EP0456847A1 - 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

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Publication number
EP0456847A1
EP0456847A1 EP90109028A EP90109028A EP0456847A1 EP 0456847 A1 EP0456847 A1 EP 0456847A1 EP 90109028 A EP90109028 A EP 90109028A EP 90109028 A EP90109028 A EP 90109028A EP 0456847 A1 EP0456847 A1 EP 0456847A1
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Prior art keywords
weight
nitrogen
powder
component
spraying
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German (de)
English (en)
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EP0456847B1 (fr
Inventor
Clemens M. Dr. Verpoort
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BERNEX GmbH
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BERNEX GmbH
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Priority to DE3816310A priority Critical patent/DE3816310A1/de
Priority to JP63151353A priority patent/JPS6417846A/ja
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Priority to DE59007940T priority patent/DE59007940D1/de
Priority to EP90109028A priority patent/EP0456847B1/fr
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    • 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 of an austenitic iron-based alloy on the surface of a component serving as a substrate by thermal spraying and a protective layer prepared by the method.
  • the pressure-electro-slag remelting process makes it possible to produce austenitic steels with a very high nitrogen content.
  • the molten steel is kept under 30 bar nitrogen overpressure for a long time and nitrogen is added to the melt via silicon nitride.
  • nitrogen-alloyed melts are cooled under pressure, the high, dissolved nitrogen content in the workpiece is maintained. It is possible to produce forgings with nitrogen contents of 0.5% by weight. Higher nitrogen contents can not be realized by melt metallurgy, since correspondingly high silicon nitride additions, which would lead to an excessively high Si content of the steel, have to be added for the introduction of nitrogen.
  • the embroidered components are characterized by a very high strength due to the interstitial nitrogen storage. With increasing nitrogen content, both the yield strength and the tensile strength increase linearly. The toughness of the material is not reduced with increasing nitrogen content. The strength of this class of material, defined as the product of yield strength and fracture toughness, is higher than that of all conventional steels. Another important feature of the technical use of these materials is their outstanding resistance to stress corrosion cracking. It turns out that the nitrogen takes over as an alloying element a protective effect, as it has previously been known only from chromium.
  • the melt of the austenitic steels is atomized in a gas atomization plant. If nitrogen is used as the atomizing gas, a slight nitridation of the powder (about 0.1-0.2 wt .-%) is achieved.
  • the nitrogen concentration of the powder can by the hot isostatic pressing process described in patent DE-C-3624622 can be further increased. Nitrogen contents of more than 1.2% by weight of nitrogen in the powder can be achieved by the process described there.
  • Thermal spraying is ansich known from many publications. These include flame spraying, plasma spraying, high-speed flame spraying, etc.
  • the materials which are to build up the surface layer are supplied to the corresponding apparatus both in wire, ribbon and powder form.
  • the methods are to be used, which use a laser beam as an energy source for heating and melting of the materials.
  • the invention has for its object to provide a method for producing a wear and corrosion-resistant surface layer of austenitsichen iron base alloy on a component serving as a substrate, in principle, the thermal spraying should be used.
  • the protective layer should have high mechanical strength even at higher temperatures, be stable for a long time and must not change chemically and physically in the course of operation.
  • the method should be inexpensive, reproducible and feasible by simple means. This object is achieved in that in the aforementioned method, the protective layer in its final state has a nitrogen content of min. 0.2% by weight.
  • Fig. 1 shows the method principle in general and a schematic representation of a powder injection device.
  • all-round protective gas atmosphere of nitrogen. 1 is to be coated, serving as a substrate component, in the present case the example of a roller or drum.
  • 2 is the wear and corrosion resistant metallic protective layer.
  • the figure shows the beginning of the application of the protective layer 2 on the component 1.
  • 3 illustrates the apparatus for thermal application of the thermal protection layer in general.
  • the reference numeral 3 is in principle for any type of device (spray gun, plasma torch, arc, etc.). In the present case, the figure applies specifically to the flame spray gun.
  • the reference numeral 4 stands for the metal powder in general. 5 indicates the supply of metal powder marked by an arrow in general.
  • FIG. 6 is the propellant gas (carrier gas) whose flow direction is indicated by an arrow.
  • a propellant are generally nitrogen or a nitrogen / argon mixture (symbols N2 or N2 / Ar) in question.
  • FIG. 7 illustrates the metal / gas jet being spun onto the surface of the component 1.
  • 8 is a shield, indicated by arrows with the symbol N2.
  • the inert gas shield consists of a nitrogen / noble gas mixture or of a pure noble gas.
  • the reference numeral 9 alternatively indicates a protective gas chamber (dash-dotted italic line using the example of a container using nitrogen as inert gas).
  • FIG. 2 the method and the apparatus for nitriding and for applying the protective layer is shown schematically.
  • 10 is Fe / Cr / Mn powder (non-nitrogenous), which in the present case serves as the starting material.
  • Figure 11 illustrates the Fe / Cr / Mn powder feed (indicated by vertical arrow) into the hot isostatic press.
  • 12 is an open container for heat treating the powders.
  • 13 means the supply of nitrogen N2 to the container 12 for the purpose of nitriding the powder 10.
  • the reference numeral 15 denotes Fe / Cr / Mn / N powder (containing nitrogen) and the vertical arrow 16 indicates the supply of this powder to the apparatus 3 (spray gun).
  • the remaining reference numerals 1, 2, 6, 7, 8 are consistent with those of FIG.
  • Fig. 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 Figs. 1 and 2 and can be taken from the latter.
  • 17 is a high-speed flame spray gun having 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, the oxygen supply (symbol O2). Of course, other hydrocarbons (propane, propylene, etc.) can be used as fuel.
  • 22 represents the inert powder propellant, which usually consists of nitrogen (symbol N2) or a nitrogen / argon mixture (symbol N2 / Ar).
  • the supply of gaseous media is indicated by arrows.
  • Fig. 4 shows the method and apparatus using nitrogenous powder and a submerged arc.
  • the component 1 is covered with a loose powder bed 23 of Fe / Cr / Mn / N powder. Under this layer of powder, a hidden arc 25 burns between non-consumable tungsten electrodes 24.
  • the process is somewhat similar to submerged arc welding, except that instead of the consumable wire forming the weld metal as tungsten rods and instead of the slag-forming inert powder metal powder forming the surface layer forms, is provided.
  • the remaining reference symbols s. FIGS. 1 and 3.
  • FIG. 5 schematically illustrates the method and apparatus 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.
  • Fig. 26 is a common wire flame spray gun into which an Fe / Cr / Mn / N wire 27 is axially inserted.
  • 28 (arrow) represents the supply of a 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.
  • Figure 6 relates to the method and apparatus using nitrogen-containing cored wires as electrodes and an open arc.
  • sprayed wires of solid Fe / Cr / Mn / N steel with high nitrogen content can also be used.
  • the wire electrode 30 of sheath wire is shown enlarged in the figure below again in longitudinal section.
  • the sheath wire is composed of a Fe / Cr / Mn / N powder core of comparatively high nitrogen content and a ductile metal or plastic shell.
  • 33 illustrates the supply of the sheathed wire 30 to be melted.
  • the open arc 34 is burning.
  • 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 preceding figures.
  • Figure 7 shows methods and apparatus using non-nitrogenous powder and post-nitriding the porous surface layer.
  • the upper picture shows the coating process using the example of a roller.
  • the non-nitrogen-containing Fe / Cr / Mn / powder 10 is spin-coated onto the component by means of a spray gun and in this way a surface layer 37 is produced.
  • the middle picture shows the nitriding process.
  • the coated component is located in an oven 38 for isothermal annealing in a nitrogen atmosphere.
  • 39 is the supply of nitrogen to nitrify the surface layer 37 (symbol and arrow N2).
  • 40 represents the nitrogen lapping of the surface layer (trajectories with arrow).
  • the nitrogen partial pressure pN2 is indicated by arrows.
  • the lower picture shows the nitriding process in the case of the pass-stitch method in longitudinal section.
  • the horizontal arrow indicates the feed direction.
  • 41 is an annular heating device (induction coil, resistance elements), which are flanked by likewise annular nitrogen sprays 42. The latter serve for flushing the porous surface layer 37 for the purpose of nitriding. This way will Similar to a zone annealing process, the protective layer 2 is formed at the exit from the heating device 41.
  • Figure 8 shows the method and apparatus using nitrogenous powder and a laser beam as the thermal energy source.
  • the surface of the component 1 is acted upon by a perpendicularly incident laser beam 43 (symbol hv).
  • Feed 16 of the nitrogen-containing Fe / Cr / Mn / N powder 15 takes place at an angle to the laser beam 43 via the feed tube 44.
  • the laser fusion zone 45 is formed, which supplies the protective layer 2 after solidification.
  • the feed direction of the component 1 is indicated by a horizontal arrow.
  • FIG. 9 shows the method and the device of a system for hot isostatic pressing for the purpose of embroidering and surface compacting.
  • the upper picture shows the component after application of the porous surface layer 37 of Fe / Cr / Mn (non-nitrogenous).
  • the picture below shows the combined nitriding and compaction process.
  • 46 is a furnace and at the same time a pressure vessel for hot-isostatic pressing and for embroidering of the coated component.
  • 47 illustrates the supply of nitrogen (symbol N2 and arrow) for hot isostatic pressing.
  • 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.
  • the metal powder 4 was in the device 3 - in the present case, a plasma torch - injected and spun by means of propellant gas 6 (in the present case, a N2 / Ar mixture) with the aid of a nitrogen shielding gas shield 8 in droplet form on the substrate.
  • the plasma flame had a temperature of 10,000 ° C and the speed of the gas jet was about 100 m / s.
  • the metal particles were nitrided up to a nitrogen content of about 0.2% by weight.
  • the thickness of the protective layer 2 averaged 0.3 mm.
  • the connection power of the device 3 (plasma torch) was 80 kW, the coating power about 4 kg / h.
  • Example 1 A container according to Example 1 was coated on its inside. In principle, the procedure was as in Example 1.
  • the metal powder 4 had the same Composition.
  • the nitrogen content of the protective layer 2 was on average 0.4% by weight.
  • a roll for the textile industry of 90 mm diameter and 1100 mm length made of low-alloy steel was provided by plasma spraying on its surface with a protective layer 2.
  • the starting material used was a powder of similar composition and particle size as described in Example 1.
  • the non-nitrogenous powder was first subjected to a pressure heat treatment in a container 12 in a hot isostatic press under 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 fed as Fe / Cr / Mn / N powder 15 into a low energy flame spray gun 3. As Teibgas 6 nitrogen was used.
  • the gas velocity was about 200 m / s, the flame spraying temperature about 2000 ° C.
  • the average thickness of the protective layer 2 reached the value of 0.5 mm.
  • the order performance was approx. 5 kg / h.
  • an average nitrogen content of 2.8% by weight could be determined analytically.
  • Example 3 a roller was provided with a protective layer 2.
  • the starting powder was 10 Fe / Cr / Mn for 2 hours in a hot isostatic press a Nitrogen atmosphere under a pressure of 5 bar at a temperature of 600 ° C subjected.
  • the finished protective layer had a nitrogen content of 3.2% by weight.
  • the high speed flame spray gun 17 was operated with propane (compare fuel supply 20) and oxygen (compare oxygen supply 21). The flame temperature was about 2400 ° C. Nitrogen was used as propellant (carrier gas) 22. Particle velocities of more than 500 m / s were achieved in the metal / gas jet 7. In order to protect the metal / gas jet 7, in which gas velocities up to 1500 m / s occurred, an inert gas shield 8 made of nitrogen was additionally used. The order performance was about 5 kg / h.
  • the protective layer 2 had a thickness of 0.8 mm and had a nitrogen content of 0.65 wt .-%.
  • a 30 mm thick steel plate (austenitic, corrosion-resistant steel) was provided with a 2 mm thick protective layer 2.
  • the submerged arc welding method using non-consumable tungsten electrodes 24 was used.
  • a nitrogen-containing Fe / Cr / Mn / N powder 15 with 1.2 wt .-% nitrogen and a max. Particle size of 60 microns used.
  • the height of the loose powder bed averaged 6-8 mm.
  • a protective gas shield 8 made of nitrogen was used.
  • the current of the arc was about 160 amps, the feed about 200 mm / min. It was achieved a weld bead of about 8 mm wide.
  • 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 method.
  • Example 5 produced by rolling and drawing a wire of about 3 mm diameter.
  • the wire flame spray gun 26 was operated with methane as fuel (20) and oxygen (21).
  • the flame temperature was about 2200 ° C, the order power 5 kg / h.
  • As propellant gas 6, nitrogen was used.
  • the gas velocity was about 200 m / s.
  • the nitrogen content of the 1.2 mm thick protective layer 2 was on average 0.6% by weight. It was worked with a shielding gas shield 8 made of nitrogen.
  • a roller (substrate 1) was provided with a wear-resistant protective layer 2 of 3 mm thickness by the arc-spraying method.
  • the roll intended for the paper industry had a diameter of 1800 mm and a length of 5000 mm and consisted of a low-alloyed steel.
  • Wire electrodes 30 were used from a sheath wire of 3.2 mm outside diameter.
  • the core 31 of the sheath wire made of pressed Fe / Cr / Mn / N powder containing 1.2% by weight of nitrogen had a diameter of 2.0 mm.
  • the 0.6 mm wall thickness envelope 32 was a very low ductility ductile iron.
  • the open arc 34 was charged with a sputtering gas 36 supplied through a sputtering nozzle 35.
  • Nitrogen was used for this. The whole thing was covered by a double shield 8 gas shield. The material application performance was at a current of 150 A about 15 kg / h. At a nitrogen content of the core 31 of 1.2 wt .-% of the nitrogen content of the protective layer 2 was still 0.75 wt .-% average.
  • a steel cylinder of 500 mm diameter and 3000 mm length was coated by the flame spraying process.
  • a non-nitrogen containing Fe / Cr / Mn powder 10 containing about 18% by weight of chromium and about 18% by weight of manganese as the starting material was used.
  • the porous surface layer 37 had an average thickness of 2 mm and had a porosity of about 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. Nitrogen feed 39 was made laterally and care was taken to ensure that the surface layer nitrogen was flushed all around 40.
  • 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. Subsequently, the porous surface layer 37 was embroidered by the continuous process.
  • the steel cylinder (substrate 1) was passed through an induction coil-shaped heater 41 flanked by annular nitrogen jets 42.
  • the surface layer 37 was brought to a temperature of 1000 ° C in a short time.
  • the feed was 60 mm / min.
  • the residence time averaged 2 minutes.
  • the nitrogen content of the finished protective layer reached the value of 0.4 wt .-%.
  • the coating was alternatively carried out by the plasma spraying process. After embroidering in the continuous process, virtually the same results were achieved.
  • a low alloy steel plate of 15 mm thickness was coated with nitrogen-containing Fe / Cr / Mn / N powder 15 via a powder feed tube 44 and locally melted and coated by means of a laser beam 43.
  • the powder in the laser melting zone 45 was firmly bonded to the substrate 1 by fusion metallurgy.
  • the nitrogen content of the finished protective layer was due to the high cooling rate on average still 0.8 wt .-%.
  • the feed was 80 mm / min.
  • a roll of 80 mm in diameter and 1200 mm in length was provided with a porous surface layer 37 of Fe / Cr / Mn (non-nitrogenous) by the flame spraying method. Then the component 1 was placed in a hot isostatic press 46 and compacted by pressure embroidering under supply 47 of nitrogen as a pressurized gas under 10 bar at a temperature of 700 ° C. The process lasted 1 hour. The result was a protective layer of 1.2 mm thickness with a nitrogen content of 1.1% by weight. In one variant, a plasma-sprayed surface layer 37 was assumed. The result was similar.
  • the invention is not limited to the embodiments.
  • the process for producing a protective layer with high resistance to wear and corrosion 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 wt .-%, using as starting material a produced by sputtering of a liquid jet of metal by a gas jet austenitic powder and by low-energy flame spraying or high-velocity flame spraying or by plasma spraying under nitrogen or a nitrogen / argon mixture as propellant gas on the surface is applied to the component and preferably as a starting material, a powder with 18 wt .-% chromium and 18 wt .-% manganese is used.
  • the powder is prepared by annealing in a nitrogen atmosphere before Spraying brought to a nitrogen content of 0.4-3.2 wt .-%, wherein it is preferably nitrated with a particle size of 5-45 microns in bulk and for at least 1 hr. Under a pressure of 1-1000 bar at exposed to a temperature of 300-800 ° C a static nitrogen atmosphere and brought in this way to a nitrogen content of 1.2 wt .-%, cooled and screened out.
  • the procedure is such that nitrogen-containing powder is used as the starting material and after the high-speed flame spraying method with a speed of min.
  • Another variant is that used as a starting material made of a block or ingot nitrogen-containing wire of 1.5-4 mm diameter and after the wire spraying by flame spraying or arc spraying under nitrogen, forming gas or a nitrogen / argon mixture on the surface of the Applied component or that a consisting of a core of nitrogen-containing austenitic metal powder and a sheath made of a ductile metal or an alloy or a plastic sheath wire is used and is applied by the wire spraying method by arc spraying on the surface of the component.
  • the component is first coated with a powder of a conventional, non-nitrogenous material by the plasma spraying process or by the high-speed flame spraying process and that the coated workpiece then in a furnace under a nitrogen atmosphere annealed under isothermal conditions or sent through the flow principle by an inductive or a resistance heater, wherein in the latter case, the surface is zonengeglüht continuously for 3-20 sec. At a temperature of 700-900 C ° and the annealing zone is simultaneously flushed with nitrogen.
  • the procedure is such that nitrogen-containing powder of an iron-based alloy is applied by means of a laser beam to the surface of the component, such that the surface and the powder particles are easily melted by the laser beam and the thus coated surface of a rapid cooling by heat removal after the Inside of the workpiece is subjected.
  • the component is provided by thermal spraying with a conventional, non-nitrogenous material with a porous surface layer and then the surface of the coated workpiece then using nitrogen as compressed gas simultaneously densified by hot isostatic pressing and nitrided.
  • the component is coated by plasma spraying under a nitrogen gas jacket by the molten metal particles are brought into contact only with nitrogen and thereby loaded with the necessary nitrogen content, wherein the plasma spraying preferably in a protective gas chamber under a pressure of 0.5 bar nitrogen is performed.

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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
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.
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

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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

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

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4124423A1 (de) * 1990-08-03 1992-02-06 Andritz Patentverwaltung Thermisches spritzschichtverfahren und anlage zu dessen durchfuehrung
EP0552004A1 (fr) * 1992-01-16 1993-07-21 United Kingdom Atomic Energy Authority Procédé de dépôt d'une couche de revêtement sur un substrat
WO1995019240A1 (fr) * 1994-01-14 1995-07-20 Castolin S.A. Revetement biphase ou polyphase
EP0721997A1 (fr) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Méthode de traitement de la surface d'un élément de soupape en titane ou alliage de titane
WO1999048747A1 (fr) * 1998-03-23 1999-09-30 Caterpillar Inc. Bague de chaine avec traitement d'extremite par soudure a l'arc offrant une resistance accrue a l'abrasion et a la corrosion, et son procede de fabrication
WO2000014332A1 (fr) * 1998-09-08 2000-03-16 Jagenberg Papiertechnik Gmbh Racle en forme de tige destinee a un dispositif de recouvrement
US6157987A (en) * 1996-03-15 2000-12-05 Micron Technology, Inc. Pixel engine data caching mechanism
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
EP1391531B2 (fr) † 2002-08-05 2008-10-08 United Technologies Corporation Procédé de production d'une couche de barrière thermique avec particules de nitrures
WO2013056961A1 (fr) * 2011-10-17 2013-04-25 Ford-Werke Gmbh Procédé de projection plasma
WO2014025244A1 (fr) * 2012-08-07 2014-02-13 Torims Toms Appareil et procédé de réparation et rénovation de surfaces de tourillon de vilebrequin in situ au moyen d'un plaquage au laser
CN104087885A (zh) * 2014-06-17 2014-10-08 宁国东方碾磨材料股份有限公司 一种耐腐蚀涂层磨段
EP3930942A4 (fr) * 2019-02-26 2023-01-18 Somnio Global Holdings, LLC Poudre d'acier à haute teneur en azote et procédés de fabrication de celle-ci
CN120350337A (zh) * 2025-06-19 2025-07-22 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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
EP3759262A4 (fr) * 2018-02-27 2021-11-03 Somnio Global Holdings, LLC Articles avec couche de protection en alliage d'azote et procédés de fabrication de ceux-ci

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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.
EP0290052A1 (fr) * 1987-05-08 1988-11-09 Castolin S.A. Procédé de fabrication de glissière sur pièces de moteurs d'automobile
EP0363047A1 (fr) * 1988-10-05 1990-04-11 United Kingdom Atomic Energy Authority Procédé de préparation d'alliages renforcés par une dispersion de nitrures

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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.
EP0290052A1 (fr) * 1987-05-08 1988-11-09 Castolin S.A. Procédé de fabrication de glissière sur pièces de moteurs d'automobile
EP0363047A1 (fr) * 1988-10-05 1990-04-11 United Kingdom Atomic Energy Authority Procédé de préparation d'alliages renforcés par une dispersion de nitrures

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Title
DISSERTATION ABSTRACTS INTERNATIONAL, Band 45, Nr. 4, Oktober 1984, Seite 1260-B, New York, US; H. BHAT et al.: "Characterization of plasma-sprayed iron- and nickel-based alloy coatings" *
HYOMEN GIJUTSU, Band 40, Nr. 1, 1989, Seiten 341-342, Osaka, JP; M. MAGOME et al.: "Characteristic of stainless steels spray deposit in an atmosphere of nitrogen" *
PATENT ABSTRACTS OF JAPAN, Band 13, Nr. 388 (C-630)[3736], 28. August 1989; & JP-A-1 136 965 (NISSHIN STEEL) 30-05-1989 *
STAINLESS STEEL, 14. - 16. September 1987, Seiten 535-540, York, GB; B.R. NIJHAWAN: "Substitute nickel-fee chromium, manganese, nitrogen austenitic stainless steels" *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4124423A1 (de) * 1990-08-03 1992-02-06 Andritz Patentverwaltung Thermisches spritzschichtverfahren und anlage zu dessen durchfuehrung
EP0552004A1 (fr) * 1992-01-16 1993-07-21 United Kingdom Atomic Energy Authority Procédé de dépôt d'une couche de revêtement sur un substrat
EP0721997A1 (fr) * 1993-10-27 1996-07-17 Fuji Oozx Inc. Méthode de traitement de la surface d'un élément de soupape en titane ou alliage de titane
WO1995019240A1 (fr) * 1994-01-14 1995-07-20 Castolin S.A. Revetement biphase ou polyphase
DE4447514A1 (de) * 1994-01-14 1996-02-01 Castolin Sa Verfahren zum Herstellen eines Hilfsmittels für das Beschichten durch thermisches Spritzen, Plasmapulver-Auftragsschweißen oder Lichtbogenschweißen
US6157987A (en) * 1996-03-15 2000-12-05 Micron Technology, Inc. Pixel engine 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
WO1999048747A1 (fr) * 1998-03-23 1999-09-30 Caterpillar Inc. Bague de chaine avec traitement d'extremite par soudure a l'arc offrant une resistance accrue a l'abrasion et a la corrosion, et son procede de fabrication
WO2000014332A1 (fr) * 1998-09-08 2000-03-16 Jagenberg Papiertechnik Gmbh Racle en forme de tige destinee a un dispositif de recouvrement
US6413314B1 (en) 1998-09-08 2002-07-02 Jagenberg Papiertechnik Gmbh Doctor rod for a coating device
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
EP1391531B2 (fr) † 2002-08-05 2008-10-08 United Technologies Corporation Procédé de production d'une couche de barrière thermique avec particules de nitrures
WO2013056961A1 (fr) * 2011-10-17 2013-04-25 Ford-Werke Gmbh Procédé de projection plasma
WO2014025244A1 (fr) * 2012-08-07 2014-02-13 Torims Toms Appareil et procédé de réparation et rénovation de surfaces de tourillon de vilebrequin in situ au moyen d'un plaquage au laser
CN104087885A (zh) * 2014-06-17 2014-10-08 宁国东方碾磨材料股份有限公司 一种耐腐蚀涂层磨段
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
EP3930942A4 (fr) * 2019-02-26 2023-01-18 Somnio Global Holdings, LLC Poudre d'acier à haute teneur en azote et procédés de fabrication de celle-ci
CN120350337A (zh) * 2025-06-19 2025-07-22 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

Also Published As

Publication number Publication date
EP0456847B1 (fr) 1994-12-07
JPS6417846A (en) 1989-01-20
DE3816310A1 (de) 1989-01-12
DE59007940D1 (de) 1995-01-19

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