, and 0.5 wt. percent Fe203 as an additive agent and having the compositional formula:
  • the ⁇ curve in FIG. l illustrates the manner in which the piezoelectric characteristic expressed in the electromechanical coupling factor in the radial mode (kr) varies with the time interval between thermal depolarization and poling. Inspection of this curve readily reveals that the piezoelectric characteristic becomes reduced with an increasing time interval between thermal depolarization and poling.
  • the reasons for the improved piezoelectric properties electric field intensity, within a shorter time interval, and according to this invention may be understood from the at a comparatively lower temperature.
  • the pre-treatment at a high inten- A well known method of reorientation of the domain sity AC electric field causes rapid reversal of the direcstructure of a ferroelectric material consists of heating 10 tion of the electric field and changes the intensity of the it above the Curie temperature to destroy the old strucfield from time to time, and hence changes the direction ture and then decreasing the temperature below the Curie of spontaneous polarization of many domains in the matepoint thereby to form a new domain structure. This procrial.
  • orientation of the domain structure that has ess is known as thermal depolarization.
  • thermal depolarization orientation of the domain structure that has ess is known as thermal depolarization.
  • a time elapse is agitated
  • thermal depolarization is advantageous tion of spontaneous polarization of each domain is varied over the conventional poling methods effected for ferroby application of a high intensity AC electric field
  • electric materials after their domain structure has been stresses are created within the material, which remain fully stabilized wil-l be evident from the illustration of for some time even after removal of the AC electric FIG. 1. field to place the structure into an unstable condition.
  • titanate zirconate ceramic which can be expressed as:
  • Another object of this invention is to provide a new depolarization method. Another object of the invention is to harness for industrial purposes the advantages of poling prior to stabilization of the domain structure.
  • a further object is to utilize the experimental information illustrated in FIG. 1 by providing a new depolarization method whereby easy and rapid synchronization with the poling process can be achieved.
  • the above problems are obviated -by a poling process characterized in that an AC electric field in excess of the coercive electric field intensity and less than the breakdown field intensity of a ferroelectric material is -applied thereto for a suitable time interval prior to poling, and thereafter a DC electric field in excess of the coercive field intensity and less than the breakdown field intensity is applied to the material.
  • FIGS. 2a, 2b and 2c illustrate the manner in which the hysteresis curve depicted on the cathode ray tube screen varies with time with an AC electric field applied to a sample of a lead titanate zirconate ceramic which can be expressed as:
  • FIG. 2a denotes the configuration of the curve obtained when the AC electric field was applied for one minute, FIG. 2b that when it was applied for 5 minutes, and FIG. 2c that when it was applied for l0 minutes.
  • the configuration of the curve thereafter remained substantially unchanged.
  • FIG. 2d shows the configuration of the hysteresis curve measured at 100 C. It was proven by our experiment that changes in the configuration of the curve of FIG. 2d at 100 C. with elapsed time were less pronounced than changes in the configuration of the -curve at room temperature with elapsed time and maniested appreciably larger 'values of Ps. app. and Pr. app. from the beginning.
  • FIG. 2d The experimental result of FIG. 2d is equivalent in :significance to the result shown in Table l which has proved that poling at high temperatures obtains more excellent piezoelectric properties than those obtained at room temperature.
  • a comparison of FIGS. 2c and 2d further reveals that both configurations are quite similar and that the values of Ps. app. and P1'. app. are approximately of the same degree.
  • FIG. 3 shows similar results of our experiment as in the case of FIG. 2 with a lead titanate zirconate ferroelectric ceramic which can be expressed as:
  • the hysteresis curves in FIG. 3 indicate that the values 'of both Ps. app. and Pr. app. at room temperature increase with increased application time of an AC electric .field to the ceramis and that the hysteresis curve measured 'with an AC voltage applied for 10 minutes at room temperature is similar in the configuration to the curve measured with the same AC voltage applied for 10 minutes at ⁇ 'an elevated temperature.
  • a method of piezoelectrically activating a ferroelectrc material characterized by comprising successive steps o applying an AC electric field of an intensity in excess of the coercive electric field intensity and less than the breakdown field intensity of said material,
  • a poling method for piezoelectrically activating a fefrroelectric material which comprises the successive steps o exposing said material to an AC electric field having an intensity in excess of the coercive electric field intensity and less than the breakdown eld intensity of said material,
  • vention can find application for materials whose electrical and exposing said material to a DC electric fiield havresistivities are too low at room temperature, because the ing an intensity in excess of the order of the coercive electrical resistivities of such materials can be sufficiently electric field intensity and less than the breakdown increased by cooling to a low temperature adapted for the electric field intensity of said material.
  • the poling process according to this invention may be said to be effective at any temperature References Cited unless the electrical resistance becomes too small to apply UNITED STATES PATENTS a high intensity electric field.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
US478572A 1964-08-10 1965-08-10 Method of piezoelectrically activating ferroelectric materials Expired - Lifetime US3359470A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4552464 1964-08-10

Publications (1)

Publication Number Publication Date
US3359470A true US3359470A (en) 1967-12-19

Family

ID=12721784

Family Applications (1)

Application Number Title Priority Date Filing Date
US478572A Expired - Lifetime US3359470A (en) 1964-08-10 1965-08-10 Method of piezoelectrically activating ferroelectric materials

Country Status (4)

Country Link
US (1) US3359470A (de)
DE (1) DE1466189B1 (de)
GB (1) GB1105415A (de)
NL (1) NL6510416A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3710465A (en) * 1970-04-23 1973-01-16 Siemens Ag Method for the subsequent adjusting of the transit time of a piezo-electric ceramic substrate for an electro-acoustical delay line
US3750056A (en) * 1972-03-10 1973-07-31 Zenith Radio Corp Acoustic surface-wave filters and methods of manufacture therefor
US10490726B2 (en) * 2014-09-11 2019-11-26 Sicpa Holding Sa Pyroelectric generator

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59205779A (ja) * 1983-05-09 1984-11-21 Daikin Ind Ltd 高分子圧電性材料の製法
JP3185226B2 (ja) * 1991-01-30 2001-07-09 株式会社村田製作所 圧電バイモルフ素子の駆動方法及び圧電バイモルフ素子
DE102010001224A1 (de) * 2010-01-26 2011-07-28 Robert Bosch GmbH, 70469 Verfahren zur Herstellung eines Piezoaktors mit einem Mehrlagenaufbau von Piezolagen und einen Piezoaktor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2538554A (en) * 1947-08-22 1951-01-16 Zenith Radio Corp Process of producing piezoelectric transducers
US2702427A (en) * 1948-03-13 1955-02-22 Roberts Shepard Method of making electromechanically sensitive material
US2706326A (en) * 1952-04-23 1955-04-19 Bell Telephone Labor Inc Polarization process for pseudocubic ferroelectrics
US2708243A (en) * 1951-02-10 1955-05-10 Clevite Corp Polycrystalline ceramic material
US3108211A (en) * 1960-08-08 1963-10-22 Electro Sonic Ind Inc Activation of ferroelectric elements

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2787520A (en) * 1952-03-07 1957-04-02 California Research Corp Process for producing piezoelectric transducers
GB727935A (en) * 1952-03-14 1955-04-13 Erie Resistor Corp Polarisation of barium titanate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2538554A (en) * 1947-08-22 1951-01-16 Zenith Radio Corp Process of producing piezoelectric transducers
US2702427A (en) * 1948-03-13 1955-02-22 Roberts Shepard Method of making electromechanically sensitive material
US2708243A (en) * 1951-02-10 1955-05-10 Clevite Corp Polycrystalline ceramic material
US2706326A (en) * 1952-04-23 1955-04-19 Bell Telephone Labor Inc Polarization process for pseudocubic ferroelectrics
US3108211A (en) * 1960-08-08 1963-10-22 Electro Sonic Ind Inc Activation of ferroelectric elements

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3710465A (en) * 1970-04-23 1973-01-16 Siemens Ag Method for the subsequent adjusting of the transit time of a piezo-electric ceramic substrate for an electro-acoustical delay line
US3750056A (en) * 1972-03-10 1973-07-31 Zenith Radio Corp Acoustic surface-wave filters and methods of manufacture therefor
US10490726B2 (en) * 2014-09-11 2019-11-26 Sicpa Holding Sa Pyroelectric generator

Also Published As

Publication number Publication date
DE1466189B1 (de) 1970-06-25
GB1105415A (en) 1968-03-06
NL6510416A (de) 1966-02-11

Similar Documents

Publication Publication Date Title
US2708244A (en) Piezoelectric transducers using lead titanate and lead zirconate
Kuwata et al. Phase transitions in the Pb (Zn1/3Nb2/3) O3-PbTiO3 system
Mueller et al. Shear response of lead zirconate titanate piezoceramics
US3359470A (en) Method of piezoelectrically activating ferroelectric materials
Qi et al. Electromechanical properties of Mn-doped Pb (In1/2Nb1/2) O3-Pb (Mg1/3Nb2/3) O3-PbTiO3 piezoelectric ceramics
Qi et al. Effect of Mn-doping on dielectric relaxation behavior of Pb (In1/2Nb1/2) O3-Pb (Mg1/3Nb2/3) O3-PbTiO3 ferroelectric ceramics
Tasson et al. Piezoelectric study of poling mechanism in lithium niobate crystals at temperature close to the curie point
US2724171A (en) Activation of ferroelectrics
US3365400A (en) Electrical devices embodying ferrielectric substances
Lawless Glasslike properties of ferroelectrics at low temperatures
Kok et al. Substrate-free thick-film lead zirconate titanate (pzt) performance measurement using berlincourt method
US2985759A (en) Ferroelectric devices
Mohamad et al. Acoustic emission from domain wall motion in ferroelectric lead germanate
Belov 1/E 2 Law: Solution of the Unsolved Problem in the Physics of Ferroelectrics
US3310720A (en) Polarization process for ceramics
Okada et al. Precise measurements of the landau-devonshire coefficients of KDP
US4565943A (en) Process for preparing polymeric piezoelectric material
US2983988A (en) Method of polarizing transducers
Mr [Odot] Z et al. Ferroelectric and ferroelastic phase transitions in (CH3NH3) 3Sb2Br9 crystals
US3465069A (en) Process for treating electrostrictive ceramic elements
GB1090037A (en) Poling method of ferroelectric ceramic bodies
Gallo et al. Alternating‐Current‐Assisted Poling of Lead Zirconate Titanate (PZT)
KR102623532B1 (ko) 납-금속 화합물 단결정의 개질방법
Sidak et al. Structural defects and electrical properties of Na 0.5 Bi 0.5 TiO 3 crystal
Alberta et al. The piezoelectric, elastic and dielectric constants for ceramics in the solid solution:(x) PbZro3−(1− x− z) Pb (Zn⅓Nb⅔) O3−(z) PbTiO3