WO1989006219A1 - Yttrium-barium-cobalt oxide conductive compositions - Google Patents
Yttrium-barium-cobalt oxide conductive compositions Download PDFInfo
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- 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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- barium
- yttrium
- compositions
- samarium
- conductive compositions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/66—Complex oxides containing cobalt and at least one other metal element containing alkaline earth metals, e.g. SrCoO3
- C01G51/68—Complex oxides containing cobalt and at least one other metal element containing alkaline earth metals, e.g. SrCoO3 containing rare earths, e.g. (La0.3Sr0.7)CoO3
-
- 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.
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- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
Abstract
Electrically conductive compositions have the formula AwBxCoyOz, where A is yttrium, 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. Further, they exhibit anomalies in their resistance and magnetic properties as a function of temperature. AB2Co3O3.5, particularly YBa2Co3O3.5, is preferred.
Description
YI I_I M-BZRΠJM-COBALT OXIDE CONDUCTIVE COMPOSITIONS
This invention relates to cobalt-containing ceramic compositions with high electrical conductivity.
Ceramics with conductivity near that of metals are relatively rare. There are circumstances, either structural or environmental, where one might prefer to use a ceramic conductor instead of a metallic one. For example, U.S. Pat. 4,422,917 discloses the use of ceramics of reduced titanium oxide ( li . Oη ) as electrode materials due to their metallic conductivity.
We describe here robust, cobalt containing ceramics that are useful as conductors.
It has now been discovered that certain cobalt-containing 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.
In preferred embodiments of the 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, -.
The 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. Alternatively, 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.
The 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.
That the conductivity of these compositions is not simply the result of the presence of bulk cobalt metal is evidenced by the magnetism as illustrated in Figure 2. Here, the compositions are apparently anti-ferromagnetic, while cobalt metal is ferromagnetic. The anti-ferromagnetiεm 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.
A more comprehensive understanding of this invention can be obtained by reference to the following examples, which are provided by way of illustration and not of limitation.
Example 1^
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- ) - «6H20) , 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. Excess ammonium carbonate (( H.^ O-, 0.33 mole) was added to make the metal carbonates. This solution was heated to 100 °C and then held for 5 min. After heating, oxalic acid was added until carbon dioxide evolution ceased and a pH of 2 was reached (about 40 g of oxalic acid required). The metal oxalate precipitate was vacuum- filtered and calcined. Typically the powder was heated to 300 °C at a ramp of 2 °C/min, held there for 1 hr, ramped to 500 °C at 7 °C/min, and then held there for 0.5 hr.
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.
Additionally, following the above procedure, compositions having samarium or lanthanum in place of the yttrium and/or calcium or strontium in place of the barium were prepared.
Example 2_
Electrical measurements of 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- -.
TABLE
Resistivities of AB Co 3,0W3.5
Element B 2 Element A - Ca (1.00) Sr (1.10) Ba (1.34)
Y (0.89) 9.0x10 (300) 1.4x10 * (0) Sm (0.96) 5.6xl0~3 (300) ca. 0 (0) La (1.01) 9.0xl0_^ (300) 0x10 2 (300) 9.0xl0_^ (300) 1.2x10 (0) ca. 0 (0) 1.5x10 (0)
1 In ohm-cm with temperature (°K) in parentheses; 300 °K values are measured; 0 °K values are extrapolated.
2 Ionic radius given in parentheses.
I = insulator (resistivity greater than 1 x 10 ohm-cm),
It appears that there is an ionic radius effect. Where an element A having a small ionic radius (e.g., yttrium) is combined with an element B also having a small ionic radius (e.g., calcium), the composition is an insulator. But where the combined ionic radii exceed a certain minimum size (e.g., by combining a small radius element A (yttrium) with a large radius element B (barium), or vice versa, or combining a large radius element A with a large radius element B), the compositions are electrically conductive.
Example 3_
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 βK moment that decreases with temperature in an anti-ferromagnetic fashion.
Claims
1. A comprosition having S the formula AWBXCo.y0Z, where A is yttrium, 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.
2. A composition according to claim 1 wherein w is about 1, x is about 2, y is about 3, and z is about 3.5.
3. A composition according to claim 1 or 2, wherein A is yttrium and B is barium.
4. A composition according to claim 1 or 2, wherein A is samarium and B is barium.
5. A composition according to claim 1 or 2 , wherein A is lanthanum.
6. A composition according to claim 5, wherein β is calcium.
7. A composition according to claim 5, wherein B is strontium.
8. A composition according to claim 5, wherein B is barium.
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 Ceased WO1989006219A1 (en) | 1988-01-05 | 1989-01-05 | Yttrium-barium-cobalt oxide conductive compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH03503520A (en) |
| WO (1) | WO1989006219A1 (en) |
Citations (4)
| 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 |
-
1989
- 1989-01-05 WO PCT/US1989/000044 patent/WO1989006219A1/en not_active Ceased
- 1989-01-05 JP JP1501958A patent/JPH03503520A/en active Pending
Patent Citations (4)
| 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 (en) | 1991-08-08 |
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