[go: up one dir, main page]

EP0456847B1 - Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué - Google Patents

Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué Download PDF

Info

Publication number
EP0456847B1
EP0456847B1 EP90109028A EP90109028A EP0456847B1 EP 0456847 B1 EP0456847 B1 EP 0456847B1 EP 90109028 A EP90109028 A EP 90109028A EP 90109028 A EP90109028 A EP 90109028A EP 0456847 B1 EP0456847 B1 EP 0456847B1
Authority
EP
European Patent Office
Prior art keywords
nitrogen
protective layer
powder
component
spraying
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
Application number
EP90109028A
Other languages
German (de)
English (en)
Other versions
EP0456847A1 (fr
Inventor
Clemens M. Dr. Verpoort
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.)
BERNEX GmbH
Original Assignee
BERNEX GmbH
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40133659&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0456847(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to DE3816310A priority Critical patent/DE3816310A1/de
Priority to JP63151353A priority patent/JPS6417846A/ja
Application filed by BERNEX GmbH filed Critical BERNEX GmbH
Priority to EP90109028A priority patent/EP0456847B1/fr
Priority to DE59007940T priority patent/DE59007940D1/de
Publication of EP0456847A1 publication Critical patent/EP0456847A1/fr
Application granted granted Critical
Publication of EP0456847B1 publication Critical patent/EP0456847B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying 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
    • B05B7/22—Spraying 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 electrically, magnetically or electromagnetically, e.g. by arc
    • B05B7/228—Spraying 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 electrically, magnetically or electromagnetically, e.g. by arc using electromagnetic radiation, e.g. laser
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step
    • 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
    • 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
    • C23C4/137—Spraying in vacuum or in an inert atmosphere
    • 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
    • C23C4/18—After-treatment
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces

Definitions

  • the invention relates to the further development and perfection of the application of protective layers using spraying methods and heat treatments of the surface zone of a workpiece.
  • the invention relates to a method for producing a protective layer with high wear and corrosion resistance from an austenitic iron-based alloy on the surface of a component serving as a substrate by thermal spraying, submerged arc welding or laser treatment, and a protective layer produced by the method.
  • Austenitic steels with a very high nitrogen content can be produced using the pressure electro-slag remelting process (DESU process).
  • DESU process pressure electro-slag remelting process
  • the steel melt is kept under a nitrogen overpressure of 30 bar for a longer time and nitrogen is alloyed into the melt over silicon nitride. If such nitrogen-alloyed melts are cooled under pressure, the high, dissolved nitrogen content in the workpiece is retained. Forgings with nitrogen contents of 0.5 percent by weight can be produced. Higher nitrogen contents cannot be achieved by melt metallurgy, since correspondingly high silicon nitride additions have to be added to introduce nitrogen, which would lead to an excessively high Si content of the steel.
  • the embroidered components are characterized by a very high strength due to the interstitial nitrogen storage.
  • the melt of the austenitic steels is atomized in a gas atomization plant. If nitrogen is used as the atomizing gas, slight nitrogen nitriding (approx. 0.1-0.2% by weight) is achieved.
  • the nitrogen concentration of the powder can be determined by the hot isostatic pressing method described in patent DE-C-3624622 can be further increased. According to the process described there, nitrogen contents of over 1.2% by weight of nitrogen in the powder can be achieved.
  • thermo spraying processes The application of surface layers of all kinds from metallic and / or ceramic materials by numerous so-called “thermal spraying processes” is known per se from many publications. These include flame spraying, plasma spraying, high-speed flame spraying, etc.
  • the materials that are to build up the surface layer are fed to the corresponding apparatus in wire, strip and powder form as starting materials. Also worth mentioning are the methods that use a laser beam as the energy source for heating and melting the materials.
  • the invention has for its object to provide a protective layer of this type and a method for its production, the protective layer having improved mechanical properties, in particular at higher temperatures and being mechanically and chemically stable in the long term, and the method being inexpensively reproducible and feasible with simple means is.
  • FIG. 2 schematically shows the method and the device for embroidering and for applying the protective layer.
  • 10 is Fe / Cr / Mn powder (not containing nitrogen), which serves as the starting material in the present case.
  • 11 shows the feed of the Fe / Cr / Mn powder (indicated by the vertical arrow) into the hot isostatic press.
  • FIG. 12 is an open container for the heat treatment of the powders.
  • 13 means the supply of nitrogen N2 to the container 12 for the nitrogen nitrogen 10.
  • the reference numeral 15 means Fe / Cr / Mn / N powder (containing nitrogen) and the vertical arrow 16 the supply of this powder to the device 3 (spray gun).
  • the remaining reference numerals 1, 2, 6, 7, 8 correspond to those in FIG. 1.
  • Figure 3 relates to the method and apparatus using nitrogenous powder and a high speed flame spray gun.
  • Reference numerals 1, 2, 7, 8, 15 and 16 are the same as in Figures 1 and 2 and can be seen from the latter.
  • 17 is a high-speed flame spray gun which has a mixing chamber 18 for generating a fuel-oxygen mixture and a combustion chamber 19.
  • 20 is the fuel supply (symbols H2; CH4) and 21 is the oxygen supply (symbol 02).
  • other hydrocarbons propane, propylene, etc.
  • 22 represents the inert powder propellant gas, which usually consists of nitrogen (symbol N2) or a nitrogen / argon mixture (symbol N2 / Ar).
  • the supply of the gaseous media is indicated by arrows.
  • Fig. 4 shows the method and the device using nitrogen-containing powder and a submerged arc.
  • the component 1 is covered with a loose powder fill 23 made of Fe / Cr / Mn / N powder. Under this powder layer, a hidden arc 25 burns between non-consumable tungsten electrodes 24.
  • the process is somewhat similar to submerged arc welding, with the difference that here instead of the consumable wire that forms the weld metal as electrodes, tungsten rods and instead of the slag-forming inert powder, metal powder that forms the surface layer forms, is provided.
  • the remaining reference symbols s. Figures 1 and 3.
  • FIG. 5 schematically shows the method and the device using a nitrogen-containing wire and a wire flame spray gun.
  • the reference numerals 1, 2, 6, 7, 8, 20 and 21 are explained in Figs. 1 and 3.
  • 26 is a common wire flame spray gun into which an Fe / Cr / Mn / N wire 27 is axially inserted.
  • 28 represents the supply of an Fe / Cr / Mn / N wire to be melted.
  • 29 are the liquid metal particles which are thrown onto the surface of the component 1 to be coated.
  • FIG. 6 relates to the method and the device using nitrogen-containing sheathed wires as electrodes and an open arc.
  • spray wires made of solid Fe / Cr / Mn / N steel with a high nitrogen content can be used.
  • the wire electrode 30 made of sheathed wire is again shown enlarged in longitudinal section in the figure below.
  • the sheath wire is composed of a core made of Fe / Cr / Mn / N powder with a comparatively high nitrogen content and a sheath made of a ductile metal or plastic.
  • 33 represents the supply of the sheathed wire 30 to be melted.
  • the open arc 34 burns.
  • 35 is the atomizing nozzle through which the atomizing propellant gas 36 is supplied (arrow N2). All other reference numerals correspond to those of the previous figures.
  • FIG. 7 shows the method and device using non-nitrogen-containing powder and subsequently embroidering the porous surface layer.
  • the picture above shows the coating process using the example of a roller.
  • the non-nitrogen-containing Fe / Cr / Mn / powder 10 is sprayed onto the component by means of a spray gun, and a surface layer 37 is produced in this way.
  • the middle picture shows the embroidery process.
  • the coated component is in a furnace 38 for isothermal annealing in a nitrogen atmosphere.
  • 39 is the supply of nitrogen for embroidering the surface layer 37 (symbol and arrow N2).
  • 40 represents the nitrogen washing around the surface layer (trajectories with arrow).
  • the nitrogen partial pressure pN2 is indicated by arrows.
  • the lower picture shows the embroidery process in the case of the continuous embroidery process in longitudinal section.
  • the horizontal arrow indicates the feed direction.
  • 41 is an annular heating device (induction coil, resistance elements), which are flanked by annular annular shower heads 42. The latter serve to wash around the porous surface layer 37 for the purpose of nitriding. That way similar to a zone annealing process, the protective layer 2 is formed at the outlet from the heating device 41.
  • FIG. 8 shows the method and the device using nitrogen-containing powder and a laser beam as a thermal energy source.
  • a vertical laser beam 43 (symbol hv) is applied to the surface of component 1.
  • Feed 16 of the nitrogen-containing Fe / Cr / Mn / N powder 15 takes place obliquely to the laser beam 43 via the feed pipe 44.
  • the laser melting zone 45 is formed, which provides the protective layer 2 after solidification.
  • the direction of advance of component 1 is indicated by a horizontal arrow.
  • FIG. 9 shows the method and the device of a plant for hot isostatic pressing for the purpose of embroidering and surface compaction.
  • the upper picture shows the component after the porous surface layer 37 made of Fe / Cr / Mn (not containing nitrogen) has been applied.
  • the picture below shows the combined embroidery and compaction process.
  • 46 is a furnace and at the same time a pressure vessel for hot isostatic pressing and for embroidering the coated component.
  • 47 represents the supply of nitrogen (symbol N2 and arrow) for hot isostatic feeding.
  • the process is represented by the symbols pN2 with arrow for the nitrogen partial pressure.
  • the latter can be 1-2000 bar, the temperature between 400 and 1100 ° C.
  • a container of 1200 mm diameter and 3000 mm length made of steel intended for chemical processes with chloride-containing media was provided with a wear and corrosion-resistant protective layer 2 made of an austenitic material by plasma spraying on the inside (see substrate).
  • the metal powder 4 was injected into the device 3 - in the present case a plasma torch - and propellant 6 (in the present case an N2 / Ar mixture) with the aid of an inert gas shield 8 made of nitrogen in droplet form onto the substrate.
  • the plasma flame had a temperature of 10,000 ° C and the speed of the gas jet was approx. 100 m / s.
  • the metal particles were nitrided up to a nitrogen content of approx. 0.2% by weight.
  • the thickness of the protective layer 2 averaged 0.3 mm.
  • the connected load of the device 3 (plasma torch) was 80 kW, the coating capacity approx. 4 kg / h.
  • Example 1 A container according to Example 1 was coated on the inside. In principle, the procedure was as in Example 1.
  • the metal powder 4 had the same Composition. However, pure nitrogen was used as the propellant gas (carrier gas) 6 and the process was carried out completely under a nitrogen atmosphere in a protective gas chamber 9 under a pressure of 1.5 bar.
  • the nitrogen content of the protective layer 2 averaged 0.4% by weight.
  • a roller for the textile industry of 90 mm in diameter and 1100 mm in length made of low-alloy steel was provided with a protective layer 2 on its surface by plasma spraying.
  • a powder of similar composition and grain size - as described under Example 1 - was used as the starting material.
  • the non-nitrogen-containing powder was first subjected to a pressure heat treatment in a container 12 in a hot isostatic press with the supply of nitrogen 13. This treatment consisted of annealing at temperatures between 350 and 850 ° C for 1 hour and a pressure of 1.5-10 bar under a nitrogen atmosphere.
  • the embroidered powder was then conveyed as Fe / Cr / Mn / N powder 15 into a low-energy flame spray gun 3. Nitrogen was used as the partial gas 6. The gas velocity was approx.
  • the flame spray temperature approx. 2000 ° C.
  • the average thickness of the protective layer 2 reached the value of 0.5 mm.
  • the application rate was approx. 5 kg / h.
  • An average amount of nitrogen of 2.8% by weight could be determined analytically on the finished protective layer 2.
  • Example 3 a roller was provided with a protective layer 2.
  • the starting powder became 10 Fe / Cr / Mn for 2 hours in a hot isostatic press Subjected nitrogen atmosphere under a pressure of 5 bar at a temperature of 600 ° C.
  • the finished protective layer had a nitrogen content of 3.2% by weight.
  • a plate cylinder (cf. substrate 1) for a printing machine was provided with a protective layer 2 by high-speed flame spraying ("Jet Kote process").
  • the plate cylinder was made of steel and had a diameter of 275 mm and a length of 1700 mm.
  • the high-speed flame spray gun 17 was operated with propane (see fuel supply 20) and with oxygen (see oxygen supply 21). The flame temperature was approx. 2400 ° C. Nitrogen was used as the propellant gas (carrier gas) 22. Particle speeds of over 500 m / s were achieved in the metal / gas jet 7.
  • a protective gas shield 8 made of nitrogen was additionally used.
  • the contract performance was approx. 5 kg / h.
  • the protective layer 2 had a thickness of 0.8 mm and had a nitrogen content of 0.65% by weight.
  • a 30 mm thick steel plate (austenitic, corrosion-resistant steel) was provided with a 2 mm thick protective layer 2.
  • the submerged arc welding process using non-consumable tungsten electrodes 24 was used for this purpose.
  • the height of the loose powder chute averaged 6-8 mm.
  • a protective gas shield 8 made of nitrogen was used.
  • the current of the arc was approx. 160 amperes, the feed approx. 200 mm / min.
  • a welding bead of approx. 8 mm width was achieved.
  • the protective layer 2 had an average nitrogen content of 1.05% by weight.
  • a roller (substrate 1) was coated by the wire flame spraying process.
  • the ingot of the composition according to. Example 5 produced by rolling and drawing a wire of about 3 mm in diameter.
  • the wire flame spray gun 26 was operated with methane as fuel (20) and oxygen (21). The flame temperature was approx. 2200 ° C, the application rate 5 kg / h. Nitrogen was used as propellant 6. The gas speed was approximately 200 m / s. The nitrogen content of the 1.2 mm thick protective layer 2 was 0.6% by weight on average.
  • a roller (substrate 1) was provided with a wear-resistant protective layer 2 of 3 mm in thickness by the wire spraying method by arc spraying.
  • the roller intended for the paper industry had a diameter of 1800 mm and a length of 5000 mm and was made of a low-alloy steel.
  • Wire electrodes 30 made of a sheath wire of 3.2 mm outer diameter were used.
  • the core 31 of the sheathed wire consisting of pressed Fe / Cr / Mn / N powder with 1.2% by weight of nitrogen, had a diameter of 2.0 mm.
  • the sleeve 32 which had a wall thickness of 0.6 mm, consisted of a ductile iron with a very low carbon content.
  • the open arc 34 was charged with an atomizing propellant 36 supplied through an atomizing nozzle 35. Nitrogen was used for this. The whole thing was encased by a double protective shield 8. The material application rate was approx. 15 kg / h at a current of 150 A. With a nitrogen content of the core 31 of 1.2% by weight, the nitrogen content of the protective layer 2 was still 0.75% by weight on average.
  • a steel cylinder 500 mm in diameter and 3000 mm in length was coated using the flame spraying process.
  • a non-nitrogen-containing Fe / Cr / Mn powder 10 with approximately 18% by weight chromium and approximately 18% by weight manganese was used as the starting material.
  • the porous surface layer 37 had an average thickness of 2 mm and had a porosity of approximately 10% by weight.
  • the coated steel cylinder was placed in a gas-tight annealing furnace 38 and for 3 hours exposed to a flowing nitrogen atmosphere under a partial pressure pN2 of 0.5 bar.
  • the supply 39 of nitrogen was from the side and care was taken to ensure that the surface layer was flushed with nitrogen 40 on all sides.
  • the annealing temperature was 750 ° C. and was kept constant (isothermal annealing).
  • the nitrogen content of the finished protective layer was determined to be 0.6% by weight.
  • a steel cylinder was coated according to example 9.
  • the porous surface layer 37 was then embroidered on by the continuous process.
  • the steel cylinder (substrate 1) was passed through a heating device 41 flanked by annular nitrogen showers 42 and consisting of an induction coil.
  • the surface layer 37 was brought to a temperature of 1000 ° C. in a short time.
  • the feed was 60 mm / min.
  • the average residence time was 2 minutes.
  • the nitrogen content of the finished protective layer reached the value of 0.4% by weight.
  • the coating was alternatively carried out by the plasma spray process. After embroidering in a continuous process, practically the same results were achieved.
  • a plate made of low-alloy steel with a thickness of 15 mm was coated with nitrogen-containing Fe / Cr / Mn / N powder 15 via a powder feed tube 44 and locally melted and coated with the aid of a laser beam 43.
  • the powder in the laser melting zone 45 was firmly connected to the substrate 1 by melt metallurgy. With a nitrogen content of approx. 1% by weight of the powder 15, the nitrogen content of the finished protective layer was due to the high cooling rate still 0.8% by weight on average.
  • the feed was 80 mm / min.
  • a roller 80 mm in diameter and 1200 mm in length was provided with a porous surface layer 37 made of Fe / Cr / Mn (not containing nitrogen) by the flame spraying process.
  • the component 1 was then placed in a hot isostatic press 46 and compressed by embroidering under pressure with the supply of nitrogen as compressed gas under 10 bar at a temperature of 700.degree. The process took 1 hour.
  • the result was a protective layer 1.2 mm thick with a nitrogen content of 1.1% by weight.
  • a plasma-sprayed surface layer 37 was assumed. The result was similar.
  • the invention is not restricted to the exemplary embodiments.
  • the process for producing a protective layer with high wear and corrosion resistance from an austenitic iron-based alloy on the surface of a component serving as a substrate by thermal spraying is carried out by selecting the parameters such that the protective layer in its final state has a nitrogen content of at least 0. 2% by weight, the starting material used being an austenitic powder produced by atomizing a liquid metal jet by means of a gas jet and by low-energy flame spraying or by high-speed flame spraying or by plasma spraying under nitrogen or a nitrogen / argon mixture as propellant gas onto the surface of the component is applied and preferably a powder with 18% by weight of chromium and 18% by weight of manganese is used as the starting material.
  • the powder is obtained by annealing in a nitrogen atmosphere before Spraying brought to a nitrogen content of 1.2 wt .-%, wherein it is preferably nitrided with a particle size of 5-45 microns in bulk and for at least 1 hour under a pressure of 1-1000 bar at a temperature of 300 -800 ° C exposed to a still nitrogen atmosphere and brought to the nitrogen content of 1.2 wt .-%, cooled and sieved.
  • the procedure is advantageously such that nitrogen-containing powder is used as the starting material and is applied to the surface of the component by the high-speed flame spraying method at a speed of at least 400 m / s or is applied to the surface of the component by the submerged arc welding method that instead of the consumable welding wire a non-consumable tungsten electrode or a plasma torch under a protective gas or nitrogen atmosphere and instead of the slag-forming ceramic powder, the nitrogen-containing iron-based alloy powder is used.
  • a nitrogen-containing wire made of a block or ingot of 1.5-4 mm diameter is used as the starting material and after the wire spraying process by flame spraying or arc spraying under nitrogen, forming gas or a nitrogen / argon mixture onto the surface of the Component applied or that a sheath wire consisting of a core of nitrogen-containing austenitic metal powder and a jacket made of a ductile metal or an alloy or a plastic is used and is applied to the surface of the component by the wire spraying method by arc spraying.
  • the component is first coated with a powder of an ordinary, non-nitrogenous material by the plasma spraying process or by the high-speed flame spraying process and then the coated workpiece in an oven under a nitrogen atmosphere annealed under isothermal conditions or sent through an inductive or resistance heating device according to the continuous flow principle, in which case the surface is continuously annealed for 3-20 seconds at a temperature of 700-900 ° C and the annealing zone is simultaneously flushed with nitrogen.
  • the procedure is advantageously such that nitrogen-containing powder of an iron-based alloy is applied to the surface of the component by means of a laser beam, in such a way that the surface and the powder particles are easily melted by the laser beam and the surface coated in this way is cooled rapidly by heat removal after the Is subjected to the inside of the workpiece.
  • the component is provided with a porous surface layer by thermal spraying with an ordinary, non-nitrogen-containing material and the surface of the coated workpiece is then subsequently compressed and nitrided using nitrogen as compressed gas by hot isostatic pressing.
  • the component is coated by plasma spraying under a nitrogen gas jacket, by only bringing the molten metal particles into contact with nitrogen and thereby loading them with the necessary nitrogen content, the plasma spraying preferably being carried out in a protective gas chamber under a pressure of 0.5 bar nitrogen is carried out.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Claims (21)

  1. Procédé de fabrication d'une couche de protection (2), avec une résistance à l'usure et à la corrosion élevée, réalisée en un alliage à base de fer austénitique, sur la surface d'un élément de construction (1) servant de substrat, par projection thermique d'un matériau de départ (10; 15; 27; 31) correspondant, avec un gaz propulseur contenant de l'azote, caractérisé en ce que la couche de protection (2) présente à son état final une teneur en azote d'au moins 0,2 % en poids, par utilisation d'un matériau de départ à teneur enrichi en azote, ou par
    enrichissement en azote lors de l'application sous atmosphère protectrice contenant de l'azote et sous pression correspondante, ou par enrichissement en azote de la couche de protection appliquée, sous atmosphère contenant de l'azote, à la température correspondante et sous la pression correspondante.
  2. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ (10; 15) est une poudre austénitique, fabriquée par pulvérisation d'un jet de métal liquide, au moyen d'un jet de gaz; et la pulvérisation thermique étant une pulvérisation à la flamme, sous faible énergie, une pulvérisation à la flamme à haute vitesse, ou une pulvérisation au plasma, avec utilisation d'azote ou d'un mélange azote/argon, à titre de gaz propulseur (22).
  3. Procédé selon la revendication 2, caractérisé en ce que le matériau de départ (10; 15; 27; 31) est une poudre d'un alliage à base de fer, à 18 % en poids de chrome et à 18 % en poids de manganèse.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que la poudre est enrichie en azote, à une teneur en azote de 0,4 à 1,2 % en poids, par recuit sous atmosphère d'azote, avant la projection thermique.
  5. Procédé selon la revendications 4, caractérisé en ce que la poudre devant être enrichie en azote est placée, avec une taille particulaire comprise entre 5 et 45 µm, en tas et en vrac, dans un récipient (12) ouvert et est exposée, au moins pendant une heure, sous une pression comprise entre 1 et 1000 bar, à une température de 300 à 800°C, à une atmosphère calme d'azote, est amenée de cette manière à la teneur en azote souhaitée, refroidie et tamisée.
  6. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ (10; 15) est une poudre contenant de l'azote; et
    la pulvérisation thermique est une pulvérisation à la flamme à haute vitesse;
       la poudre (11) est appliquée sur la surface de l'élément de construction (1) en un jet métal/gaz (7) à une vitesse d'au moins 400 m/s.
  7. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ (27) est une fil métallique de diamètre 1,5 à 4 mm, contenant de l'azote, fabriqué à partir d'un bloc ou d'une barre; et
    la pulvérisation thermique est une pulvérisation à la flamme sur fil, avec utilisation d'azote, gaz de formation-activation ou d'un mélange azote/argon, servant de gaz propulseur (22).
  8. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ est une poudre austénitique contenant de l'azote, amenée, à titre de noyau (31), dans un fil de gainage faisant office d'enveloppe (32) et composé d'un métal ductile ou d'un alliage ou d'une matière synthétique; et
    la pulvérisation thermique est une pulvérisation sur fil, effectuée par pulvérisation à l'arc électrique, en utilisant de l'azote comme gaz propulseur (22).
  9. Procédé selon la revendication 1, caractérisé en ce que l'élément de construction (1) est d'abord recouvert d'une poudre (37) en matériau de départ (11) ne contenant pas d'azote, suivant le procédé de pulvérisation au plasma ou suivant le procédé de pulvérisation à la flamme à haute vitesse; et
    l'élément de construction revêtu est ensuite porté à incandescence dans un four (38), sous atmosphère d'azote et dans des conditions isothermes, ou passé, suivant le principe de circulation, dans un dispositif de chauffage (41) chauffé par induction ou par résistance, où, dans ce dernier cas, la surface est portée à incandescence par zones de façon continue, pendant 3 à 20 s, à une température de 700 à 900 °C, et la zone d'incandescence est simultanément balayée avec de l'azote (42).
  10. Procédé selon la revendication 1, caractérisé en ce que l'élément de construction (1) est d'abord recouvert d'une poudre (37) en matériau de départ (11) ne contenant pas d'azote, avec une couche de surface poreuse; et
    la couche de surface de l'élément de construction (1) est ensuite simultanément recomprimée et enrichie en azote, avec utilisation d'azote sous forme de gaz sous pression , par compression isostatique opérée à chaud.
  11. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ (10) ne contient pas d'azote et la pulvérisation thermique est une pulvérisation au plasma,
    une enveloppe protectrice en azote étant placée autour des particules métalliques rendues liquides par la fusion.
  12. Procédé selon la revendication 11, caractérisé en ce que la pulvérisation au plasma est effectuée dans une chambre de gaz protecteur (9), sous une pression d'azote de 0,5 bar.
  13. Procédé de fabrication d'une couche de protection (2), avec une résistance à l'usure et à la corrosion élevée, réalisée en un alliage à base de fer austénitique, sur la surface d'un élément de construction (1) servant de substrat, par soudage à l'arc électrique sous flux de poudre inférieur, comportant les étapes de :
       recouvrement de l'élément de construction (1) d'une masse pulvérulente en vrac (23), en un matériau de départ (16) correspondant, contenant de l'azote; et
       soudage de la masse pulvérulente en vrac (23) par application d'un arc électrique (25) entre des électrodes en tungstène (24) non-consommables;
       de manière que la couche de protection (2) présente à son état final une teneur en azote d'au moins 0,2 % en poids.
  14. Procédé de fabrication d'une couche de protection (2), avec une résistance à l'usure et à la corrosion élevée, réalisée en un alliage à base de fer austénitique, sur la surface d'un élément de construction (1) servant de substrat, par irradiation laser, comportant les étapes de :
       irradiation par un rayon laser (43) sur la surface de l'élément de construction (1); et
       amenée d'un matériau de départ (15) correspondant, contenant de l'azote, pour constituer sur la surface une zone protectrice laser (45), qui constitue après solidification la couche de protection (2);
       la surface de l'élément de construction (1), ainsi que les particules de poudre (15) étant légèrement fondues par le rayon laser et la surface recouverte de cette manière étant soumise à un refroidissement rapide, par extraction de chaleur en direction de l'intérieur de l'élément de construction (1);
       de sorte que la couche de protection présente à son état final une teneur en azote d'au moins 0,2 % en poids.
  15. Elément de construction (1) métallique, portant sur lui une couche de protection (2) en alliage austénitique à base de fer, présentant une résistance à l' usure et à la corrosion élevée, fabriqué suivant le procédé selon les revendications 1 à 14 et 21;
       caractérisé en ce que la couche de protection (2) présente une teneur en azote d'au moins 0,2 % en poids.
  16. Elément de construction (1) métallique, avec une couche de protection (2) selon la revendication 15, caractérisé par la composition suivante de la couche de protection (2) :
       Cr = 18,25 % en poids
       Mn = 19,41 % en poids
       Ni = 0,70 % en poids
       Mo = 0,06 % en poids
       Si = 0,42 % en poids
       C = 0,063 % en poids
       P ≦ 0,03 % en poids
       S ≦ 0,004 % en poids
       N = 0,80 % en poids
       Fe = le reste.
  17. Elément de construction (1) métallique, avec une couche de protection (2) selon la revendication 15, caractérisé par la composition suivante de la couche de protection (2) :
       Cr = 18,50 % en poids
       Mn = 0,84 % en poids
       Ni = 13,50 % en poids
       Mo = 4,58 % en poids
       Si = 1,73 % en poids
       C = 0,03 % en poids
       N = 0,55 % en poids
       Fe = le reste.
  18. Elément de construction (1) métallique, avec une couche de protection (2) selon la revendication 15, caractérisé par la composition suivante de la couche de protection (2) :
       Cr = 17,00 % en poids
       Mn = 2,40 % en poids
       Ni = 12,90 % en poids
       Mo = 4,30 % en poids
       Si = 1,40 % en poids
       C = 0,10 % en poids
       N = 0,71 % en poids
       Fe = le reste.
  19. Elément de construction (1) métallique, avec une couche de protection (2) selon la revendication 15, caractérisé par la composition suivante de la couche de protection (2) :
       Cr = 20,80 % en poids
       Mn = 5,30 % en poids
       Ni = 3,00 % en poids
       Si = 1,60 % en poids
       C = 0,06 % en poids
       N = 0,85 % en poids
       Fe = le reste.
  20. Elément de construction (1) métallique, avec une couche de protection (2) selon la revendication 15, caractérisé par la composition suivante de la couche de protection (2) :
       Cr = 12,86 % en poids
       Mn = 18,85 % en poids
       Ni = 1,74 % en poids
       Mo = 0,70 % en poids
       Si = 0,56 % en poids
       C = 0,059 % en poids
       N = 0,24 % en poids
       Fe = le reste.
  21. Procédé selon la revendication 1, caractérisé en ce que le matériau de départ (27) est un fil métallique présentant une teneur en azote ou ne comportant pas d'azote; et la pulvérisation par voie thermique, est une pulvérisation du fil au plasma qui est effectuée avec utilisation d'azote comme gaz propulseur (6).
EP90109028A 1987-06-26 1990-05-14 Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué Expired - Lifetime EP0456847B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE3816310A DE3816310A1 (de) 1987-06-26 1988-05-13 Verfahren zur anreicherung von titan in der unmittelbaren oberflaechenzone eines bauteils aus einer mindestens 2,0 gew.-% titan enthaltenden nickelbasis-superlegierung und verwendung der nach dem verfahren angereicherten oberflaeche
JP63151353A JPS6417846A (en) 1987-06-26 1988-06-21 Method for directly enriching titanium in surface zone of structural material and titanium enriched surface zone
EP90109028A EP0456847B1 (fr) 1987-06-26 1990-05-14 Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué
DE59007940T DE59007940D1 (de) 1987-06-26 1990-05-14 Verfahren zur Herstellung einer Schutzschicht mit hohem Verschleiss- und Korrosionswiderstand aus einer austenitischen Eisenbasislegierung und nach dem Verfahren hergestellte Schutzschicht.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242587 1987-06-26
EP90109028A EP0456847B1 (fr) 1987-06-26 1990-05-14 Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué

Publications (2)

Publication Number Publication Date
EP0456847A1 EP0456847A1 (fr) 1991-11-21
EP0456847B1 true EP0456847B1 (fr) 1994-12-07

Family

ID=40133659

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90109028A Expired - Lifetime EP0456847B1 (fr) 1987-06-26 1990-05-14 Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué

Country Status (3)

Country Link
EP (1) EP0456847B1 (fr)
JP (1) JPS6417846A (fr)
DE (2) DE3816310A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019168893A1 (fr) * 2018-02-27 2019-09-06 Somnio Global Holdings, Llc Articles avec couche de protection en alliage d'azote et procédés de fabrication de ceux-ci

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT404905B (de) * 1990-08-03 1999-03-25 Andritz Ag Maschf Anlage zum aufbringen einer spritzschicht auf eine ebene oder gekrümmte fläche eines werkstückes
GB9200880D0 (en) * 1992-01-16 1992-03-11 Atomic Energy Authority Uk A method of producing a surface coating upon a substrate
JPH07119420A (ja) * 1993-10-27 1995-05-09 Fuji Oozx Inc チタン又はチタン合金製エンジンバルブの表面処理方法
DE4447514C2 (de) * 1994-01-14 1996-07-25 Castolin Sa Verfahren zur Herstellung eines Hilfsmittels zum thermischen Spritzen und seine Verwendung als Pulverfüllung von Fülldraht
US5761720A (en) * 1996-03-15 1998-06-02 Rendition, Inc. Pixel engine pipeline processor data caching mechanism
US6074022A (en) * 1998-03-23 2000-06-13 Caterpillar Inc. Track bushing having arc welded end treatment for improved abrasion and corrosion resistance, and a process for making the same
DE19840951A1 (de) * 1998-09-08 2000-03-09 Jagenberg Papiertech Gmbh Rakelstange für eine Beschichtungsvorrichtung
DE19960353A1 (de) * 1999-12-14 2001-06-21 Dechema Deutsche Gesellschaft Fuer Chemisches Apparatewesen, Chemische Technik Und Biotechnologie Ev Verfahren zur Herstellung einer Diffusionsbarriere zur Lebensdauererhöhung von Hochtemperatur-Schutzschichten
DE19963223A1 (de) * 1999-12-27 2001-06-28 Volkswagen Ag Stahlhaltiges Material für eine Plasmaabscheidung
DE10033980A1 (de) * 2000-07-13 2002-01-24 Voith Paper Patent Gmbh Verfahren zur Vorbehandlung einer Faserstoffsuspension sowie Garnitur zur Durchführung des Verfahrens
US6833203B2 (en) † 2002-08-05 2004-12-21 United Technologies Corporation Thermal barrier coating utilizing a dispersion strengthened metallic bond coat
EP1522375A1 (fr) * 2003-10-06 2005-04-13 Siemens Aktiengesellschaft Procédé de fabrication d'un système multicouche
RU2486277C2 (ru) * 2010-11-02 2013-06-27 Федеральное государственное унитарное предприятие "Научно-производственный центр газотурбостроения "Салют" (ФГУП "НПЦ газотурбостроения "Салют") Способ формирования покрытия на рабочей охлаждаемой лопатке газовой турбины из никелевого сплава
DE102011084608A1 (de) * 2011-10-17 2013-04-18 Ford-Werke Gmbh Plasmaspritzverfahren
LV14659B (lv) * 2012-08-07 2013-06-20 Toms Torims Iekārta un metode kloķvārpstu gultņu kakliņu virsmu remontam un atjaunošanai, pielietojot uzkausēšanu ar lāzeru
CN104087885B (zh) * 2014-06-17 2016-09-14 宁国东方碾磨材料股份有限公司 一种耐腐蚀涂层磨段
WO2020176616A1 (fr) * 2019-02-26 2020-09-03 Somnio Global Holdings, Llc Poudre d'acier à haute teneur en azote et procédés de fabrication de celle-ci
CN120350337B (zh) * 2025-06-19 2025-10-10 中国航发沈阳黎明航空发动机有限责任公司 一种γ-TiAl材料涡轮叶片锯齿冠耐磨涂层镀覆方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR719270A (fr) * 1931-06-30 1932-02-03 Changement des qualités de la surface d'organes ou de pièces quelconques par l'apport, la fixation et, s'il y a lieu, le traitement d'un métal auquel on garde en tout ou en partie ses qualités d'origine
DE942484C (de) * 1942-10-31 1956-05-03 Hans Biel Verfahren zur Herstellung von Metallschichten durch Zerstaeubung
GB1182242A (en) * 1966-02-11 1970-02-25 United States Borax Chem Improvements in or relating to Nitrides.
DE3715325A1 (de) * 1987-05-08 1988-11-24 Castolin Sa Verfahren zum herstellen von gleitflaechen auf teilen von fahrzeugmotoren
US4999052A (en) * 1988-10-05 1991-03-12 United Kingdon Atomic Energy Authority Method of producing nitrogen-strengthened alloys

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Handbook of Stainless Steels, McGraw-Hill Book Company, 1977, Seite 1-7 und 4-14 *
JIS H 9301, 1977 *
Oberflächenveredeln und Plattieren von Metallen, VEB Verlag für Grundstoffindustrie 1978, Seiten 239-248 *
Stahlschlüssel, 1986, Seiten 336 und 367 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019168893A1 (fr) * 2018-02-27 2019-09-06 Somnio Global Holdings, Llc Articles avec couche de protection en alliage d'azote et procédés de fabrication de ceux-ci

Also Published As

Publication number Publication date
DE3816310A1 (de) 1989-01-12
JPS6417846A (en) 1989-01-20
DE59007940D1 (de) 1995-01-19
EP0456847A1 (fr) 1991-11-21

Similar Documents

Publication Publication Date Title
EP0456847B1 (fr) Procédé pour la fabrication d'un revêtement protecteur, résistant à l'usure et la corrosion, en alliage de fer austénitique et revêtement ainsi fabriqué
DE2632739C3 (de) Verfahren zum thermischen Aufspritzen eines selbsthaftenden Nickel-Aluminium- oder-Nickel-Titan-Überzugs auf ein Metallsubstrat
DE69108963T2 (de) Verschleissfeste Titannitridbeschichtung und Verfahren zum Aufbringen.
DE1446207B2 (de) Aus mehreren bestandteilen bestehendes flammspritzmaterial
DE4321673A1 (de) Thermisches Sprühen von Zusammensetzungen aus Metall und Feststoffschmiermitteln unter Verwendung von Draht als Ausgangsmaterial
DE3433698A1 (de) Verfahren zur oberflaechenbehandlung eines werkstueckes
DE2818304A1 (de) Verfahren und vorrichtung zum plasmaspritzen eines ueberzugmaterials auf eine unterlage
EP0915184A1 (fr) Procédé de fabrication d'une couche de céramique sur un substrat métallique
DE3306142A1 (de) Verfahren zur herstellung eines zweiphasigen oder mehrphasigen metallischen materials
DE2208070A1 (de) Plasma-flammgespritzte titancarbidwerkzeugstahl-ueberzuege auf metallsubstraten, die so gebildeten verbundwerkstoffe und verfahren zu deren herstellung
WO2001079575A1 (fr) Acier allie a l'azote, compacte par pulverisation, procede permettant de le produire et materiau composite produit a partir dudit acier
DE102020003426A1 (de) Verfahren und Vorrichtung zur additiven Fertigung unter Schutzgas
EP3314033B1 (fr) Alliage ferreux destiné à la réalisation de couches protectrices anti-usure appliquées par voie thermique
DE2100237A1 (de) Wolframlegierung und Verfahren zu ihrer Herstellung
DE2043275A1 (de) Verfahren und Vorrichtung zum Her stellen hochgradig reiner Metallpulver
DE2725752A1 (de) Verfahren zur oberflaechenbehandlung von metall in einem wirbelbettsystem
DE3726073C1 (de) Verfahren zur Herstellung von duennwandigem Halbzeug und dessen Verwendungen
DE2715914C2 (fr)
DE102021112151A1 (de) Vorrichtung und Verfahren zum Herstellen von Metallpulver unter Verwendung einer Induktions- und einer Zwischenspule
DE69022064T2 (de) Verfahren zum ändern eines oberflächenbereiches eines werkstückes.
DE60217380T2 (de) Hitzbeständiger stahl mit verbesserter katalytischer karbonatations- und verkokungsbeständigkeit
DE952586C (de) Verfahren zur Herstellung von spratzigen Metallpulvern
DE2818720B1 (de) Verfahren und Vorrichtung zur Herstellung von Metallpulver
DE4139956C2 (de) Verfahren zur Herstellung von verschleißbeständigen Borierschichten auf metallischen Gegenständen sowie Metallgegenstand mit einer verschleißbeständigen Borierschicht
DE102009004201A1 (de) Lichtbogendrahtspritzverfahren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19910515

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19930129

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19941207

Ref country code: GB

Effective date: 19941207

Ref country code: NL

Effective date: 19941207

Ref country code: FR

Effective date: 19941207

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19941207

REF Corresponds to:

Ref document number: 59007940

Country of ref document: DE

Date of ref document: 19950119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950307

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19941207

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: CASTOLIN S.A.

Effective date: 19950907

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBL Opposition procedure terminated

Free format text: ORIGINAL CODE: EPIDOS OPPC

PLBM Termination of opposition procedure: date of legal effect published

Free format text: ORIGINAL CODE: 0009276

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION PROCEDURE CLOSED

27C Opposition proceedings terminated

Effective date: 19960408

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970603

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970612

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990302

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO