EP1098849A1 - Method for preparing a composite bimevox electrolyte, use of said composite for separating oxygen from a gas mixture - Google Patents
Method for preparing a composite bimevox electrolyte, use of said composite for separating oxygen from a gas mixtureInfo
- Publication number
- EP1098849A1 EP1098849A1 EP99926562A EP99926562A EP1098849A1 EP 1098849 A1 EP1098849 A1 EP 1098849A1 EP 99926562 A EP99926562 A EP 99926562A EP 99926562 A EP99926562 A EP 99926562A EP 1098849 A1 EP1098849 A1 EP 1098849A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bimevox
- oxygen
- electrolyte
- compound
- compounds
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0233—Chemical processing only
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0046—Nitrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
Definitions
- the subject of the invention is a process for the preparation of a solid composite electrolyte consisting of at least one compound from the BIMEVOX family and the use of said composite for extracting oxygen from the air or from a gaseous mixture containing it.
- a solid composite electrolyte consisting of at least one compound from the BIMEVOX family and the use of said composite for extracting oxygen from the air or from a gaseous mixture containing it.
- the solid electrolytes used are generally stabilized zirconia, as described for example in the American patent published under the number US 4,879,016, or oxides derived from Bi 4 V 2 On, as described in the international patent application published under the number WO 91/01274 and known under the generic name of BIMEVOX.
- the latter in which a variable fraction of vanadium is replaced by a metal chosen, in particular from alkaline earth metals, transition metals, rare earths or elements from groups III to V of the periodic table of Mendeursev chemical elements , are conductors by O 2 ′ ions and their anionic conductivity at 500 ° C is of the same order of magnitude as that, at 800 ° C, of stabilized zirconia.
- the partial substitution of the constituent elements of Bi 4 V 2 On stabilizes the structural type of the gamma phase and maintains, in the network of O 2 " ions, a rate of vacancies sufficient to allow anionic conductivity.
- BIMEVOX are used in electrochemical cells, such as those described in international patent applications published under the WO 94/06544 and WO 94/06545, and in cells operating by electrochemical semi-permeability, such as those described in the French patent application published under the number FR 2698016.
- synthesis parameters is understood to mean essentially the size of the starting particles as well as, during sintering, the temperatures, the rates of rise and fall in temperature and the hold times at a given temperature.
- metal chosen as dopant and its content between 0% and 50%, it is necessary to very precisely define the sintering conditions. These will directly affect the grain size of the sintered material, which itself governs the stability and quality of the electrical and mechanical properties of BIMEVOX. It has thus been observed that a rise of a few tens of degrees in the sintering temperatures, for example 800 ° C.
- BICOVOX .10 Bi 2 C ⁇ o , ⁇ Vo, 9 ⁇ 3 , 55 , hereinafter referred to as BICOVOX .10, has the consequence of modifying the electrical properties of the material, and that an excessive rise in temperature has the effect of promoting an abnormal crystal growth of the BIMEVOX grains, then leading to a microstructure of the non-homogeneous material in which the size grain size exceeds the critical value by 5 ⁇ m. Under these conditions, on the one hand the mechanical properties are degraded and the electrical resistivity increases and on the other hand the electrical properties are no longer, neither stable over time, nor during thermal cycles.
- the Applicant has therefore sought to develop a process for the preparation of a solid electrolyte comprising at least one compound from the BIME family.
- VOX which allows the control of the grain size of the material after sintering and which thus leads to reinforced mechanical properties compared to said BIMEVOX material alone, without however deteriorating the electronic and ionic properties of said material.
- the subject of the invention is a process for the preparation of a solid composite electrolyte consisting of at least one compound from the BIMEVOX family, characterized in that it comprises: a) at least one step of preparation of a mixture of one or more compounds from the BIMEVOX family with one or more chemically inert compounds, b) at least one step of compacting the mixture obtained at the end of step a), and c) at least one step of sintering during which the temperature reaches, during a non-zero time interval, a value greater than the optimal sintering temperature of said compound of the BIMEVOX family.
- BIMEVOX By at least one compound of the BIMEVOX family, it is meant that it can be a single or a mixture of these said compounds.
- BIMEVOX By the generic term of BIMEVOX, it is designated the oxides derived from Bi 4 V 2 On, in which a variable fraction of vanadium is replaced by a metal, and in particular the compounds of formula (I):
- - M ' represents one or more vanadium substitution elements chosen from those having an oxidation number less than, equal to or greater than 5, the limit values of x, y and therefore z being functions of the nature of the Substitutes M and M '.
- M ′ is as defined above, being there non-zero and is, more particularly greater than or equal to approximately 0.05 and less than or equal to 0.5.
- M - M ' is advantageously selected from alkali metals, alkaline earth metals, transition metals, elements from groups III to V of the periodic classification of the chemical elements of Mendeursev, or from rare earths.
- M 'represents a transition metal it is more particularly chosen from zinc, copper, manganese, nickel, cobalt, iron or cadmium atoms.
- M 'represents an alkaline earth metal it is more particularly chosen from calcium, strontium or barium atoms.
- M 'can also represent an atom of indium, aluminum or antimony.
- M 'can also represent a tin, titanium or ruthenium atom.
- M 'can also represent a nobium, tantalum or phosphorus atom.
- M 'can also represent an alkali metal atom such as sodium or, as a metal having an oxidation state equal to 2, represent a Pb atom.
- formula (III) (Bi 2-x M x O 2 ) (VO z ) (III) in which x is non-zero and M is as defined above and is more particularly chosen from rare earths such as lanthanum.
- chemically inert compounds denotes any compound which does not interact chemically with the BIMEVOX (s).
- the materials chosen are more particularly carbides, such as tungsten carbide or silicon carbide, nitrides, such as silicon nitride or oxides, such as titanium oxide, alumina or BiVO 4 or else zirconia, cerium oxide, hafnium oxide, or thorine, said zirconia, cerium oxide, hafnium oxide, or thorine being stabilized by one or more compounds chosen from oxides of yttrium, barium, magnesium, calcium, strontium, scandium or lanthanum.
- Step a) of the process described above consists either of mechanically mixing the BIMEVOX compound (s) with one or more chemically inert compounds, or of depositing, by successive impregnation, one or more precursor salts containing the chemically inert agent (s), then calcining under air.
- the dispersion after caicination of oxide particles, for example of zirconium or of titanium is carried out relatively homogeneously on the surface of the compound or mixture of BIMEVOX compounds.
- step a) the chemically inert compound (s) are added during the synthesis of the BIMEVOX compound (s), either in the form of oxide if this synthesis is carried out by solid-solid route, or in the form of salt if this synthesis is carried out by co-precipitation.
- the mixture resulting from stage a) of the process as defined above comprises up to 30% by volume of chemically inert compound and stage a) is implemented with starting compounds having an average grain size of about 1 ⁇ m (10 6 meters).
- step b) of the process as defined above is carried out under a compaction pressure of between 1500 bars and 4000 bars; the mixture thus compacted has a raw compactness ratio of between approximately 30% and 70%;
- optimum sintering temperature, in step c) of the process as defined above is meant the temperature which can be reached for a given material, in the present case a compound or a mixture of BIMEVOX compounds, controlling crystal growth until the grain size after sintering is less than 5 ⁇ m and preferably less than 3 ⁇ m.
- Step c) of the process, as defined above is in particular carried out at a temperature which can generally exceed 700 ° C., often 800 ° C., and, more particularly, greater than 820 ° C.
- its subject is an electrochemical cell in which the solid electrolyte, consisting of one or more BIMEVOX derivatives mixed with one or more chemically compounds inert thereafter called, immiscible phase or inert phase, is obtained by the process as defined above and is either in contact with two so-called volume electrodes, respectively an anode and a cathode porous to gases, or constitutes in itself , a homogeneous structure made up of one or more composite solid electrolyte derivatives (BIMEVOX + immiscible phase) with dynamic electrodes created "in situ", reversible and self-adapting.
- the solid electrolyte consisting of one or more BIMEVOX derivatives mixed with one or more chemically compounds inert thereafter called, immiscible phase or inert phase
- homogeneous structure it is signified in the preceding definition that, unlike the devices of the state of the art, such as the cell with volume electrode mentioned above, which consist of a solid electrolyte and two electrodes connected to collectors current, said electrodes being able to be distinguished physically from said electrolyte, the homogeneous structure, is a core of one or more BIMEVOX behaving both as electrolyte and as electrodes.
- a current collector the function of which is only to allow the circulation of electric current by bringing the electrons to the cathode and by collecting them at the anode
- an electrode the function of which is to catalyze electrochemical dissociation.
- reversible it is meant in the preceding definition, that the device can operate in one direction or another by simply reversing the polarity of the current generator.
- self-adapting it means that the device adapts by itself. to the two types of functions mentioned above, namely: the dynamic function and the reversibility function.
- the thickness of the “electrode zones” and of the “electrolyte zone” of said structure varies in particular as a function of the temperature and the intensity of the electric current which are applied to it, and that this dynamic character thus makes it possible to regulate the flow oxygen extraction.
- its subject is a ceramic membrane, operating according to the principle of electrochemical semi-permeability, in which this ceramic membrane conductive by O 2 " ions and consisting of one or more mixed BIMEVOX derivatives to one or more chemically inert compounds called subsequently, immiscible phase, is obtained by the process as defined above
- the cell When the cell, as defined above, based on solid electrolytes, operates by electrochemistry, it is inserted in an electric current supply circuit allowing the creation of a potential difference between its opposite faces, via current collectors.
- These current collectors which ensure both the supply of electrons to the cathode and their evacuation to the anode, must naturally be made of a metal, or of a metal alloy, compatible with BIMEVOX, as for example, the gold, silver, platinum, palladium, copper or stainless steel.
- the shape of the current collectors is determined so as to optimize the supply of electrons to the cathode and their evacuation from the anode.
- each of the current collectors of the electrochemical cell used is located inside the electrode layer or, where appropriate, the homogeneous structure; when the collector is a grid, it preferably has several tens of knots / cm 2 .
- the electrochemical cell used is in particular a planar structure with parallel faces or a hollow cylindrical structure with circular or oval section, comprising two coaxial cylindrical faces.
- An elementary electrochemical cell with volume electrodes can be represented by the diagram (A): CC / BIMEVOX'-CE '/ composite electrolyte (BIMEVOX + inert phase) / BIMEVOX'-CE "/ CC (A) in which CC and CC represent the anode and cathode current collectors, BIMEVOX'-CE 'and BIMEVOX "-CE” represent the two characteristic constituents of volume electrodes in variable proportions, that is to say say on the one hand a BIMEVOX and / or on the other hand an electronic conductor (CE), in particular a metal or a metal oxide.
- CE electronic conductor
- This metal or the metal of the metal oxide may be different or identical with respect to the metals of BIMEVOX.
- the metals ME 'and ME "from BIMEVOX' and BIMEVOX" can be identical or different from that or those contained in the composite electrolyte BIMEVOX-inert phase.
- the weight proportions vary, for example from 0 to 100% of one of the constituents of the volume electrode and from 100 to 0% of the other (apart from other chemical compounds possibly also present in the volume electrodes).
- An elementary electrochemical cell with dynamic electrodes created "in situ”, reversible and self-adapting can be represented by the diagram (B):
- the metals ME 'and ME "of BIMEVOX' and BIMEVOX" can be identical or different from that or those contained in the composite electrolyte BIMEVOX-inert phase
- the invention also relates to a composition consisting of a mixture containing at least 70% by volume of one or more compounds of the BIMEVOX family with up to 30% by volume of at least one or more chemically inert compounds chosen from carbides, such as tungsten carbide or silicon carbide, nitrides , such as silicon nitride or oxide, such as titania, alumina, BiVO 4, zirconia, ceria, hafnia, or has thoria, said zirconia , cerium oxide, hafnium oxide, or thorin being stabilized by one or more compounds chosen from oxides of yttrium, barium, magnesium, calcium, strontium, scandium or lanthanum; particularly a composition as defined above, in which the compound of the BIMEVOX family is a compound of
- the devices using solid electrolyte, prepared by the method as defined above, are used to extract oxygen from a gas mixture or to analyze the oxygen present in a given gas atmosphere.
- the method is implemented for removing oxygen from the gaseous atmosphere which is above food products, in particular fresh food products or above baths of frying oils for improve their conservation.
- the experiment described below illustrates the invention without however limiting it.
- BIMEVOX-based cells In order to highlight the importance of the second phase on the crystal growth of the grains and therefore on the mechanical and electrical properties of the materials, four BIMEVOX-based cells, with a 10% ME content, were carried out .
- the BIMEVOX chosen is: Bi 2 Co 0 og O 5 35 (noted BICO-VOX.10).
- the average particle size is less than or equal to a micron.
- the final compactness obtained varies between 95 and 97%.
- the pellets after shaping and sintering are covered by gold electrodes deposited in the form of a lacquer. Once applied, it is dried at around 100 ° C.
- the organic binder is removed by baking at 700 ° C / 0.5 h.
- the characterizations of the microstructure of sintered materials were carried out by scanning electron microscopy (SEM).
- SEM scanning electron microscopy
- the electrical properties of the materials were determined by impedance spectroscopy first at 150 ° C and then the conductivity measurements were carried out between 150 and 600 ° C.
- Analysis of SEM photos of the first three samples reveals: for sample (a), a homogeneous microstructure, the maximum grain size not exceeding 10 ⁇ m; for sample (b), an inhomogeneous microstructure with the presence of grains of a few tens of microns having cracks.
- Figure 1 includes the impedance diagrams of samples (a), (b) and (c) at 150 ° C:
- HF high frequencies
- LF low frequencies
- Figure 2 compares the electrical conductivities of samples (a), (b), (c) and (d), as a function of temperature, in Arrhenius coordinates: Sample (b) shows the generally observed curve for these materials, with a "jump" in conductivity towards 450 ° C.
- Sample (a) shows an Arrhenius curve without conductivity jump to 450 ° C with only a change in activation energy (0.37 eV at high temperature and 0.64 eV at temperature below 400 ° C ).
- the curve is perfectly reversible during thermal cycles.
- the conductivity at ordinary temperature is seven times higher than in the case of sample (b).
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9808522 | 1998-07-03 | ||
FR9808522A FR2780717B1 (en) | 1998-07-03 | 1998-07-03 | PROCESS FOR THE PREPARATION OF A BIMEVOX-BASED COMPOSITE ELECTROLYTE, USE OF SAID COMPOSITE IN THE SEPARATION OF OXYGEN FROM A GASEOUS MIXTURE |
PCT/FR1999/001559 WO2000001619A1 (en) | 1998-07-03 | 1999-06-29 | Method for preparing a composite bimevox electrolyte, use of said composite for separating oxygen from a gas mixture |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1098849A1 true EP1098849A1 (en) | 2001-05-16 |
Family
ID=9528221
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99926562A Withdrawn EP1098849A1 (en) | 1998-07-03 | 1999-06-29 | Method for preparing a composite bimevox electrolyte, use of said composite for separating oxygen from a gas mixture |
Country Status (8)
Country | Link |
---|---|
US (1) | US6207038B1 (en) |
EP (1) | EP1098849A1 (en) |
JP (1) | JP2002519838A (en) |
CN (1) | CN1307542A (en) |
FR (1) | FR2780717B1 (en) |
IL (1) | IL139948A0 (en) |
WO (1) | WO2000001619A1 (en) |
ZA (1) | ZA200007797B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100315894B1 (en) * | 1999-12-30 | 2001-12-24 | 박호군 | Solid State Facilitated Transport Membranes for Alkene Separation Using Polymer Electrolytes |
FR2817860B1 (en) | 2000-12-07 | 2003-09-12 | Air Liquide | PROCESS FOR THE PREPARATION OF A LOW THICKNESS CERAMIC MATERIAL WITH CONTROLLED SURFACE POROSITY GRADIENT, CERAMIC MATERIAL OBTAINED, ELECTROCHEMICAL CELL AND CERAMIC MEMBRANE COMPRISING THE SAME |
FR2826956B1 (en) * | 2001-07-04 | 2004-05-28 | Air Liquide | PROCESS FOR PREPARING A LOW THICKNESS CERAMIC COMPOSITION WITH TWO MATERIALS, COMPOSITION OBTAINED, ELECTROCHEMICAL CELL AND MEMBRANE COMPRISING IT |
KR100449068B1 (en) * | 2002-10-09 | 2004-09-18 | 한국전자통신연구원 | Method for manufacturing cathode electrode for lithium secondary battery by using vanadium oxide |
JP5194411B2 (en) * | 2005-09-30 | 2013-05-08 | 大日本印刷株式会社 | Solid oxide fuel cell |
JP5194410B2 (en) * | 2005-09-30 | 2013-05-08 | 大日本印刷株式会社 | Solid oxide fuel cell |
US8617456B1 (en) | 2010-03-22 | 2013-12-31 | The United States Of America As Represented By The Secretary Of The Air Force | Bulk low-cost interface-defined laminated materials and their method of fabrication |
US9162931B1 (en) * | 2007-05-09 | 2015-10-20 | The United States Of America As Represented By The Secretary Of The Air Force | Tailored interfaces between two dissimilar nano-materials and method of manufacture |
US9120245B1 (en) | 2007-05-09 | 2015-09-01 | The United States Of America As Represented By The Secretary Of The Air Force | Methods for fabrication of parts from bulk low-cost interface-defined nanolaminated materials |
US20110198530A1 (en) * | 2010-02-18 | 2011-08-18 | New Mexico Technical Foundation | Method of Producing a Bismuth Vanadium Oxide Derivative of Bi4V2O11 Using Molten Salt Synthesis, and Product Produced |
JP5858030B2 (en) * | 2013-12-13 | 2016-02-10 | トヨタ自動車株式会社 | Control device for exhaust gas sensor containing self-healing ceramic material |
TWI766637B (en) * | 2021-04-06 | 2022-06-01 | 國立臺北科技大學 | Planar solid electrolyte oxygen separator |
CN113426261A (en) * | 2021-08-26 | 2021-09-24 | 湖南大学 | Method for electrochemically removing oxygen in mixed gas |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4675260A (en) * | 1984-11-12 | 1987-06-23 | Nippon Telegraph And Telephone Corporation | Lithium battery including vanadium pentoxide base amorphous cathode active material |
FR2649970B1 (en) * | 1989-07-18 | 1992-08-28 | Univ Lille Flandres Artois | |
US5273628A (en) * | 1992-05-11 | 1993-12-28 | Gas Research Institute | Mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
FR2720080B1 (en) | 1994-05-19 | 1997-03-21 | Air Liquide | Composite structure comprising a solid electrolyte and at least one volume electrode. |
-
1998
- 1998-07-03 FR FR9808522A patent/FR2780717B1/en not_active Expired - Fee Related
-
1999
- 1999-06-29 IL IL13994899A patent/IL139948A0/en unknown
- 1999-06-29 WO PCT/FR1999/001559 patent/WO2000001619A1/en not_active Application Discontinuation
- 1999-06-29 CN CN99808097A patent/CN1307542A/en active Pending
- 1999-06-29 EP EP99926562A patent/EP1098849A1/en not_active Withdrawn
- 1999-06-29 JP JP2000558031A patent/JP2002519838A/en active Pending
- 1999-07-02 US US09/346,308 patent/US6207038B1/en not_active Expired - Fee Related
-
2000
- 2000-12-21 ZA ZA200007797A patent/ZA200007797B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0001619A1 * |
Also Published As
Publication number | Publication date |
---|---|
IL139948A0 (en) | 2002-02-10 |
FR2780717B1 (en) | 2000-08-18 |
FR2780717A1 (en) | 2000-01-07 |
ZA200007797B (en) | 2002-02-22 |
WO2000001619A1 (en) | 2000-01-13 |
US6207038B1 (en) | 2001-03-27 |
CN1307542A (en) | 2001-08-08 |
JP2002519838A (en) | 2002-07-02 |
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Inventor name: BOIVIN, JEAN-CLAUDE Inventor name: MAIRESSE, GAETAN Inventor name: DEL GALLO, PASCAL Inventor name: LAGRANGE, GILLES Inventor name: KLEITZ, MICHEL Inventor name: FOULETIER, JACQUES Inventor name: STEIL, MARLU, CESAR |
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