EP0764955B1 - Matériau magnétique composite à perméabilité et pertes réduites - Google Patents
Matériau magnétique composite à perméabilité et pertes réduites Download PDFInfo
- Publication number
- EP0764955B1 EP0764955B1 EP96401962A EP96401962A EP0764955B1 EP 0764955 B1 EP0764955 B1 EP 0764955B1 EP 96401962 A EP96401962 A EP 96401962A EP 96401962 A EP96401962 A EP 96401962A EP 0764955 B1 EP0764955 B1 EP 0764955B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wafers
- magnetic
- magnetic material
- material according
- binder
- 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
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
- H01F1/37—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent
Definitions
- the present invention relates to a magnetic material composite with reduced permeability and losses at frequencies below about 100 MHz.
- the material is intended to produce in particular cores inductors or transformers.
- Magnetic materials with reduced permeability currently available on the market have strong induction (greater than around 10 mT) very high losses which mean that today magnetic components are the most bulky components of converters.
- induction greater than around 10 mT
- low permeability and low losses at high frequency are contradictory characteristics.
- An inductance of a few micro-Henrys will include a few turns or a core with low permeability.
- a small number of turns brought to a potential difference high generates high magnetic induction in the nucleus. Like the losses in the nucleus are at least proportional to the square of the induction, they grow very quickly when the number of turns decreases. To get reduced losses, it takes a large number of turns which imposes a core with low permeability.
- inductors with a composite magnetic core with distributed air gap. These materials are made of ferromagnetic alloys powder dispersed in a dielectric binder. Radiation losses are reduced compared to the nuclei with localized air gap.
- powders iron and iron carbonyl powders whose permeability ranges from approximately 5 to 250 and the powders based on iron-nickel alloys whose permeability ranges from about 14 to 550.
- the losses in these materials are 15 to 20 times greater than those of massive power ferrites under the same conditions of frequency, induction and temperature.
- Document DE-A-42 14 376 also discloses a material magnetic for power core composed of a homogeneous mixture of ferrite and synthetic material.
- the present invention provides a composite magnetic material which, when subjected to a magnetic field, presents both reduced losses and permeability for frequencies below about 100 MHz.
- This composite magnetic material has losses approximately three to five times weaker than that of magnetic materials composites available on the market and permeability around 10 to 100 times weaker than spinel type ferrites, at lower frequencies at around 100 MHz.
- the composite magnetic material according to the invention comprises magnetic particles dispersed in a binder dielectric, these particles being magnetic ceramic plates polycrystalline oriented so that their main faces are substantially parallel to the magnetic field.
- the binder is advantageously a resin, fluid in a first then hardening time, such as an epoxy, phenolic resin, polyimide or acrylic based.
- the plates are oriented in strata, separated by binder.
- Each layer can have several plates separated by binder forming an air gap or a single plate.
- Platelets belonging to neighboring strata are preferably either staggered or in columns.
- platelets including square, the torus or the torus portion. The choice depends on the final form of the magnetic core made with the material thus obtained.
- the pouring slip can be obtained by mixing the ceramic powder, at least one binder, at least one solvent and optionally a deflocculent.
- the orientation of the plates can be manual. We can stack the pads on top of each other then compress them to break them.
- Orientation can also be done by vibration or by a field magnetic.
- the invention also relates to a core produced with such a material. magnetic composite as well as an inductor or transformer having such a core.
- the composite magnetic material according to the invention comprises polycrystalline magnetic ceramic plates dispersed in a binder.
- the main faces of the plates are oriented substantially parallel to the magnetic field.
- the process for developing the composite magnetic material makes it possible to control the shape of the platelets and their positioning in the composite so as to control its permeability and his losses.
- magnetic ceramic plates can be to do it by a classic technique of making ceramics. This technique is used in particular for the manufacture of alumina substrates, of multilayer ceramic boxes or capacitors.
- the raw materials necessary to obtain magnetic ceramic can be mixed and ground in a jar containing steel balls in aqueous phase. This operation has for purpose of mixing and reducing the grain size of the different constituents so as to make them more responsive.
- the mixture is then dried and Thames.
- the powder thus obtained can be pre-sintered in an oven so to obtain the desired crystalline phase. This operation is often called chamotte.
- a second grinding can follow the chamotte to reduce the grains which have grown during the chamotte operation. This second grinding can be done under the same conditions as the first grinding.
- a casting slip can be obtained by mixing the powder regrind with organic binders, solvents and possibly a deflocculent. This mixture can be done in a jar with beads steel using a mechanical stirrer. The slip after a rest for allow the air bubbles formed during agitation to rise again strip casting on a bench on which a strip of mylar slides, by example, driven at constant speed. The bench is covered with a tunnel to avoid dust deposits and to slow down the evaporation of solvents. A knife held parallel to the mylar strip by screws micrometric forms an opening through which the slip passes. This opening determines the thickness of the cast strip. After evaporation and drying, the casting strip can be peeled off and cut using a cookie cutters. This ease of obtaining complex parts, toroids by example, is very interesting. Machining of massive ferrites is slow and expensive because it requires diamond tools.
- These plates can be cut into squares, for example, 2mm x 2mm or 4mm x 4mm or 7mm x 7mm. Thin toroids or portions of thin toroids (eighth, quarter, half) can also be cut.
- the inserts are sintered to ensure cohesion of the powder grains.
- Sintering is done, especially for Mn-Zn ferrites under partial pressure of oxygen controlled in order to fix the level of divalent iron in platelets.
- the plates are oriented and incorporated into a fluid binder, an Araldite type resin (registered trademark) for example, which ensures the mechanical cohesion of the composite material after hardening.
- a fluid binder an Araldite type resin (registered trademark) for example, which ensures the mechanical cohesion of the composite material after hardening.
- the grinding is done with steel balls in water deionized.
- the mixture is dried in an oven and sieved through a 400 ⁇ m opening sieve.
- Chamotte is done at 1100 ° C with a bearing time in air 3 hours.
- the new grinding is carried out under the same conditions as the first. It is followed by a new drying and sieving.
- the wafers are cut and then sintered.
- the thickness of the plates varies between 100 ⁇ m and 130 ⁇ m.
- the resin is poured before or after orientation, it depends on the orientation method used.
- Orientation can be manual. This method applies for larger wafers, in particular the toroids, the portions of torus, the squares of 7 mm x 7 mm.
- Figures 2a, 2b show an O-ring of material magnetic according to the invention. It is made from plates 10 in torus shape. We stack several on top of each other in strata. The stack is placed in a mold and the binder 20, type resin epoxy, phenolic, polyimide or acrylic based, for example, is paid.
- the binder 20 fills the spaces between the different strata.
- FIG. 2c is a top view of an O-ring obtained with this method and Figure 2d is a section.
- the different strata bear the reference 2.
- the binder fills the spaces on the one hand between the broken pieces 1 of the same torus and on the other hand between the different strata 2 of tori.
- the pieces 1 are then separated by air gaps 3 in resin.
- Two layers 2 are also separated by a layer 4 of resin.
- the binder is fluid at first, and then hardens.
- Figures 3a, 3b show a variant of an O-ring according to the invention. It is obtained from square plates 5. They are arranged layer by layer next to each other flat in a crown leaving a space 6 or between them. Two pads neighboring strata are staggered.
- FIGs 4a, 4b again show a variant of a core toroid according to the invention.
- the plates 7 are eighths of a torus. They are arranged layer by layer next to each other flat, in crown by leaving a space or gap between them. Platelets 7 of two neighboring strata coincide, they form columns. They could also have been staggered as in the figures 3a, 3b.
- the plates are placed in a closed transparent container by a holey plug.
- the container is placed in the air gap of a electro magnet.
- a magnetic field is created in the air gap. Doing turn the container on itself in the magnetic field, the plates are regularly arranged in several strata and visual control is easy.
- the position of the pads can be fixed by pushing in the plug to keep the strata in contact.
- the binder can be added before or after orientation.
- the losses of an iron-carbonyl composite toroid at 30 mT amount to at least 2.5 W / cm 3 at 80 ° C.
- a core according to the invention has losses equal to 0.5 W / cm 3 as illustrated in FIG. 5b, hence a gain of a factor of 5.
- Figures 6a, 6b schematically show a inductor and a transformer according to the invention.
- the inductance of FIG. 6a comprises an O-ring core made of composite magnetic material according to the invention.
- This core is formed of plates 70 in quarter torus dispersed in the dielectric binder. There are several layers separated by the binder and each layer has four plates 70 separated by an air gap 71.
- Around the core is a coil 72.
- the magnetic field H establishing itself in the nucleus is materialized by the circle in dotted lines.
- the transformer of Figure 6b has an E-shaped core with rectangular legs including a central 760 and two ends 761, made of composite magnetic material according to the invention.
- This core comprises square plates 73 embedded in the binder.
- Two windings 74, 75 around the extreme legs 761 contribute to forming the primary and the secondary of the transformer.
- the two coils could have been around the central leg 760.
- the magnetic field H establishing itself in the nucleus is materialized by the dotted lines.
- the main faces of the plates are substantially parallel to the magnetic field H .
- the cores according to the invention have been represented in torus or in E but the invention is not limited to these types. It applies to others types in U, in pots etc ...
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Soft Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
- Coils Or Transformers For Communication (AREA)
Description
- fer-carbonyle : pertes supérieures à 1,5 W/cm3
- fer-nickel : pertes supérieures à 2 W/cm3
- la réalisation d'une poudre magnétique céramique ;
- la réalisation, à partir de la poudre magnétique céramique d'une barbotine de coulage ;
- la découpe des plaquettes dans une pellicule de la barbotine séchée ;
- le frittage des plaquettes ;
- l'élaboration du matériau magnétique composite à partir des plaquettes frittées, dispersées dans le liant et dont les faces principales sont orientées par rapport au champ magnétique.
- la figure 1 illustre l'évolution du pourcentage en oxygène de l'atmosphère pendant la phase de refroidissement du frittage des plaquettes ;
- les figures 2a, 2b, 2c, 2d deux exemples d'un noyau selon l'invention en vue de dessus et en coupe réalisé à partir de plaquettes en forme de tore ;
- les figures 3a, 3b un autre exemple d'un noyau selon l'invention en vue de dessus et de face ;
- les figures 4a, 4b, encore un exemple d'un noyau selon l'invention en vue de dessus et de face ;
- les figures 5a, 5b l'évolution des pertes totales d'un noyau selon l'invention en fonction de la température et de l'induction respectivement à 300 kHz et à 1 MHz ; (mesures réalisées en laboratoire)
- les figures 6a, 6b respectivement une inductance et un transformateur selon l'invention.
- la poudre précédemment obtenue ;
- deux solvants : éthanol et trichloréthylène ;
- des liants organiques : polyéthylène-glycol, diéthyl-hexylephtalate et polyvinyl-butyral ;
- un défloculent éventuel.
- une montée en température à 600°C en 12 heures sous air ;
- une montée en température de 600°C à 1220°C en 6 heures ;
- un palier à 1220°C pendant 1 heure 30 ;
- une descente en température de 1220°C à 1200°C avec ajustement du pourcentage d'oxygène à 2,6 % dans l'atmosphère en 15 minutes ;
- un palier à 1200°C pendant 15 minutes avec le même pourcentage d'oxygène ;
- un refroidissement de 100°C par heure avec baisse du pourcentage d'oxygène suivant la loi Log(PO2) = f(1/T) représentée sur la figure 1. PO2 est le pourcentage d'oxygène et T la température.
- plaquettes 4 mm x 4 mm en quinconce
- taux de charge volumique compris entre 21 et 29 %
- perméabilité 17
- plaquettes 4 mm x 4 mm en colonnes
- taux de charge volumique compris entre 18 et 25 %
- perméabilité 17
- T = 30°C
- plaquettes 7 mm x 7 mm en quinconce
- taux de charge compris entre 28 et 40 %
- perméabilité 60
- T = 60°C
- plaquettes 2 mm x 2 mm orientées sous champ magnétique
- taux de charge volumique compris entre 30 et 42 %
- perméabilité 40
- T = 60°C
- plaquettes en 1/8 de tore, 8 strates
- taux de charge volumique compris entre 39 et 55 %
- perméabilité 60
- T = 60°C
- plaquettes en tore 12 strates
- taux de charge volumique compris entre 59 et 83 %
- perméabilité 60
- T = 60°C
- Plaquettes en tore empilées, cassées, imprégnées
- taux de charge volumique compris entre 40 et 56 %
- perméabilité 60
- T = 60°C
Claims (18)
- Matériau magnétique composite présentant des pertes et une perméabilité réduites lorsqu'il est soumis à un champ magnétique à des fréquences inférieures à environ 100 MHz, caractérisé en ce qu'il comporte plusieurs strates (2) formées d'une ou plusieurs plaquettes (10) réalisées à partir d'une poudre de céramique magnétique polycristalline, les plaquettes étant dispersées dans un liant (20), orientées de manière à ce que leurs faces principales soient sensiblement parallèles au champ magnétique et sans contact les unes avec les autres.
- Matériau magnétique selon la revendication 1, caractérisé en ce que la céramique magnétique polycristalline est un ferrite de type spinelle répondant à la formule MxZnyFe2+εO4 avec x+y+ε = 1, où M est un ion manganèse ou nickel.
- Matériau magnétique selon l'une des revendications 1 ou 2, caractérisé en ce que le liant est une résine époxyde, phénolique, polyimide ou à base acrylique.
- Matériau magnétique selon l'une des revendications 1 à 3, caractérisé en ce que, lorsqu'une strate comporte plusieurs plaquettes (5), elles sont séparées par du liant constituant un entrefer (6).
- Matériau magnétique selon l'une des revendications 1 à 4, caractérisé en ce que les plaquettes (5) appartenant à des strates voisines sont en quinconce.
- Matériau magnétique selon l'une des revendications 1à 5, caractérisé en ce que les plaquettes (7) appartenant à des strates voisines sont en colonne.
- Matériau magnétique selon l'une des revendications 1 à 6, caractérisé en ce que les plaquettes sont des carrés, des tores ou des portions de tore.
- Matériau magnétique selon l'une des revendications 1 à 7, caractérisé en ce que les plaquettes (10) sont cassées en morceaux (1).
- Procédé d'élaboration du matériau magnétique composite selon l'une des revendications 1 à 8, caractérisé en ce qu'il comprend les étapes suivantes :la réalisation d'une poudre magnétique céramique ;la réalisation, à partir de la poudre magnétique céramique d'une barbotine de coulage ;la découpe des plaquettes dans une pellicule de la barbotine séchée ;le frittage des plaquettes ;l'élaboration du matériau magnétique composite à partir des plaquettes frittées dispersées dans le liant et dont les faces principales sont orientées par rapport au champ magnétique.
- Procédé selon la revendication 9, caractérisé en ce que la barbotine de coulage est obtenue en mélangeant la poudre céramique, au moins un liant, au moins un solvant et éventuellement un défloculent.
- Procédé selon l'une des revendications 9 ou 10, caractérisé en ce que l'orientation des plaquettes est manuelle.
- Procédé selon l'une des revendications 9 à 11, caractérisé en ce que les plaquettes sont empilées les unes sur les autres puis comprimées pour les casser.
- Procédé selon l'une des revendications 9 à 12, caractérisé en ce que les plaquettes sont déposées les unes à côté des autres, strates par strates.
- Procédé selon l'une des revendications 9 ou 10, caractérisé en ce que les plaquettes sont orientées par vibration.
- Procédé selon l'une des revendications9 ou 10, caractérisé en ce que les plaquettes sont orientées par un champ magnétique.
- Noyau magnétique caractérisé en ce qu'il est réalisé dans un matériau magnétique selon l'une des revendications 1 à 8.
- Inductance caractérisée en ce qu'elle comporte un noyau selon la revendication 16.
- Transformateur caractérisé en ce qu'il comporte un noyau selon la revendication 16.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9510952A FR2738949B1 (fr) | 1995-09-19 | 1995-09-19 | Materiau magnetique composite a permeabilite et pertes reduites |
FR9510952 | 1995-09-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0764955A1 EP0764955A1 (fr) | 1997-03-26 |
EP0764955B1 true EP0764955B1 (fr) | 2000-11-29 |
Family
ID=9482685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96401962A Expired - Lifetime EP0764955B1 (fr) | 1995-09-19 | 1996-09-13 | Matériau magnétique composite à perméabilité et pertes réduites |
Country Status (7)
Country | Link |
---|---|
US (1) | US6120916A (fr) |
EP (1) | EP0764955B1 (fr) |
JP (1) | JPH09129434A (fr) |
AT (1) | ATE197855T1 (fr) |
CA (1) | CA2185930A1 (fr) |
DE (1) | DE69611072T2 (fr) |
FR (1) | FR2738949B1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59903559D1 (de) | 1998-07-10 | 2003-01-09 | Epcos Ag | Magnetisierbares erzeugnis, seine verwendung sowie ein verfahren zu seiner herstellung |
FR2795855B1 (fr) * | 1999-06-29 | 2001-10-05 | Thomson Csf | Ferrites a faibles pertes |
DE10000523A1 (de) * | 2000-01-08 | 2001-07-26 | Inst Maschinen Antriebe Und El | Ferrit-Compound-Material mit hoher elektromagnetischer Absorption im Frequenzbereich von 20 MHz bis 40 GHz |
US20030112110A1 (en) * | 2001-09-19 | 2003-06-19 | Mark Pavier | Embedded inductor for semiconductor device circuit |
JP2003124538A (ja) * | 2001-10-16 | 2003-04-25 | Sony Corp | 情報記憶装置およびその情報記憶装置を実装した電子機器 |
US6610415B2 (en) * | 2001-10-26 | 2003-08-26 | Koslow Technologies Corporation | Magnetic or magnetizable composite product and a method for making and using same |
US7353587B2 (en) * | 2004-11-01 | 2008-04-08 | Vlt, Inc. | Forming distributed gap magnetic cores |
FR2879593B1 (fr) * | 2004-12-20 | 2007-03-02 | Thales Sa | Materiau ferrite a faibles pertes en hyperfrequence et procede de fabrication |
US20100059258A1 (en) * | 2008-08-19 | 2010-03-11 | Xu Yang | Ferrite Mosaic and Magnetic Core Structure for Passive Substrate for Switched-Mode Power Supply Module |
JP2011222727A (ja) * | 2010-04-08 | 2011-11-04 | Iq Four:Kk | トロイダルコアとこれを用いた高周波トロイダルコイル及び高周波トロイダルトランス |
JP5374537B2 (ja) * | 2010-05-28 | 2013-12-25 | 住友電気工業株式会社 | 軟磁性粉末、造粒粉、圧粉磁心、電磁部品及び圧粉磁心の製造方法 |
DE102013225875A1 (de) * | 2013-12-13 | 2015-07-02 | Siemens Aktiengesellschaft | Führung eines magnetischen Flusses |
DE102014202531A1 (de) * | 2014-02-12 | 2015-08-13 | Siemens Aktiengesellschaft | Hochspannungstransformatorvorrichtung mit einstellbarer Streuung, Wechselrichterschaltung mit einer Hochspannungstransformatorvorrichtung und Verwendung einer Hochspannungstransformatorvorrichtung |
WO2020170783A1 (fr) * | 2019-02-22 | 2020-08-27 | 三菱電機株式会社 | Dispositif de bobine et dispositif de conversion de puissance |
CN111875368B (zh) * | 2020-07-17 | 2022-08-09 | 中国电子科技集团公司第九研究所 | 一种低磁导率铁氧体磁性介质材料、其制备方法及应用 |
JP7428098B2 (ja) * | 2020-07-31 | 2024-02-06 | Tdk株式会社 | インダクタ部品及びこれを用いたdcdcコンバータ |
CN112538253A (zh) * | 2020-12-07 | 2021-03-23 | 陕西生益科技有限公司 | 一种磁介电树脂组合物、包含其的层压板及其印刷电路板 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3255052A (en) * | 1963-12-09 | 1966-06-07 | Magnetics Inc | Flake magnetic core and method of making same |
US3535200A (en) * | 1967-09-18 | 1970-10-20 | Gen Motors Corp | Multilayered mechanically oriented ferrite |
US3927930A (en) * | 1972-07-10 | 1975-12-23 | Polaroid Corp | Light polarization employing magnetically oriented ferrite suspensions |
NL8004200A (nl) * | 1980-07-22 | 1982-02-16 | Philips Nv | Kunststofgebonden electromagnetische component en werkwijze voor het vervaardigen daarvan. |
JPS5996532A (ja) * | 1982-11-25 | 1984-06-04 | Fuji Photo Film Co Ltd | 磁気記録体 |
US4595440A (en) * | 1983-12-08 | 1986-06-17 | Memron Inc. | Transfer process for forming magnetic disk memories |
DE4214376A1 (de) * | 1992-04-30 | 1993-11-04 | Siemens Matsushita Components | Magnetisches material fuer leistungsuebertragerkerne |
US5413903A (en) * | 1993-10-12 | 1995-05-09 | Eastman Kodak Company | Element having a transparent magnetic recording layer containing barium ferrite particles |
US5643686A (en) * | 1994-01-06 | 1997-07-01 | Tokyo Magnetic Printing Co., Ltd. | Magnetic recording medium and method for manufacturing the same |
US5700594A (en) * | 1995-02-09 | 1997-12-23 | Eastman Kodak Company | Magnetic medium capable of supporting both longitudinal and perpendicular recording, and method of making same |
FR2740259B1 (fr) * | 1995-10-24 | 1997-11-07 | Thomson Csf | Noyau magnetique mixte |
-
1995
- 1995-09-19 FR FR9510952A patent/FR2738949B1/fr not_active Expired - Fee Related
-
1996
- 1996-09-09 US US08/711,272 patent/US6120916A/en not_active Expired - Fee Related
- 1996-09-13 EP EP96401962A patent/EP0764955B1/fr not_active Expired - Lifetime
- 1996-09-13 DE DE69611072T patent/DE69611072T2/de not_active Expired - Fee Related
- 1996-09-13 AT AT96401962T patent/ATE197855T1/de not_active IP Right Cessation
- 1996-09-18 CA CA002185930A patent/CA2185930A1/fr not_active Abandoned
- 1996-09-18 JP JP8266569A patent/JPH09129434A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE69611072T2 (de) | 2001-05-10 |
ATE197855T1 (de) | 2000-12-15 |
FR2738949A1 (fr) | 1997-03-21 |
US6120916A (en) | 2000-09-19 |
CA2185930A1 (fr) | 1997-03-20 |
JPH09129434A (ja) | 1997-05-16 |
DE69611072D1 (de) | 2001-01-04 |
FR2738949B1 (fr) | 1997-10-24 |
EP0764955A1 (fr) | 1997-03-26 |
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