EP0135826A1 - Appareil pour la pulvérisation thermique d'un plasma - Google Patents

Appareil pour la pulvérisation thermique d'un plasma Download PDF

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Publication number
EP0135826A1
EP0135826A1 EP84110175A EP84110175A EP0135826A1 EP 0135826 A1 EP0135826 A1 EP 0135826A1 EP 84110175 A EP84110175 A EP 84110175A EP 84110175 A EP84110175 A EP 84110175A EP 0135826 A1 EP0135826 A1 EP 0135826A1
Authority
EP
European Patent Office
Prior art keywords
nozzle
combustion chamber
gas
jet
bundling
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.)
Granted
Application number
EP84110175A
Other languages
German (de)
English (en)
Other versions
EP0135826B1 (fr
Inventor
Manfred Oechsle
Uwe Szieslo
Karl-Peter Streb
Wolfgang Simm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ECG Immobilier SA
Original Assignee
Castolin SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Castolin SA filed Critical Castolin SA
Priority to AT84110175T priority Critical patent/ATE24420T1/de
Publication of EP0135826A1 publication Critical patent/EP0135826A1/fr
Application granted granted Critical
Publication of EP0135826B1 publication Critical patent/EP0135826B1/fr
Expired legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05HPLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00Generating plasma; Handling plasma
    • H05H1/24Generating plasma
    • H05H1/26Plasma torches
    • H05H1/32Plasma torches using an arc
    • H05H1/42Plasma torches using an arc with provisions for introducing materials into the plasma, e.g. powder, liquid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/20Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion
    • B05B7/201Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle
    • B05B7/205Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed by flame or combustion downstream of the nozzle the material to be sprayed being originally a particulate material
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05HPLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00Generating plasma; Handling plasma
    • H05H1/24Generating plasma
    • H05H1/26Plasma torches
    • H05H1/32Plasma torches using an arc
    • H05H1/34Details, e.g. electrodes, nozzles
    • H05H1/36Circuit arrangements

Definitions

  • the invention relates to a device for the thermal spraying of build-up welding materials, consisting of a coolable beam bundling nozzle with a space on the feed side to accommodate devices for controllable supply of the operating components, namely operating gases and build-up welding material.
  • the mouth of the carrier gas powder outlet channel is arranged directly in the region of the junction into the jet bundling channel of the bundling nozzle, the expanded space around the nozzle only serving for the oxygen supply, which through an annular gap Carrier gas powder stream is added.
  • the nozzle is not designed to be adjustable, so that there are no possibilities for adaptation to different powders.
  • the entire device must be ignited from the front, which is also not without danger.
  • the invention is therefore based on the object to provide a device with comparatively low spray losses, which, working according to the so-called differential pressure principle, on the one hand does not require or does not require much more than previously required for flame spraying in terms of apparatus expenditure, but on the other hand with adapted variability the combustion chamber allows the use of all combustible gases, but in particular also acetylene and different wettable powders and with which, in particular, the ignition or start-up process should also be able to be controlled safely.
  • the expanded space is designed as a combustion chamber with a flow-accelerating transition contour for the confluence of the bundling nozzle det and an axially adjustable, differential pressure-charged burner nozzle or a nozzle holder with a nozzle is arranged in the combustion chamber with respect to the mouth of the beam bundling nozzle and that an ignition electrode which can be set on the nozzle is also arranged in the wall of the combustion chamber and this with an electrode after the flushing the bundling nozzle and before the supply of the fuel gas switching element is provided.
  • the solution given is easiest to implement by combining the jet nozzle with a flame spray gun in such a way that the variability of the combustion chamber volume is retained. However, one remains dependent on the performance data of the spray gun used in each case. If you do not want to be able to process wire as a spray additive in addition to powder, the nozzle holder is designed as a correspondingly adapted nozzle assembly while maintaining the basic principle.
  • the solution according to the invention results in the following advantages with regard to the application layers: With high-melting materials (oxides, cermets, high-melting metals, etc.), it has been shown that a significantly better layer quality can be achieved.
  • the tightness in the application layer is significantly increased compared to conventional flame spray applications.
  • the adhesive strength is also significantly improved due to the higher kinetic energy of the spray particles, and there is also no impairment of the sprayed-on layer by powder particles which have baked in the beam bundling channel and which sooner or later become detached again. Through the Bün the spray jet, the otherwise unavoidable spray losses for targeted applications are significantly reduced.
  • the ignition device equipped with an electrode it has also proven essential for the device's long-term operability to be able to withdraw the electrode from the combustion chamber after it has been ignited, in order not to disturb the flow in the combustion chamber on the one hand and on the other to not to hinder the adaptation of the combustion chamber volume to the respective circumstances.
  • combustion chamber wall is also designed to be coolable.
  • the residence time of the powder particles in the combustion chamber can be influenced thereby, ie the powder is preheated in an adapted manner or brought to the desired temperature in a targeted manner and even before it reaches the jet nozzle at high speed.
  • a flow-accelerating transition contour is present between the combustion chamber and the confluence with the beam bundling channel, advantageously with respect to the device axis with a convex shape, which is of particular importance in the present case insofar as otherwise, since the pulse at least melted particles emerge from the combustion chamber, the powder particles can already start in the junction area of the beam focusing channel. If this area does not fully grow when the flow is unfavorable, such approaches lead to the risk of tearing off and if such tearing particles get into the application layer, this does not lead to optimal coating results.
  • both high-melting and low-melting spray additives can be sprayed, and finally there is the possibility of supplying atomizing or additional gases, which make it possible to influence the operation of the device in a targeted manner.
  • the beam bundling nozzle is therefore advantageously designed in several parts, which will be explained in more detail.
  • the device When the device is designed with a nozzle assembly, powder conveyance is carried out by an external powder conveying system during powder spraying, so that uniform powder conveyance is made possible.
  • the wire In the case of processing wire as a spray additive, the wire is also fed via an external feed device of known type for the wire.
  • additional devices for forming such a jacket flow can then also be made in the half on the confluence, preferably in the area before the confluence, which can also be generated, for example, by supplying inert gas.
  • the injected gas which may also be a fuel gas, then forms a cladding layer in the channel, and baking of molten particles is practically no longer possible.
  • the inner channel of the jet bundling nozzle does not have to be cylindrical, but can also be designed to widen conically towards the nozzle mouth.
  • the solution according to the invention creates a device which is conceivably simple in its construction, part of which can even be a conventional flame spray gun, which can be adapted to all by simple adaptability of the combustion chamber volume this area is accessible to conventional fuel gases or fuel gas mixtures and the. ensures a safe ignition process.
  • the size of the combustion chamber is therefore variable and only the gases burned out in the combustion chamber reach the beam bundle channel under acceleration. Since the powder particles thus also only get into the combustion chamber, they are melted or melted there in an adapted manner and in this state reach the bundling channel.
  • the arrangement of a retractable ignition electrode in the combustion chamber is essential in order to ensure the ignition of only a relatively small mixture of fuel gas in the combustion chamber when the device is started up.
  • the essential parts of the device are the flame spray gun 6 ′′, which is only indicated by dashed lines, an adapter 3 containing the combustion chamber 2, the beam focusing nozzle 1 and the ignition device with electrode 7.
  • the flame spray gun 6 ′′ requires no further explanation, as is known per se .
  • the adapter 3 must of course be dimensioned with respect to its receiving bore so that the head 6 'of the flame spray gun 6 ", in which the burner nozzle 5 is seated, can be used in the adapter 3, specifically with suitable elements in different positions to fix the To be able to adapt combustion chamber 2 to the respective requirements
  • the ignition device with the ignition electrode 7 is also arranged so that it can be adjusted with respect to its longitudinal axis, so that the suitable ignition distance to the nozzle 5 can be set and an ignition arc or ignition spark can briefly occur for ignition.
  • the ignition device is designed as follows:
  • the electrode 7 forms the armature of a magnetic coil 11 which, when excited, brings the electrode 7 to the nozzle 5 against the action of a return spring 12 in the ignition position (dashed line). In this position, the ignition current is switched on by a limit switch 13 (FIG. 6). After ignition, coupled with current cutoff of the coil 11, the electrode 7 is reset from the combustion chamber 2 by the spring 12. It is essential for the ignition process that the ignition does not take place only when the combustion chamber 2 is filled, but immediately at the beginning of the inflow of an ignitable gas mixture into the combustion chamber.
  • the jet bundling nozzle 1 including the adapter 3 is water-cooled, wherein the cooling channels 14, 15 are connected to a connecting line 16.
  • the coolant inflow connection 17 for both cooling channels 14, 15 is arranged in the attachment area of the jet bundling nozzle 18 to the adapter 3, and a common coolant outflow connection 19 is provided for both channels 14, 15.
  • the beam bundling nozzle 1 can be formed from individual parts 22 which can be connected to one another and which are connected to one another with regard to the passage of coolant by bypass lines 23, provided that not every individual part 22 is provided with separate inflow and outflow connections.
  • one or more gas supply openings 21 are provided at the end on the adapter side, as shown schematically in FIG. 4. Furthermore, such openings 21 'can additionally be provided in the region of the mouth-side half of the steel bundling nozzle 1, for example in the flow shadow of a gradation 24 (on the right in FIG. 4). These embodiments can also be used in the device according to FIG. 2.
  • the part which is movable or adjustable with respect to the combustion chamber 2 (flame spray gun 6 "or nozzle holder 6 according to FIG. 2) is advantageously provided with a marking or with an adjustable stop in order to ensure that the part in question with its for the ignition process Nozzle 5 is brought into the correct ignition distance from electrode 7.
  • the ignition device or the electrode 7 is expediently arranged in the plug-in region 3 'of the adapter 3 containing the combustion chamber 2, so that the access opening in the adapter wall for the electrode 7 is covered even when the volume of the combustion chamber 2 is set to the greatest extent, which is in consideration of the high temperatures in the combustion chamber 2 is advantageous.
  • the embodiment according to FIG. 2 differs from that described in FIG. 1 practically only in that instead of the spray gun a correspondingly adapted nozzle assembly or nozzle holder 6 is provided and one is therefore no longer bound to the performance data of the flame spray gun 6 " 2, the conveying elements for the wire-shaped spray material are not shown for the flame spray gun and the nozzle holder according to FIG. 2, since such elements are generally known.
  • the nozzle holder 6 according to FIG of course, also be equipped with a connection for a powder storage container or for a powder supply line.
  • Corresponding parts of this embodiment according to FIG. 2 are therefore designated with corresponding reference numerals which are provided with a dash index.
  • the flame spray gun or the nozzle assembly, the electrode and corresponding connecting lines are not shown.
  • the convex design of the transition contour 4 ′ from the combustion chamber 2 into the beam bundling channel 25 can be seen particularly clearly here, which widens somewhat conically toward the mouth 26.
  • Such an extension can also be provided in the embodiments according to FIGS. 1, 2.
  • the wall of the beam focusing channel 25 is formed as a molded body 27 made of porous, gas-permeable material.
  • the porous molded body 27 is with a ; Compressed gas feedable cavity 28 to which the compressed gas is fed through a compressed gas feed connection 29.
  • the molded body 27 is formed, for example, from sintered A1 2 0 3 or zr03 or mixed forms thereof. Since the molded body 27 is gas-permeable over its entire surface, a constantly renewing gas cushion is formed in the sense of the aforementioned jacket flow, it being entirely possible to additionally arrange openings 21 in the immediate vicinity of the overflow contour 4 '.
  • the pressure gas supplied through the connection 29 can also be a combustion gas. act gas for an additional acceleration of the entire flow in the beam focusing channel 25 provides.
  • Corresponding relays K 6 , K 2 , K 3 , K4 and corresponding circuit elements delayed on and off delay ensure the necessary functional sequence according to FIG. 7 on the device, t 3 representing the actual operating phase.
  • the curves shown are of course only of qualitative importance.
  • E.g. illustrates the ignition curve that the ignition current only flows in the time interval t 2 , in which the fuel gas only begins to flow in.
  • the electrode curve shows that the electrode is withdrawn immediately after the interval t 2 .
  • the fuel gas supply drops immediately, but the oxygen supply can continue to run a little for purging purposes.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical & Material Sciences (AREA)
  • Nozzles (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pressure-Spray And Ultrasonic-Wave- Spray Burners (AREA)
  • Glass Compositions (AREA)
  • Arc Welding In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
EP84110175A 1983-08-30 1984-08-27 Appareil pour la pulvérisation thermique d'un plasma Expired EP0135826B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84110175T ATE24420T1 (de) 1983-08-30 1984-08-27 Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833331216 DE3331216A1 (de) 1983-08-30 1983-08-30 Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen
DE3331216 1983-08-30

Publications (2)

Publication Number Publication Date
EP0135826A1 true EP0135826A1 (fr) 1985-04-03
EP0135826B1 EP0135826B1 (fr) 1986-12-30

Family

ID=6207788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84110175A Expired EP0135826B1 (fr) 1983-08-30 1984-08-27 Appareil pour la pulvérisation thermique d'un plasma

Country Status (12)

Country Link
US (1) US4711627A (fr)
EP (1) EP0135826B1 (fr)
JP (1) JPS60502243A (fr)
AT (1) ATE24420T1 (fr)
AU (1) AU573259B2 (fr)
BR (1) BR8407043A (fr)
CA (1) CA1215225A (fr)
DE (2) DE3331216A1 (fr)
IN (1) IN161699B (fr)
MX (1) MX163708B (fr)
SU (1) SU1493095A3 (fr)
WO (1) WO1985000991A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3620201A1 (de) * 1986-06-16 1987-12-17 Castolin Gmbh Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen
DE3620183A1 (de) * 1986-06-16 1987-12-17 Castolin Gmbh Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen
EP0249790A2 (fr) * 1986-06-16 1987-12-23 Castolin S.A. Appareil de pulvérisation thermique de produits de soudure
DE3930726A1 (de) * 1989-09-14 1991-03-28 Matthaeus Heinz Dieter Vorrichtung zum thermischen verspritzen von pulvern, draehten od. dgl.
DE4219992A1 (de) * 1991-12-23 1993-06-24 Osu Maschinenbau Gmbh Thermisches spritzverfahren und spritz- und beschleunigungsduese zur erzeugung von metallschichten
EP0585203A1 (fr) * 1992-08-24 1994-03-02 Sulzer Metco AG Appareil de pulvérisation par plasma

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JPS61259777A (ja) * 1985-05-13 1986-11-18 Onoda Cement Co Ltd 単ト−チ型プラズマ溶射方法及び装置
JPH0622719B2 (ja) * 1985-05-13 1994-03-30 小野田セメント株式会社 複ト−チ型プラズマ溶射方法及びその装置
US5262206A (en) * 1988-09-20 1993-11-16 Plasma Technik Ag Method for making an abradable material by thermal spraying
US5019686A (en) * 1988-09-20 1991-05-28 Alloy Metals, Inc. High-velocity flame spray apparatus and method of forming materials
DE3903888C2 (de) * 1989-02-10 1998-04-16 Castolin Sa Vorrichtung zum Flammspritzen
DE3903887C2 (de) * 1989-02-10 1998-07-16 Castolin Sa Vorrichtung zum Flammspritzen von pulverförmigen Werkstoffen mittels autogener Flamme
US5074802A (en) * 1989-09-12 1991-12-24 Hypertherm, Inc. Pneumatic-electric quick disconnect connector for a plasma arc torch
WO1991012085A1 (fr) * 1990-02-14 1991-08-22 Institut Problem Materialovedenia Imeni I.N.Frantsevicha Akademii Nauk Ukrainskoi Ssr Installation de detonation de gaz pour l'application de revetements
US5575636A (en) * 1994-06-21 1996-11-19 Praxair Technology, Inc. Porous non-fouling nozzle
CH693083A5 (de) * 1998-12-21 2003-02-14 Sulzer Metco Ag Düse sowie Düsenanordnung für einen Brennerkopf eines Plasmaspritzgeräts.
US7164095B2 (en) 2004-07-07 2007-01-16 Noritsu Koki Co., Ltd. Microwave plasma nozzle with enhanced plume stability and heating efficiency
US20060052883A1 (en) * 2004-09-08 2006-03-09 Lee Sang H System and method for optimizing data acquisition of plasma using a feedback control module
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
SE529056C2 (sv) 2005-07-08 2007-04-17 Plasma Surgical Invest Ltd Plasmaalstrande anordning, plasmakirurgisk anordning och användning av en plasmakirurgisk anordning
TW200742506A (en) 2006-02-17 2007-11-01 Noritsu Koki Co Ltd Plasma generation apparatus and work process apparatus
JP4620015B2 (ja) * 2006-08-30 2011-01-26 株式会社サイアン プラズマ発生装置およびそれを用いるワーク処理装置
US7928338B2 (en) 2007-02-02 2011-04-19 Plasma Surgical Investments Ltd. Plasma spraying device and method
CN102441505A (zh) * 2007-05-09 2012-05-09 诺信公司 用于粉末喷枪的喷嘴
US7589473B2 (en) 2007-08-06 2009-09-15 Plasma Surgical Investments, Ltd. Pulsed plasma device and method for generating pulsed plasma
US8735766B2 (en) 2007-08-06 2014-05-27 Plasma Surgical Investments Limited Cathode assembly and method for pulsed plasma generation
CN102204414B (zh) * 2008-08-20 2014-10-22 视觉动力控股有限公司 产生用于对衬底表面进行构图的等离子体放电的设备
US20100074810A1 (en) * 2008-09-23 2010-03-25 Sang Hun Lee Plasma generating system having tunable plasma nozzle
GB0819359D0 (en) * 2008-10-22 2008-11-26 Intrinsiq Materials Ltd Plasma torch
US7921804B2 (en) * 2008-12-08 2011-04-12 Amarante Technologies, Inc. Plasma generating nozzle having impedance control mechanism
US20100201272A1 (en) * 2009-02-09 2010-08-12 Sang Hun Lee Plasma generating system having nozzle with electrical biasing
US20100254853A1 (en) * 2009-04-06 2010-10-07 Sang Hun Lee Method of sterilization using plasma generated sterilant gas
US8613742B2 (en) 2010-01-29 2013-12-24 Plasma Surgical Investments Limited Methods of sealing vessels using plasma
US20110229649A1 (en) * 2010-03-22 2011-09-22 Baranovski Viatcheslav E Supersonic material flame spray method and apparatus
US9089319B2 (en) 2010-07-22 2015-07-28 Plasma Surgical Investments Limited Volumetrically oscillating plasma flows
DE102012000816A1 (de) * 2012-01-17 2013-07-18 Linde Aktiengesellschaft Verfahren und Vorrichtung zum thermischen Spritzen
BR112014017304B1 (pt) * 2012-01-27 2021-06-22 Oerlikon Metco (Us) Inc. Pistola de pulverização térmica com ponta de bocal removível, sistema de pistola de pulverização térmica e método de revestimento de substrato com a utilização da mesma
WO2022047227A2 (fr) 2020-08-28 2022-03-03 Plasma Surgical Investments Limited Systèmes, procédés et dispositifs pour générer un flux de plasma étendu principalement radialement

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DE1564123A1 (de) * 1966-03-03 1970-02-12 Inst Plasmaphysik Gmbh Einrichtung zum Erzeugen eines heissen Plasmastrahles

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3620201A1 (de) * 1986-06-16 1987-12-17 Castolin Gmbh Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen
DE3620183A1 (de) * 1986-06-16 1987-12-17 Castolin Gmbh Vorrichtung zum thermischen spritzen von auftragsschweisswerkstoffen
EP0249790A2 (fr) * 1986-06-16 1987-12-23 Castolin S.A. Appareil de pulvérisation thermique de produits de soudure
US4805836A (en) * 1986-06-16 1989-02-21 Castolin S.A. Device for the thermal spray application of welding materials
EP0249790A3 (en) * 1986-06-16 1989-03-15 Castolin S.A. Apparatus for thermally spraying welding products
DE3930726A1 (de) * 1989-09-14 1991-03-28 Matthaeus Heinz Dieter Vorrichtung zum thermischen verspritzen von pulvern, draehten od. dgl.
DE4219992A1 (de) * 1991-12-23 1993-06-24 Osu Maschinenbau Gmbh Thermisches spritzverfahren und spritz- und beschleunigungsduese zur erzeugung von metallschichten
EP0585203A1 (fr) * 1992-08-24 1994-03-02 Sulzer Metco AG Appareil de pulvérisation par plasma

Also Published As

Publication number Publication date
DE3461750D1 (en) 1987-02-05
MX163708B (es) 1992-06-15
BR8407043A (pt) 1985-07-30
WO1985000991A1 (fr) 1985-03-14
AU573259B2 (en) 1988-06-02
SU1493095A3 (ru) 1989-07-07
JPS60502243A (ja) 1985-12-26
JPH0416217B2 (fr) 1992-03-23
IN161699B (fr) 1988-01-16
EP0135826B1 (fr) 1986-12-30
US4711627A (en) 1987-12-08
ATE24420T1 (de) 1987-01-15
AU3315584A (en) 1985-03-29
CA1215225A (fr) 1986-12-16
DE3331216A1 (de) 1985-03-14

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