WO1989006219A1 - Yttrium-barium-cobalt oxide conductive compositions - Google Patents

Yttrium-barium-cobalt oxide conductive compositions Download PDF

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Publication number
WO1989006219A1
WO1989006219A1 PCT/US1989/000044 US8900044W WO8906219A1 WO 1989006219 A1 WO1989006219 A1 WO 1989006219A1 US 8900044 W US8900044 W US 8900044W WO 8906219 A1 WO8906219 A1 WO 8906219A1
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WO
WIPO (PCT)
Prior art keywords
barium
yttrium
compositions
samarium
conductive compositions
Prior art date
Application number
PCT/US1989/000044
Other languages
English (en)
French (fr)
Inventor
Mark Thompson
Adam Tanous
Original Assignee
Raychem Corporation
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 Raychem Corporation filed Critical Raychem Corporation
Publication of WO1989006219A1 publication Critical patent/WO1989006219A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
    • C01G51/68—Cobaltates containing alkaline earth metals, e.g. SrCoO3 containing rare earth, e.g. La0.3Sr0.7CoO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/80—Constructional details
    • H10N60/85—Superconducting active materials
    • H10N60/855—Ceramic superconductors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties

Definitions

  • This invention relates to cobalt-containing ceramic compositions with high electrical conductivity.
  • compositions are electrically conductive. They have the formula AwBxCoy02 , where A is y -ttrium, samarium, or lanthanum;
  • B is calcium, strontium, or barium, provided that B is barium if A is yttrium or samarium; and w is about 0.5 to about 1.5, x is about 1.5 to about 2.5, y is about 2.5 to about 3.5, and z is less than about 6.5.
  • Figure 1 shows a graph plotting the resistivity versus temperature of a typical composition of this invention.
  • Figure 2 shows a graph of the magnetic susceptibility versus temperature of the same composition.
  • a B Co 0 w is about 1, x is about 2, y is about 3, and z is about 3.5, that is, AB-Co-O, -.
  • a preferred combination of A and B is ytrrium and barium, in particular YBa ⁇ Co-O- -.
  • Another preferred combination of A and B is lanthanum and barium, in particular LaBa ⁇ Co-O, -.
  • compositions of this invention can be prepared by hydrogen reduction of a precursor composition having the aforementioned elements A, B, Co, and 0, but with a higher oxygen content (i.e., z is about 8 or higher).
  • the precursor composition can be prepared by physically mixing the appropriate oxides of A, B, and Co and sintering at about 1200 °C in air.
  • the precursor can be prepared by a coprecipitation technique, for example by preparing the metal oxalates from solutions of the corresponding metal nitrates followed by heating in air.
  • the precursor composition is heated at about 600 °C in an atmosphere of about 5% hydrogen in nitrogen. This hydrogen treatment or reduction results in the complete disappearance of the parent compound (by X-ray diffraction) and the formation of a new phase. There is no X-ray diffraction evidence for the presence of bulk metallic cobalt.
  • the resistivity of the new phase i.e. the composition of this
  • _2 invention is no greater than about 9 x 10 ohm-cm at 300 °K.
  • compositions of this invention are useful as conductors. They are electrically conductive at about 300 °K, that is, about ambient temperature. Further, they exhibit anomalies in their resistance and magnetic properties as a function of temperature. Resistance and magnetic anomalies may be indicative of superconductivity in these compositions.
  • compositions are apparently anti-ferromagnetic, while cobalt metal is ferromagnetic.
  • the anti-ferromagneti ⁇ m cannot arise from CoO impurities either, as CoO has a Neel temperature of 290 °K while the compositions of this invention have Neel temperatures above 300 °K.
  • This example illustrates the preparation of compositions of this invention using a coprecipitation technique to prepare the precursor composition.
  • a solution of metal nitrates was prepared by dissolving 0.02 mole (7.66 g) of yttrium nitrate hexahydrate (Y(NO- ) - «6H 2 0) , 0.04 mole (10.45 g) of barium nitrate (Ba(NO,) 2 )r and 0.06 mole (17.46 g) of cobalt nitrate hexahydrate (Co(NO, ) 2 '6H-0) in 400 mL of deionized water.
  • Samples were prepared by pressing the calcined powder into bars at 10.7 kpsi. The bars were fired in air at 1200 °C for 4 hr. Upon cooling, silver electrodes (Ferrox 3350) were painted on the samples. The electrode binder was burned out by heating the samples for 10 min at 450 °C. A final heat treatment was done under flowing hydrogen-nitrogen gas (5:95%). The samples were ramped at 5 °C/min to 650 °C and held there for 1 hr and then allowed to cool in the hydrogen- nitrogen furnace.
  • compositions having samarium or lanthanum in place of the yttrium and/or calcium or strontium in place of the barium were prepared.
  • compositions made according to Example 1 were made in a temperature controlled environment (cryostat) using a four-probe technique. Typically, a sample was powered with 10 milliamps of direct current. The voltage measured across the part was then used to calculate resistivities. A sample's resistivity as a function of temperature was determined by taking this measurement as the sample was cooled from room temperature to 20 °K.
  • Figure 1 shows a plot of resistivity, in ohn-cm, versus temperature, in °K, for a typical yttrium-barium-cobalt-oxygen sample.
  • Table I provides a comparison of the 300 °K and extrapolated 0 °K resistivities for compositions having various permutations of yttrium, samarium, and lanthanum versus calcium, strontium, and barium in the preferred compositions of the formula AB-Co-O- -.
  • Element B 2 Element A - Ca (1.00) Sr (1.10) Ba (1.34)
  • I insulator (resistivity greater than 1 x 10 ohm-cm),
  • Magnetic susceptibilities were determined with an SHE Squid Magnetometer.
  • Figure 2 shows a plot of the magnetic susceptibility, in emu/mole, versus temperature, in °K, for a typical yttrium-barium-cobalt-oxygen sample.
  • the magnetic behavior of YBa ⁇ Co-O- - shows a large positive 300 ⁇ K moment that decreases with temperature in an anti-ferromagnetic fashion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Conductive Materials (AREA)
PCT/US1989/000044 1988-01-05 1989-01-05 Yttrium-barium-cobalt oxide conductive compositions WO1989006219A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14353388A 1988-01-05 1988-01-05
US143,533 1988-01-05

Publications (1)

Publication Number Publication Date
WO1989006219A1 true WO1989006219A1 (en) 1989-07-13

Family

ID=22504483

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/000044 WO1989006219A1 (en) 1988-01-05 1989-01-05 Yttrium-barium-cobalt oxide conductive compositions

Country Status (2)

Country Link
JP (1) JPH03503520A (ja)
WO (1) WO1989006219A1 (ja)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804674A (en) * 1971-05-19 1974-04-16 Hitachi Ltd Oxygen electrode material
US4045375A (en) * 1975-06-20 1977-08-30 Koshi Arita Highly electron-conductive composition
US4133778A (en) * 1976-04-19 1979-01-09 Olin Corporation Electrode with lanthanum-containing perovskite surface
US4357426A (en) * 1980-12-22 1982-11-02 Murata Manufacturing Co., Ltd. Humidity sensitive ceramics

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804674A (en) * 1971-05-19 1974-04-16 Hitachi Ltd Oxygen electrode material
US4045375A (en) * 1975-06-20 1977-08-30 Koshi Arita Highly electron-conductive composition
US4133778A (en) * 1976-04-19 1979-01-09 Olin Corporation Electrode with lanthanum-containing perovskite surface
US4357426A (en) * 1980-12-22 1982-11-02 Murata Manufacturing Co., Ltd. Humidity sensitive ceramics

Also Published As

Publication number Publication date
JPH03503520A (ja) 1991-08-08

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