EP0596830B1 - Appareil de pulvérisation par plasma - Google Patents
Appareil de pulvérisation par plasma Download PDFInfo
- Publication number
- EP0596830B1 EP0596830B1 EP93810729A EP93810729A EP0596830B1 EP 0596830 B1 EP0596830 B1 EP 0596830B1 EP 93810729 A EP93810729 A EP 93810729A EP 93810729 A EP93810729 A EP 93810729A EP 0596830 B1 EP0596830 B1 EP 0596830B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plasma
- anode
- channel
- cathode
- spray gun
- 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
Links
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/34—Details, e.g. electrodes, nozzles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/34—Details, e.g. electrodes, nozzles
- H05H1/3484—Convergent-divergent nozzles
Definitions
- the present invention relates to a plasma spraying device with an indirect plasmatron for spraying powdery material, in particular for coating workpiece surfaces.
- plasma sprayers For spraying powdery material in the molten state, plasma sprayers are used which work with an indirect plasmatron, i.e. a plasma generator with an electrically non-current-carrying plasma jet flowing out of a nozzle.
- an indirect plasmatron i.e. a plasma generator with an electrically non-current-carrying plasma jet flowing out of a nozzle.
- the plasma is generated by an arc and passed through a plasma channel to an outflow nozzle, a distinction being made between devices with a short arc and those with a long arc.
- Foot migrations can be particularly pronounced in plasma cartridges, which work with a short arc, a pin-shaped cathode being immersed in a one-piece, nozzle-shaped anode (for example in accordance with DE-GM 1 932 150), since anode nozzles with an axial extension with this electrode arrangement have both axial and peripheral Migration of the arc base can occur.
- At least axial foot point hikes can also be expected in a similar plasma spraying device according to DE 33 12 232, which has several cathodes instead of one.
- an axial base point migration results from the fact that an arc burning between a cathode and a nozzle-shaped anode is drawn out under the influence of the plasma flow to a point of the anode furthest from the cathode, then tears off at this point and at one of the Cathode at the closest point of the anode again starts.
- this process is repeated more or less periodically with a repetition frequency in the order of several kilohertz.
- the voltage changes associated with the changes in length of the arc can lead to large power fluctuations (up to approximately ⁇ 30%) and corresponding intensity fluctuations in the free plasma beam.
- the spray material supplied to the plasma jet is treated very unevenly.
- the radial temperature profile of the free plasma jet also runs asymmetrically, i.e. that the hot core of the plasma jet experiences a certain deflection from the longitudinal axis of the plasma cartridge.
- This effect is further supported by the fact that the plasma flowing out of the anode nozzle at the base of the arc, i.e. at an eccentric point in the arrangement, is additionally heated.
- Such a deflection of the plasma core is particularly serious in connection with a peripheral migration of the base of the arc.
- This creates a kind of precession movement of the plasma jet which usually runs irregularly and, when the spray material is supplied externally from a stationary supply device, also results in an uneven thermal treatment of the spray material.
- a plasma spraying device the plasmatron of which works with a long arc and, for example according to EP 0 249 238 A2, one with an anode ring ring and has a number of annular, electrically isolated neutrodes formed from each other.
- a plasmatron of this type still shows a pronounced peripheral migration of the arc base at the ring-shaped anode, provided the arc starts from a single cathode, as is the case, for example, with the plasma spraying device according to EP 0 249 238 A2.
- the situation is similar to that of the example of a short-arc plasma platrons described above. In this case too, the result is an uneven treatment of the spray material supplied from the side.
- the plasma spraying device shown in longitudinal section has three rod-shaped cathodes 1, which run parallel to one another and are evenly distributed in a circle around the central longitudinal axis 2 of the device, furthermore an annular anode 3 distanced from the cathodes 1 and a plasma guide channel 4 extending from the cathodes 1 to the anode 3.
- the plasma guide channel 4 is isolated from one another by a number of annular, electrically insulated Neutrodes 6 to 12 and the annular anode 3 are formed.
- the cathode rods 1 are anchored in a cathode support 13 made of insulating material.
- a sleeve-shaped anode carrier 14 made of insulating material, which surrounds the neutrodes 6 to 12 and the anode 3.
- the whole is held together by three metal sleeves 15, 16 and 17, the first sleeve 15 being screwed to the end on the end face and the second sleeve 16 being screwed to the first circumference, while the third sleeve 17 is loosely anchored on the one hand to the second sleeve 16 and on the other hand is screwed circumferentially to the anode carrier 14.
- the third sleeve 17 also presses with an inwardly directed flange 18 against the anode ring 3 and thus holds the elements forming the plasma guide channel 4 together, the neutrode 6 closest to the cathodes being supported on an inner collar 19 of the anode carrier 4.
- the free ends of the cathode rods 1 carry cathode pins 20, which are made of an electrically and thermally particularly conductive and also high-melting material, for example tungsten.
- the cathode pins 20 are eccentric to the respective one Axis of the cathode rods 1 is arranged so that their longitudinal axes are closer to the central longitudinal axis 2 than those of the cathode rods 1.
- a central insulating body 21 made of high-melting, in particular glass-ceramic material, from which the cathode pins 20 are made, is attached to the cathode carrier 13 on the side facing the plasma guide channel 4 protrude into the cavity 22 of the inlet nozzle formed by the first neutrode 6.
- the exposed part of the outer circumferential surface of the insulating body 21 is located radially opposite a part of the nozzle wall and forms with this wall part an annular channel 23 for the inlet of the plasma gas into the nozzle cavity 22.
- the plasma gas PG is fed through a transverse channel 26 provided in the cathode carrier 13, which transitions into a longitudinal channel 27, from which the plasma gas reaches an annular space 28 and from there into the annular channel 23.
- a distributor ring 29 is provided on the insulating body 20 and has a plurality of through bores 30 which connect the annular space 28 to the annular channel 23.
- the elements forming the plasma guide channel 4, namely the anode 3 and the neutrodes 6 to 12, are electrically insulated from one another by ring disks 31 made of insulating material, for example boron nitride, and are connected to one another in a gastight manner by means of sealing rings 32.
- the plasma guide channel 4 has a constriction zone 33 in the region near the cathode and widens after this Constriction zone 33 towards the anode 3 to a diameter which is at least 1.5 times as large as the channel diameter at the narrowest point of the constriction zone 33. After this expansion, the plasma guide channel 4 extends cylindrically to its anode-side end.
- the anode 3 is made up of an outer ring 34, for example of copper, and an inner ring 35 of an electrically and thermally particularly conductive and also high-melting material, for example tungsten.
- the neutrode 6 closest to the cathode rods 1 extends over the entire constriction zone 33, so that the channel wall 52 unites beyond the narrowest point of the constriction zone has a steady course.
- the parts directly exposed to the arc and plasma heat are largely water-cooled.
- various cavities for the circulation of the cooling water KW are provided in the cathode holder 13, in the cathode rods 1 and in the anode holder 14.
- the cathode holder 13 has three annular spaces 36, 37 and 38, which are connected to connecting lines 39, 40 and 41, respectively, and the anode holder 14 has an annular space 42 in the area of the anode 3 and one surrounding all neutrodes in the area of the neutrodes 6 to 12 Cavity 43 on.
- Cooling water KW is supplied via the connecting lines 39 and 41.
- the cooling water of the connecting line 39 first passes through a longitudinal channel 44 to the annular space 42 surrounding the most thermally stressed anode 3.
- the cooling water flows through the cavity 43 of the lateral surface of the neutrodes 6 to 12 back through a longitudinal channel 45 into the annular space 37
- Connection line 41 flows into an annular space 38 and from this into a cavity 46 of the cathode rods 1, which is divided by a cylindrical partition 47.
- the cooling water also arrives from the cathode rods 1 into the annular space 37, from which it flows out via the connecting line 40.
- the approximate course of the individual arcs 50 (two visible) is also indicated schematically in the figure. Their anode-side base points are distributed evenly over the inner circumference of the anode ring 3. Furthermore, the beginning section of the free plasma jet PS emerging axially symmetrically from the plasma channel 4 is indicated by dashed lines.
- the supply of the spray material, for example metal powder, into the free plasma jet PS takes place with the aid of a ring arrangement 51 made of temperature-resistant material placed on the anode-side metal sleeve 17, which is provided with channels 52 in the form of radial bores, to which the spray material SM is supplied with a carrier gas via connecting lines 53 is fed.
- a ring arrangement 51 made of temperature-resistant material placed on the anode-side metal sleeve 17, which is provided with channels 52 in the form of radial bores, to which the spray material SM is supplied with a carrier gas via connecting lines 53 is fed.
- two radial bores are diametrically opposite one another.
- a ring arrangement with only one channel 52 or one with more than two, for example three, channels can also be present be in the latter case, the channels are preferably arranged evenly distributed over the circumference of the ring assembly 51.
- the channels are preferably arranged evenly distributed over the circumference of the ring assembly 51.
- an axial guide tube can be provided which passes through the cathode holder 13 and the insulating body 21 centrally.
- the entire arc energy that is to say not only the energy portion which passes from the arc into the free plasma jet, can be used in a known manner to melt the spray material.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma Technology (AREA)
- Coating By Spraying Or Casting (AREA)
- Nozzles (AREA)
- Electrostatic Spraying Apparatus (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Claims (9)
- Appareil de projection au plasma avec plasmatron indirect pour la pulvérisation de matériau en poudre, en particulier pour le revêtement de surfaces de pièces, caractérisée par la combinaison des caractéristiques suivantes :a) le plasmatron présente un dispositif à cathodes, une anode (3) annulaire et espacée du dispositif à cathodes (1) et un canal à plasma s'étendant du dispositif à cathodes jusqu'à l'anode ;b) le dispositif à cathodes présente plusieurs cathodes (1, 20) disposées et réparties en cercle autour de l'axe longitudinal (2) du canal à plasma (4) ;c) le canal à plasma (4) est constitué par la bague d'anode (3) et un nombre de neutrodes (6 à 12) de forme annulaire et isolée électriquement les unes des autres ; etd) sur l'extrémité côté anode du plasmatron sont prévus des moyens (51) pour l'arrivée latérale du matériau de projection (SM) dans le jet de plasma (PS) libre.
- Appareil de projection au plasma selon la revendication 1, caractérisé en ce que les moyens pour l'arrivée du matériau de projection (SM) comprennent un dispositif annulaire (51) posé sur l'extrémité (17) côté anode du plasmatron, qui présente au moins un canal (52) allant de l'extérieur vers l'intérieur, à l'extrémité extérieure duquel aboutit une conduite de raccordement (53).
- Appareil de projection au plasma selon la revendication 2, caractérisé en ce que le canal (52) va dans le sens radial.
- Appareil de projection au plasma selon la revendication 2, caractérisé en ce que le canal est disposé en oblique dans un plan axial du dispositif annulaire et est orienté vers l'avant ou vers l'arrière par rapport à la direction du jet de plasma (PS) libre.
- Appareil de projection au plasma selon la revendication 2, caractérisé en ce qu'on prévoit deux canaux (52) qui sont diamétralement opposés.
- Appareil de projection au plasma selon la revendication 2, caractérisé en ce qu'il existe plusieurs canaux qui sont disposés et répartis régulièrement à la périphérie du dispositif annulaire (51).
- Appareil de projection au plasma selon la revendication 1, caractérisé en ce qu'on prévoit en supplément des moyens pour l'arrivée axiale de matériau de projection sur l'extrémité côté cathode du plasmatron.
- Appareil de projection au plasma selon la revendication 7, caractérisé en ce qu'il est prévu comme moyen supplémentaire un tuyau central qui est orienté dans le sens axial vers le canal à plasma (4) et dépasse dans la cavité (22) de la neutrode (6) située la plus près des cathodes (1, 20).
- Plasmatron selon la revendication 1, caractérisé en ce que le canal à plasma (4) présente une zone de rétrécissement (33) dans la zone proche de la cathode du trajet de l'arc et s'élargit à partir de cette zone de rétrécissement en direction de l'anode (3).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE9215133U | 1992-11-06 | ||
DE9215133U DE9215133U1 (de) | 1992-11-06 | 1992-11-06 | Plasmaspritzgerät |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0596830A1 EP0596830A1 (fr) | 1994-05-11 |
EP0596830B1 true EP0596830B1 (fr) | 1996-05-08 |
Family
ID=6885751
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93810729A Expired - Lifetime EP0596830B1 (fr) | 1992-11-06 | 1993-10-18 | Appareil de pulvérisation par plasma |
Country Status (6)
Country | Link |
---|---|
US (1) | US5406046A (fr) |
EP (1) | EP0596830B1 (fr) |
JP (1) | JP3287373B2 (fr) |
AT (1) | ATE137905T1 (fr) |
CA (1) | CA2102284C (fr) |
DE (2) | DE9215133U1 (fr) |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE9215133U1 (de) * | 1992-11-06 | 1993-01-28 | Plasma-Technik Ag, Wohlen | Plasmaspritzgerät |
US5514848A (en) * | 1994-10-14 | 1996-05-07 | The University Of British Columbia | Plasma torch electrode structure |
DE19610015C2 (de) * | 1996-03-14 | 1999-12-02 | Hoechst Ag | Thermisches Auftragsverfahren für dünne keramische Schichten und Vorrichtung zum Auftragen |
DE19540587A1 (de) * | 1995-10-31 | 1997-05-07 | Bosch Gmbh Robert | Plasmabrenner |
US6213049B1 (en) | 1997-06-26 | 2001-04-10 | General Electric Company | Nozzle-injector for arc plasma deposition apparatus |
FR2779316B1 (fr) * | 1998-05-29 | 2000-08-25 | Aerospatiale | Dispositif de melange de gaz froid en sortie de torche a plasma |
US7662468B2 (en) * | 2000-10-06 | 2010-02-16 | Brock Usa, Llc | Composite materials made from pretreated, adhesive coated beads |
US6669106B2 (en) | 2001-07-26 | 2003-12-30 | Duran Technologies, Inc. | Axial feedstock injector with single splitting arm |
SE523135C2 (sv) * | 2002-09-17 | 2004-03-30 | Smatri Ab | Plasmasprutningsanordning |
US7557324B2 (en) * | 2002-09-18 | 2009-07-07 | Volvo Aero Corporation | Backstream-preventing thermal spraying device |
SE525927C2 (sv) * | 2002-09-18 | 2005-05-31 | Volvo Aero Corp | Anordning för termisk sprutning |
US7244477B2 (en) * | 2003-08-20 | 2007-07-17 | Brock Usa, Llc | Multi-layered sports playing field with a water draining, padding layer |
US20050089678A1 (en) * | 2003-08-20 | 2005-04-28 | Mead Steven R. | Multi-layered floorig composite including an acoustic underlayment |
US7759599B2 (en) * | 2005-04-29 | 2010-07-20 | Sulzer Metco (Us), Inc. | Interchangeable plasma nozzle interface |
SE529056C2 (sv) | 2005-07-08 | 2007-04-17 | Plasma Surgical Invest Ltd | Plasmaalstrande anordning, plasmakirurgisk anordning och användning av en plasmakirurgisk anordning |
SE529053C2 (sv) * | 2005-07-08 | 2007-04-17 | Plasma Surgical Invest Ltd | Plasmaalstrande anordning, plasmakirurgisk anordning och användning av en plasmakirurgisk anordning |
SE529058C2 (sv) * | 2005-07-08 | 2007-04-17 | Plasma Surgical Invest Ltd | Plasmaalstrande anordning, plasmakirurgisk anordning, användning av en plasmakirurgisk anordning och förfarande för att bilda ett plasma |
US20090140082A1 (en) * | 2005-12-06 | 2009-06-04 | Lucian Bogdan Delcea | Plasma Spray Nozzle System |
US7928338B2 (en) * | 2007-02-02 | 2011-04-19 | Plasma Surgical Investments Ltd. | Plasma spraying device and method |
US8735766B2 (en) * | 2007-08-06 | 2014-05-27 | Plasma Surgical Investments Limited | Cathode assembly and method for pulsed plasma generation |
CA2695902C (fr) * | 2007-08-06 | 2016-01-05 | Plasma Surgical Investments Limited | Ensemble cathodique et procede de generation de plasma pulse |
US7589473B2 (en) * | 2007-08-06 | 2009-09-15 | Plasma Surgical Investments, Ltd. | Pulsed plasma device and method for generating pulsed plasma |
FR2943209B1 (fr) | 2009-03-12 | 2013-03-08 | Saint Gobain Ct Recherches | Torche a plasma avec injecteur lateral |
US8237079B2 (en) * | 2009-09-01 | 2012-08-07 | General Electric Company | Adjustable plasma spray gun |
US9315888B2 (en) | 2009-09-01 | 2016-04-19 | General Electric Company | Nozzle insert for thermal spray gun apparatus |
FR2952786B1 (fr) | 2009-11-17 | 2012-06-08 | Centre Nat Rech Scient | Torche a plasma et procede de stabilisation d'une torche a plasma |
US8613742B2 (en) * | 2010-01-29 | 2013-12-24 | Plasma Surgical Investments Limited | Methods of sealing vessels using plasma |
US9089319B2 (en) | 2010-07-22 | 2015-07-28 | Plasma Surgical Investments Limited | Volumetrically oscillating plasma flows |
EP2535437A1 (fr) | 2011-06-16 | 2012-12-19 | RH Optronic ApS | Procédé de revêtement au plasma de rouleaux et rouleau revêtu au plasma |
DE102011114406A1 (de) | 2011-09-26 | 2013-03-28 | Klaus Landes | Plasmaspritzgerät |
WO2013130046A2 (fr) * | 2012-02-28 | 2013-09-06 | Sulzer Metco (Us), Inc. | Pistolet à plasma en cascade étendu |
US9272360B2 (en) | 2013-03-12 | 2016-03-01 | General Electric Company | Universal plasma extension gun |
CH712835A1 (de) * | 2016-08-26 | 2018-02-28 | Amt Ag | Plasmaspritzvorrichtung. |
CN110315178A (zh) * | 2019-07-03 | 2019-10-11 | 阳江市高功率激光应用实验室有限公司 | 焊枪结构及具有该焊枪结构的熔覆系统 |
IL300972A (en) | 2020-08-28 | 2023-04-01 | Plasma Surgical Invest Ltd | Systems, methods and devices for producing radially expanded plasma flow |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3524962A (en) * | 1967-06-02 | 1970-08-18 | Air Reduction | Aspirating plasma torch nozzle |
BE789373A (fr) * | 1971-10-22 | 1973-01-15 | Europ De Soc | Corps de pistolet a plasma |
US3707615A (en) * | 1971-11-12 | 1972-12-26 | Metco Inc | Nozzle for a plasma generator |
US3839618A (en) * | 1972-01-03 | 1974-10-01 | Geotel Inc | Method and apparatus for effecting high-energy dynamic coating of substrates |
FR2171469A5 (fr) * | 1972-02-01 | 1973-09-21 | Air Liquide | |
CH597925A5 (fr) * | 1975-12-01 | 1978-04-14 | Alusuisse | |
NL7600738A (nl) * | 1976-01-23 | 1977-07-26 | Plasmainvent Ag | Inrichting voor het plasma-spuiten. |
CH607540A5 (fr) * | 1976-02-16 | 1978-12-29 | Niklaus Mueller | |
US4122292A (en) * | 1976-09-13 | 1978-10-24 | Viktor Nikolaevich Karinsky | Electric arc heating vacuum apparatus |
DD143545A1 (de) * | 1979-05-16 | 1980-08-27 | Erhard Hayess | Kuehlkanal fuer kaskadenboegen und kaskadenplasmatrons |
GB2116810B (en) * | 1982-02-15 | 1986-01-08 | Ceskoslovenska Akademie Ved | Method for stabilization of low-temperature plasma of an arc burner, and the arc burner for carrying out said method |
US4818837A (en) * | 1984-09-27 | 1989-04-04 | Regents Of The University Of Minnesota | Multiple arc plasma device with continuous gas jet |
US4780591A (en) * | 1986-06-13 | 1988-10-25 | The Perkin-Elmer Corporation | Plasma gun with adjustable cathode |
DE3642375A1 (de) * | 1986-12-11 | 1988-06-23 | Castolin Sa | Verfahren zur aufbringung einer innenbeschichtung in rohre od. dgl. hohlraeume engen querschnittes sowie plasmaspritzbrenner dafuer |
US4788408A (en) * | 1987-05-08 | 1988-11-29 | The Perkin-Elmer Corporation | Arc device with adjustable cathode |
US5043548A (en) * | 1989-02-08 | 1991-08-27 | General Electric Company | Axial flow laser plasma spraying |
US5008511C1 (en) * | 1990-06-26 | 2001-03-20 | Univ British Columbia | Plasma torch with axial reactant feed |
DE4105407A1 (de) * | 1991-02-21 | 1992-08-27 | Plasma Technik Ag | Plasmaspritzgeraet zum verspruehen von festem, pulverfoermigem oder gasfoermigem material |
DE4105408C1 (fr) * | 1991-02-21 | 1992-09-17 | Plasma-Technik Ag, Wohlen, Ch | |
DE9215133U1 (de) * | 1992-11-06 | 1993-01-28 | Plasma-Technik Ag, Wohlen | Plasmaspritzgerät |
-
1992
- 1992-11-06 DE DE9215133U patent/DE9215133U1/de not_active Expired - Lifetime
-
1993
- 1993-10-18 AT AT93810729T patent/ATE137905T1/de not_active IP Right Cessation
- 1993-10-18 EP EP93810729A patent/EP0596830B1/fr not_active Expired - Lifetime
- 1993-10-18 DE DE59302504T patent/DE59302504D1/de not_active Expired - Lifetime
- 1993-10-28 US US08/144,685 patent/US5406046A/en not_active Expired - Lifetime
- 1993-11-02 CA CA002102284A patent/CA2102284C/fr not_active Expired - Lifetime
- 1993-11-05 JP JP27714093A patent/JP3287373B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP3287373B2 (ja) | 2002-06-04 |
EP0596830A1 (fr) | 1994-05-11 |
US5406046A (en) | 1995-04-11 |
ATE137905T1 (de) | 1996-05-15 |
DE9215133U1 (de) | 1993-01-28 |
CA2102284C (fr) | 1999-03-30 |
JPH06228730A (ja) | 1994-08-16 |
DE59302504D1 (de) | 1996-06-13 |
CA2102284A1 (fr) | 1994-05-07 |
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