WO1990011969A1 - Oxyde de cuivre a valence mixte partiellement substitue par le fluor, procede de synthese et composant en contenant - Google Patents
Oxyde de cuivre a valence mixte partiellement substitue par le fluor, procede de synthese et composant en contenant Download PDFInfo
- Publication number
- WO1990011969A1 WO1990011969A1 PCT/FR1990/000257 FR9000257W WO9011969A1 WO 1990011969 A1 WO1990011969 A1 WO 1990011969A1 FR 9000257 W FR9000257 W FR 9000257W WO 9011969 A1 WO9011969 A1 WO 9011969A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper oxide
- oxide according
- fluorine
- equal
- copper
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C04B35/45—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 copper oxide or solid solutions thereof with other oxides
- C04B35/4521—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 copper oxide or solid solutions thereof with other oxides containing bismuth oxide
- C04B35/4525—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 copper oxide or solid solutions thereof with other oxides containing bismuth oxide also containing lead oxide
-
- 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
- C01P2006/32—Thermal 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
- C01P2006/40—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
- the present invention relates to new mixed valence copper oxides with a structure derived from perowskite.
- compositions having at least partially a structure derived from perowskite.
- copper oxides have structures generally qualified as oxygen deficient, which means that there is not enough oxygen to fill all the available sites of the perowskite. In fact, they have oxygen overstoichiometric zones compared to copper at the degree of oxidation +2. This overstoichiometry is probably related to their characteristic of being superconductive at relatively high temperatures.
- one of the aims of the present invention is to provide copper oxides whose network is similar to these compounds with a laminated structure, which has electrical properties but which do not have these disadvantages of being of laminated structure involving a high apparent density.
- the solitary doubled cations are the bismuth and / or lead cations. It is advantageous to introduce the fluoride in the form of lead fluoride. Thus, there is at least one lead atom for two fluorine atoms when the introduction is carried out in this way.
- the substitution of oxygen with fluorine is accompanied by the substitution of a cation of valence n by a cation of valence n-1.
- this substitution is the substitution of bismuth for a lead.
- bismuth plus lead is preferably comprised between 1, 8 and 2; y - x is thus between -0.2 and 0.
- 3 - w + w ' is less than or equal to 3 and greater than or equal to 2.7.
- x is greater than 0.1 and less than or equal to 1, preferably between approximately 0.3 and 0.9.
- the value of y is preferably greater than 0.1.
- z which indicates the substitution rate is preferably between 0.1 and 2, preferably between 0.2 and 1.8.
- w between 0 and 2; advantageously between 0.5 and 1.5; preferably between 0.5 and 1.
- the mixed valence copper oxides according to the present invention no longer have the laminated structure described above and no longer have as high void rates as in those from which they are deduced.
- the sintering temperatures are often of the order of 100 ° C. below the sintering temperature of the superconductive ceramic compositions from which said oxides are derived.
- Another object of the present invention is to provide a process for the manufacture of new oxides of mixed valence. These synthesis methods are derived from the usual synthesis methods in the matter by replacing one or more oxides totally or partially with one or more fluorides. It is desirable that the fluorides be chosen in such a way that they do not melt at the sintering and synthesis temperature.
- the synthesis of copper oxides of mixed valence is carried out by a process comprising the following steps: a) grinding and mixing of the oxides and of fluoride (s) in proportion necessary to lead to the desired compound; b) compression of the mixtures obtained in a) in the form of pellets; c) subjecting these pellets to heating at temperatures between 600 and 850 ° C. preferably between 650 and 750 ° C for half to two days; d) rapid cooling to room temperature.
- One of the most elegant ways to add fluoride is to add fluoride in the form of lead fluoride.
- the substitution of oxygen with a fluorine is carried out simultaneously with the substitution of a trivalent element with a divalent element or of a bivalent element with a monovalent element.
- the substitution of bismuth or of another trivial element by lead it is desirable to replace a bismuth atom with a lead atom introduced half in the form of lead oxide and half in form of lead fluoride (PbF.
- the copper oxides according to the present invention can enter into the constitution of electrical or electronic components, in particular because of their superconductive properties.
- Example A mixed valence copper oxide was prepared from
- the pellets thus obtained are brought to a temperature of approximately 700 ° C. under a nitrogen atmosphere for approximately 24 hours, then are cooled to ambient temperature in 15 minutes.
- the pellets are ground to a particle size between 10 and about 20 micrometers.
- the samples used for physical characterizations are prepared in the form of bars of 12 x 2 x 0.5 mm 3 , the powders with a particle size between 10 and 20 micrometers, are pressed under 4
- the method used is that of the four points: 1 contact at each end of the bar, 2 contacts on one of the faces.
- the contacts are made either by silver lacquer or by diffusion of indium in the frit by means of ultrasound.
- a current generator (model 103A - Adret Electronique) sends in the sample, by the external points, a direct current (5.10 ⁇ mA ⁇ I. 109.99 mA).
- the voltage between the center points is measured using a Keithley digital multimeter with a resolution of 1 ⁇ V.
- the sample is a sintered bar a few millimeters in length.
- a SQUID magnetometer To accurately determine the critical temperature, a SQUID magnetometer is used. The sample is placed in a uniform magnetic field. A stepping motor moves the sample in captive coils. The flow inside the coils is precisely determined using a SQUID. The signal measured according to the displacement makes it possible to calculate the magnetic moment, according to the temperature and the applied field.
- the magnetic properties chi f (K) and of resistivity R / R - ⁇ - as a function of K are reported respectively in FIGS. 1 and 2. The remarkable qualities of this compound are noted.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR89/04770 | 1989-04-11 | ||
FR8904770A FR2645524B1 (fr) | 1989-04-11 | 1989-04-11 | Oxyde de cuivre a valence mixte partiellement substitue par le fluor, procede de synthese et composant en contenant |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990011969A1 true WO1990011969A1 (fr) | 1990-10-18 |
Family
ID=9380598
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1990/000257 WO1990011969A1 (fr) | 1989-04-11 | 1990-04-10 | Oxyde de cuivre a valence mixte partiellement substitue par le fluor, procede de synthese et composant en contenant |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0467981A1 (fr) |
JP (1) | JPH04506506A (fr) |
FR (1) | FR2645524B1 (fr) |
WO (1) | WO1990011969A1 (fr) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0283024A2 (fr) * | 1987-03-20 | 1988-09-21 | Sumitomo Electric Industries Limited | Méthode de fabrication d'un supra conducteur en céramique |
EP0308305A1 (fr) * | 1987-09-15 | 1989-03-22 | Thomson-Csf | Matériau supraconducteur |
-
1989
- 1989-04-11 FR FR8904770A patent/FR2645524B1/fr not_active Expired - Fee Related
-
1990
- 1990-04-10 JP JP50695090A patent/JPH04506506A/ja active Pending
- 1990-04-10 WO PCT/FR1990/000257 patent/WO1990011969A1/fr not_active Application Discontinuation
- 1990-04-10 EP EP19900907135 patent/EP0467981A1/fr not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0283024A2 (fr) * | 1987-03-20 | 1988-09-21 | Sumitomo Electric Industries Limited | Méthode de fabrication d'un supra conducteur en céramique |
EP0308305A1 (fr) * | 1987-09-15 | 1989-03-22 | Thomson-Csf | Matériau supraconducteur |
Non-Patent Citations (3)
Title |
---|
American Institute of Physics, Conference Proceedings, No. 165, 1988, American Institute of Physics, B.A. RICHERT et al.: "Atomic Substitution in YBa2Cu3O7: Modification of the Electronic Structure", pages 277-283 * |
Applied Physics Letters, Volume 52, No. 10, 7 Mars 1988, American Institute of Physics, N.P. BANSAL et al.: "Effect of Fluoride Doping on the Transition Temperature of YBa2Cu3O6.5+delta", pages 838-840 * |
Japanese Journal of Applied Physics, Volume 27, No. 12, Decembre 1988, A. OOTA et al.: "The Effect of Pb Addition on Superconductivity in Bi-Sr-Ca-Cu-O", pages L2289-L2292 * |
Also Published As
Publication number | Publication date |
---|---|
EP0467981A1 (fr) | 1992-01-29 |
FR2645524B1 (fr) | 1992-01-17 |
JPH04506506A (ja) | 1992-11-12 |
FR2645524A1 (fr) | 1990-10-12 |
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