EP0256049A1 - Process for producing a titanium-carbide containing wear-resistant coating on a metal base. - Google Patents

Process for producing a titanium-carbide containing wear-resistant coating on a metal base.

Info

Publication number
EP0256049A1
EP0256049A1 EP87900795A EP87900795A EP0256049A1 EP 0256049 A1 EP0256049 A1 EP 0256049A1 EP 87900795 A EP87900795 A EP 87900795A EP 87900795 A EP87900795 A EP 87900795A EP 0256049 A1 EP0256049 A1 EP 0256049A1
Authority
EP
European Patent Office
Prior art keywords
alloy
weight
tic
following elements
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87900795A
Other languages
German (de)
French (fr)
Other versions
EP0256049B1 (en
Inventor
Hans-Theo Steine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ECG Immobilier SA
Original Assignee
Castolin SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4186733&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0256049(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Castolin SA filed Critical Castolin SA
Publication of EP0256049A1 publication Critical patent/EP0256049A1/en
Application granted granted Critical
Publication of EP0256049B1 publication Critical patent/EP0256049B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • 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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C4/129—Flame 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
    • C23C4/18—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/937—Sprayed metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component

Definitions

  • the present invention relates to a method for producing a wear-resistant layer according to the preamble of patent claim 1.
  • German patent DE 2208070 describes a method of this type, in which a metallic base body is provided with a thin, wear-resistant layer of up to a maximum of about 0.635 mm thick, the spraying being carried out by plasma flame spraying and the material used having a grain size of, for example, the order of magnitude. 44 / + 88 ⁇ m.
  • the layer is spray-quenched when sprayed on thanks to the cooling effect of the base body, thereby creating a microstructure consisting of titanium carbide grains dispersed in a base material, the base material being formed by an austenite conversion product containing martensite. Without further heat treatment, this leads to a • relatively hard layer in which rounded titanium carbide grains are present as a result of the plasma spraying process.
  • the layers that can be produced in this way are very limited in their thickness, preferably from 0.381 mm to 0.254 mm and 0.127 mm, since otherwise the structure mentioned would result in very high internal stresses.
  • the small thickness corresponds to the same limited lifetime.
  • the mechanical machinability is also very limited and the elasticity of the layer is extremely low due to the small grain size of the spraying material and the structure made up of the smallest lamellae.
  • Wear-resistant coatings which were produced by Flamrospritzen without melting and have a high hardness due to the storage of hard materials such as carbides, silicides, borides, etc. or consist of hard alloys, show a strong sensitivity to crack formation due to the occurrence of internal stresses in the layer.
  • the achievable layer thickness is very limited.
  • the object of the invention is to provide a method for producing wear-resistant layers of great hardness, with which layers having a considerably longer life than those of the known layers can be produced, and which furthermore enables mechanical processing after spraying and is relatively problem-free with regard to internal stresses in the layer is.
  • the layer has a lamellar structure with relatively large lamellae corresponding to the particle size, which results in greater elasticity of the layer. It should also be noted that the coefficient of expansion of the layer is very close to the coefficient of expansion of the matrix alloy.
  • Adhesive layer applied 0.1 mm thick. It was a
  • Powder of the composition in percent by weight, 95.0 Ni,
  • a wear-resistant layer was then applied to the adhesive layer
  • composition of the wettable powder in percent by weight, and the grain size we followed:
  • the coated shaft was machined and brought to the finished size.
  • shaft had a value of 420 Hv, after heat treatment the hardness was
  • the sliding surface of 100 x 100 mm of a sliding plate of 50 mm thickness was coated in the following way. After preparing the sliding surface by blasting with corundum, the plate was preheated to 100 ° C. and then an adhesive layer - 0.1 mm thick - was applied. A commercially available adhesive layer powder (Castolin 51000) was applied by autogenous flame spraying. Subsequently, a wear-resistant layer of 1.2 mm thickness was also applied by autogenous flame spraying without subsequent melting, the composition of the wettable powder (grain size -150 / + 37 ⁇ m) in weight percent being the following:
  • An axis of 40.0 mm in diameter was treated in the following manner to achieve high wear resistance.
  • the axis was provided with a wear-resistant layer of 1.5 mm thickness by autogenous flame spraying under the usual working conditions, the composition of the spraying material in weight percent being chosen as follows: 33.0 TiC in a matrix alloy of 0.35 C, 2.0 Cr, 1.0 Cu, 2.0 Mo, balance Fe.
  • the grain size was in the range -150 / + 37 ⁇ m.
  • the surface was then machined and removed to the desired finish by grinding, the surface layer remaining 1 mm thick.
  • the finished part was kept in a muffle furnace at 500 ° C. for five hours.
  • the hardness of the layer before the heat treatment was 400 Hv, after the heat treatment a hardness of 680 Hv was measured.
  • a wearing part with the dimensions 200 x 60 x 30 mm was coated on one of the areas of 200 x 60 mm in the following way.
  • the surface to be coated was prepared by blasting with corundum, on this surface a powdery spray material of grain size -150 / + 37 ⁇ ⁇ m au ⁇ , in weight percent, 16.5 TiC with a matrix alloy of 0.5 C, 14.0 Cr , 0.5 Cu, 14.0 Mo, 3.5 W, remainder Ni applied by autogenous flame spraying without subsequent melting under normal conditions.
  • the wear-resistant layer had a thickness of 2.2 mm and was then machined, the thickness of the layer being 2.0 mm was brought.
  • the wear part was then kept in a muffle furnace at 450 ° C. for five hours.
  • the hardness was 380 Hv before the heat treatment and rose to 550 Hv after the heat treatment.
  • Example 4 The procedure of Example 4 was repeated analogously with a spray material of the composition, in percent by weight, 20.0 TiC in a matrix alloy of 0.5 C, 14.0 Cr, 0.5 Cu, 14.0 Mo, 5.0 W, Rest Co. The hardness of the heat-treated part reached 530 Hv.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

Une matière frittée, contenant des particules agglomérées ou des particules alliées contenant 10-50% en poids de carbure de titane et un alliage de fer et/ou de nickel ou un alliage de cobalt, est déposée par pulvérisation à la flamme sur une épaisseur d'au moins 1 mm. Elle est soumise ensuite à un traitement thermique à une température comprise entre 400 et 650°C après un éventuel façonnage mécanique. Le procédé permet la fabrication de couches résistant à l'usure, de dureté élevée et d'épaisseur relativement grande, assurant une longue durée, évitant les tensions intérieures et donnant la possibilité d'un façonnage mécanique après la pulvérisation.A sintered material, containing agglomerated particles or alloyed particles containing 10-50% by weight of titanium carbide and an iron and / or nickel alloy or a cobalt alloy, is deposited by flame spraying on a thickness d '' at least 1 mm. It is then subjected to a heat treatment at a temperature between 400 and 650 ° C after possible mechanical shaping. The process allows the manufacture of wear-resistant layers, of high hardness and of relatively large thickness, ensuring a long duration, avoiding internal tensions and giving the possibility of mechanical shaping after spraying.

Description

VERFAHREN ZUR HERSTELLUNG EINER VERSCHLEISSFESTE , TITANKARBID ENTHALTENDEN SCHICHT AUF EINEM METALLISCHEN GRÜNDKÖRPERMETHOD FOR PRODUCING A WEAR-RESISTANT LAYER, CONTAINING TITANIUM CARBIDE, ON A METAL BASE
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer verschleissfesten Schicht gema'ss dem Oberbegriff des Patentanspruchs 1.The present invention relates to a method for producing a wear-resistant layer according to the preamble of patent claim 1.
Die deutsche Patentschrift DE 2208070 beschreibt ein Verfahren dieser Art, bei dem ein metallischer Grundkörper mit einer dünnen verschleissfesten Schicht von bis zu maximal etwa 0,635 mm Dicke versehen wird, wobei das Aufspritzen durch Plasma-Flammspritzen erfolgt und der verwendete Werkstoff eine Korngrösse von beispielsweise grössenordnungsmässig -44/+88 um aufweist.German patent DE 2208070 describes a method of this type, in which a metallic base body is provided with a thin, wear-resistant layer of up to a maximum of about 0.635 mm thick, the spraying being carried out by plasma flame spraying and the material used having a grain size of, for example, the order of magnitude. 44 / + 88 µm.
Bei diesem bekannten Verfahren ist es wesentlich, dass die Schicht beim Aufspritzen dank der Kühlwirkung des Grundkörpers drastisch abgeschreckt wird und dadurch eine Mikrostruktur entsteht, die aus in einer Grundmasse diεpergierten Titankarbidkörnern besteht, wobei die Grundmasse durch ein Martensit enthaltendes Austenit-Umwandlungsprodukt gebildet wird. Dies führt bereits ohne weitere Wärmebehandlung zu einer • relativ harten Schicht, in der infolge des Plasma-Spritzverfahrens abgerundete Titankarbidkörner vorhanden sind.In this known method, it is essential that the layer is spray-quenched when sprayed on thanks to the cooling effect of the base body, thereby creating a microstructure consisting of titanium carbide grains dispersed in a base material, the base material being formed by an austenite conversion product containing martensite. Without further heat treatment, this leads to a • relatively hard layer in which rounded titanium carbide grains are present as a result of the plasma spraying process.
Die so herstellbaren Schichten sind jedoch in ihrer Dicke sehr begrenzt, vorzugsweise wird von 0,381 mm bis 0,254 mm und 0,127 mm gesprochen, da die erwähnte Struktur sonst sehr hohe innere Spannungen zur Folge hätte. Der geringen Dicke entspricht eine gleicher assen begrenzte Lebens¬ dauer. Daneben sind auch der mechanischen Bearbeitbarkeit sehr enge Grenzen gesetzt und die Elastizität der Schicht ist infolge der kleinen Kornqrösse des Spritzwerkstoffs und der dieser entsprechenden Struktur aus kleinsten Lamellen äusserst gering. Verschleissfeste Beschichtungen, die durch Flamrospritzen ohne Einschmelzen hergestellt wurden und durch Einlagerung von Hartstoffen, wie Karbiden, Siliciden, Boriden usw., eine hohe Härte aufweisen oder aus Hartlegierungen bestehen, zeigen eine starke Empfindlichkeit gegen Rissbildung infolge des Auftretens von inneren Spannungen in der Schicht. Die erzielbare Schichtdicke ist dadurch sehr beschränkt.However, the layers that can be produced in this way are very limited in their thickness, preferably from 0.381 mm to 0.254 mm and 0.127 mm, since otherwise the structure mentioned would result in very high internal stresses. The small thickness corresponds to the same limited lifetime. In addition, the mechanical machinability is also very limited and the elasticity of the layer is extremely low due to the small grain size of the spraying material and the structure made up of the smallest lamellae. Wear-resistant coatings, which were produced by Flamrospritzen without melting and have a high hardness due to the storage of hard materials such as carbides, silicides, borides, etc. or consist of hard alloys, show a strong sensitivity to crack formation due to the occurrence of internal stresses in the layer. The achievable layer thickness is very limited.
Andererseits führt die Verwendung von selbstfliessenden Legierungen, die nach dem Einschmelzen eine hohe Härte erreichen, für viele Anwendungen zu übermässig hohen Temperaturen während des Einschmelzvorgangs, die sich auf das Grundmaterial im Hinblick auf einen Verzug, eine Versprödung und andere Beeinflussungen sehr ungünstig auswirken.On the other hand, the use of self-flowing alloys, which reach a high hardness after melting, leads to excessively high temperatures during the melting process for many applications, which have a very unfavorable effect on the base material with regard to warpage, embrittlement and other influences.
Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung verschleiεsfester Schichten von grosser Härte zu schaffen, mit dem Schichten von wesentlich höherer Lebensdauer als die der bekannten Schichten erzeugt werden können und das zudem eine mechanische Bearbeitung nach dem Aufspritzen ermöglicht und relativ problemlos bezüglich innerer Spannungen in der Schicht ist.The object of the invention is to provide a method for producing wear-resistant layers of great hardness, with which layers having a considerably longer life than those of the known layers can be produced, and which furthermore enables mechanical processing after spraying and is relatively problem-free with regard to internal stresses in the layer is.
Dies wird erfindungsgemäss durch die im kennzeichnenden Teil des Patentanspruchs 1 angegebenen Verfahrensmerkmale erzielt. Die Ansprüche 2 bis 10 beschreiben besondere Ausführungsformen des erfindungsge ässen Verfahrens.This is achieved according to the invention by the method features specified in the characterizing part of patent claim 1. Claims 2 to 10 describe special embodiments of the method according to the invention.
Es hat sich überraschenderweise herausgestellt, dass beim autogenen Flammspritzen, ohne nachträgliches Einschmelzen, von Titankarbid in einer metallischen Matrix, zunächst eine mechanisch gut bearbeitbare Schicht entsteht, die durch eine anschliessende Wärmebehandlung bei relativ niedriger Temperatur eine Aushärtung erfährt, wobei im Endzustand eine Härte von 500 bis 700 Hv entsteht. Im Gegensatz zu dem erwähnten Verfahren, das mittels Plasma-Flammspritzen durchgeführt wird, wird bei dem vorliegenden Verfahren der Schichtwerkstoff während des Spritzvorganges in der autogenen Flamme praktisch homogen geschmolzen, wobei das Titankarbid in der Matrixlegierung gelöst ist. Die derart erhaltene Schicht von austenitiεchem Charakter l sst sich mechanisch gut bearbeiten. Bei der darauffolgenden Wärmebehandlung wird das Titankarbid dann sehr feinkörnig und gleichmässig verteilt ausgeschieden.Surprisingly, it has been found that during autogenous flame spraying, without subsequent melting, of titanium carbide in a metallic matrix, a layer that is easy to process mechanically is first created, which is hardened by subsequent heat treatment at a relatively low temperature, with a hardness of 500 in the final state up to 700 Hv. In contrast to the mentioned method, which is carried out by means of plasma flame spraying, in the present method the layer material is melted practically homogeneously in the autogenous flame during the spraying process, the titanium carbide being dissolved in the matrix alloy. The layer of austenitic character obtained in this way can be machined well. In the subsequent heat treatment, the titanium carbide is then separated out in a very fine-grained and evenly distributed manner.
Die Schicht weist eine Lamellenstruktur mit relativ grossen, der Partikelgrδsse entsprechenden Lamellen auf, wodurch eins grössere Elastizität der Schicht entsteht. Ferner ist zu bemerken, dass der Ausdehnungskoeffizient der Schicht sehr nahe dem Ausdehnungskoeffizienten der Matrixlegierung ist.The layer has a lamellar structure with relatively large lamellae corresponding to the particle size, which results in greater elasticity of the layer. It should also be noted that the coefficient of expansion of the layer is very close to the coefficient of expansion of the matrix alloy.
Bei dem vorliegenden Verfahren treten demnach praktisch keine inneren Spannungen auf und es lässt sich daher eine Schichtdicke bis über 3 mm erzielen, wobei die Wärmebehandlung ohne Schwierigkeiten durchführbar ist.Accordingly, in the present method there are practically no internal stresses and it is therefore possible to achieve a layer thickness of more than 3 mm, and the heat treatment can be carried out without difficulty.
Die anschliesεenden Beispiele veranschaulichen die Ergebnisse des erfindungsgemäsεen Verfahrenε.The following examples illustrate the results of the method according to the invention.
Beiεpiel 1Example 1
Eine Welle von 50 mm Durchmesser, die einer sehr starkenA shaft 50 mm in diameter, which is a very strong one
Verschleiεεbeanεpruchung εtandhalten soll, wurde zunächst in folgender Weise beschichtet.Was intended to withstand wear, was first coated in the following manner.
Nach einer Vorbereitung durch Strahlen mit Korund wurde dieAfter preparation by blasting with corundum, the
Welle auf 150°C vorgewärmt und anschliessend eineWave preheated to 150 ° C and then one
Haftεchicht von 0,1 mm Dicke aufgebracht. Dabei wurde einAdhesive layer applied 0.1 mm thick. It was a
Pulver der Zusammensetzung, in Gewichtsprozent, 95,0 Ni,Powder of the composition, in percent by weight, 95.0 Ni,
5,0 AI mit einem autogenen Flammspritzgerät in üblicher5.0 AI with an autogenous flame sprayer in the usual
Weise aufgespritzt.Way sprayed.
Auf die Haftschicht wurde sodann eine verschleiεsfesteA wear-resistant layer was then applied to the adhesive layer
Schicht von 1,8 mm Dicke ebenfallε durch autogenes Flammεpritzen mit den üblichen Parametern, ohne nachtr glicheε Einεch elzen aufgebracht, wobei dieLayer of 1.8 mm thickness also by autogenous Flame spraying with the usual parameters, without subsequent Einselch applied, the
Zuεam enεetzung deε Spritzpulverε, in Gewichtεprozent, und die Korngröεεe wir folgt waren :Composition of the wettable powder, in percent by weight, and the grain size we followed:
33,0 TiC mit einer Matrixlegierung von 0,9 C, 1,0 Cr, 0,333.0 TiC with a matrix alloy of 0.9 C, 1.0 Cr, 0.3
Cu, 0,5 Mo, 1,9 Mn, 1,0 Si, 0,2 V, Rest Fe. KorngrösseCu, 0.5 Mo, 1.9 Mn, 1.0 Si, 0.2 V, balance Fe. Grain size
-150/+37 μ .-150 / + 37μ.
Die beεchichtete Welle wurde spanabhebend bearbeitet und auf das Fertigmass gebracht.The coated shaft was machined and brought to the finished size.
Anschliessend wurde sie während fünf Stunden in einemThen she was in one for five hours
Muffelofen auf 550°C gehalten. Die Härte der beεchichtetenMuffle furnace kept at 550 ° C. The hardness of the coated
Welle hatte nach der mechanischen Bearbeitung einen Wert von 420 Hv, nach der Wärmebehandlung wurde eine Härte vonAfter mechanical processing, shaft had a value of 420 Hv, after heat treatment the hardness was
640 Hv gemessen.640 Hv measured.
Beispiel 2Example 2
Die Gleitfläche von 100 x 100 mm einer Gleitplatte von 50 mm Dicke wurde in folgender Weise beschichtet. Nach einer Vorbereitung der Gleitfläche durch Strahlen mit Korund wurde die Platte auf 100°C vorgewärmt und anschliesεend eine Haftεchicht - von 0,1 mm Dicke aufgebracht. Dabei wurde ein handelεüblicheε Haftεchicht-Pulver (Castolin 51000) durch autogenes Flammspritzen aufgetragen. Im Anschluss daran wurde eine verschleiεεfeεte Schicht von 1,2 mm Dicke ebenfallε durch autogeneε Flammspritzen ohne nachträgliches Einschmelzen aufgebracht, wobei die Zusammensetzung des Spritzpulvers (Korngrδsεe -150/+37 jum) in Gewichtεprozent die folgende war :The sliding surface of 100 x 100 mm of a sliding plate of 50 mm thickness was coated in the following way. After preparing the sliding surface by blasting with corundum, the plate was preheated to 100 ° C. and then an adhesive layer - 0.1 mm thick - was applied. A commercially available adhesive layer powder (Castolin 51000) was applied by autogenous flame spraying. Subsequently, a wear-resistant layer of 1.2 mm thickness was also applied by autogenous flame spraying without subsequent melting, the composition of the wettable powder (grain size -150 / + 37 μm) in weight percent being the following:
32% TiC in einer Matrixlegierung von 0,2 C, 0,5 Cr, 0,5 Cu, 6,0 Mo, 15,0 Ni, 0,7 AI, 9,0 Co, 0,7 Ti, 0,1 Nb, Reεt Fe. Die beεchichtete Oberfläche wurde εpanabhebend bearbeitet. Danach wurde die Gleitplatte während vier Stunden in einem Schutzσasofen bei 450°C behandelt. Die Härte der Gleitfläche vor der thermischen Behandlung betrug 450 Hv, die nach der Wärmebehandlung gemessene Härte betrug 650 Hv. Bei εpiel 332% TiC in a matrix alloy of 0.2 C, 0.5 Cr, 0.5 Cu, 6.0 Mo, 15.0 Ni, 0.7 AI, 9.0 Co, 0.7 Ti, 0.1 Nb, Reεt Fe. The coated surface was machined to remove chips. The slide plate was then treated in a protective gas oven at 450 ° C. for four hours. The hardness of the sliding surface before the thermal treatment was 450 Hv, the hardness measured after the heat treatment was 650 Hv. Example 3
Eine Achεe von 40,0 mm Durchmesser wurde zur Erzielung einer hohen Verschleiεsfestigkeit in folgender Weise behandelt.An axis of 40.0 mm in diameter was treated in the following manner to achieve high wear resistance.
Nach einer Vorbereitung der Oberfläche durch Strahlen mit Korund wurde die Achse durch autogenes Flammspritzen unter den üblichen Arbeitsbedingungen mit einer verschleiεsfesten Schicht von 1,5 mm Dicke verεehen, wobei die Zusammensetzung des Spritzwerkstoffes in Gewichtsprozent wie folgt gewählt wurde : 33,0 TiC in einer Matrixlegierung von 0,35 C, 2,0 Cr, 1,0 Cu, 2,0 Mo, Rest Fe. Die Korngrösse war im Bereich -150/+37 um.After preparation of the surface by blasting with corundum, the axis was provided with a wear-resistant layer of 1.5 mm thickness by autogenous flame spraying under the usual working conditions, the composition of the spraying material in weight percent being chosen as follows: 33.0 TiC in a matrix alloy of 0.35 C, 2.0 Cr, 1.0 Cu, 2.0 Mo, balance Fe. The grain size was in the range -150 / + 37 µm.
Die Oberfläche wurde anschlieεεend εpanabhebend bearbeitet und durch Schleifen auf das gewünschte Fertigmaεs gebracht, wobei die Oberflächenschicht eine Dicke von 1 mm behielt.The surface was then machined and removed to the desired finish by grinding, the surface layer remaining 1 mm thick.
Nach der mechanischen Bearbeitung wurde daε fertige Teil in einem Muffelofen während fünf Stunden auf 500°C gehalten. Die Härte der Schicht vor der Wärmebehandlung betrug 400 Hv, nach der Wärmebehandlung wurde eine Härte von 680 Hv gemessen.After the mechanical processing, the finished part was kept in a muffle furnace at 500 ° C. for five hours. The hardness of the layer before the heat treatment was 400 Hv, after the heat treatment a hardness of 680 Hv was measured.
Beispiel 4Example 4
Ein Verschleiεsteil mit den Abmessungen 200 x 60 x 30 mm wurde auf einer der Flächen von 200 x 60 mm in folgender Weise beschichtet.A wearing part with the dimensions 200 x 60 x 30 mm was coated on one of the areas of 200 x 60 mm in the following way.
Die zu beschichtende Fläche wurde durch Strahlen mit Korund vorbereitet, auf diese Fläche wurde ein pulverför iger Spritzwerkstoff der Korngrösεe -150/+37 ^αm auε, in Gewichtεprozent, 16,5 TiC mit einer Matrixlegierung von 0,5 C, 14,0 Cr, 0,5 Cu, 14,0 Mo, 3,5 W, Rest Ni durch autogenes Flammspritzen ohne nachträgliches Einschmelzen unter üblichen Bedingungen aufgetragen. Die verschleissfeste Schicht hatte eine Dicke von 2,2 mm und wurde anschliessend mechanisch bearbeitet, wobei die Dicke der Schicht auf 2,0 mm gebracht wurde. Danach wurde das Verschleiεsteil in einem Muffelofen während fünf Stunden auf 450°C gehalten. Die Härte betrug vor der Wärmebehandlung 380 Hv und stieg nach der Wärmebehandlung auf 550 Hv.The surface to be coated was prepared by blasting with corundum, on this surface a powdery spray material of grain size -150 / + 37 ^ αm auε, in weight percent, 16.5 TiC with a matrix alloy of 0.5 C, 14.0 Cr , 0.5 Cu, 14.0 Mo, 3.5 W, remainder Ni applied by autogenous flame spraying without subsequent melting under normal conditions. The wear-resistant layer had a thickness of 2.2 mm and was then machined, the thickness of the layer being 2.0 mm was brought. The wear part was then kept in a muffle furnace at 450 ° C. for five hours. The hardness was 380 Hv before the heat treatment and rose to 550 Hv after the heat treatment.
Beispiel 5Example 5
Das Verfahren von Beispiel 4 wurde analog wiederholt mit einem Spritzwerkstoff der Zusammensetzung, in Gewichtεprozent, 20,0 TiC in einer Matrixlegierung von 0,5 C, 14,0 Cr, 0,5 Cu, 14,0 Mo, 5,0 W, Rest Co. Die Härte des wär ebehandelten Teils erreichte den Wert von 530 Hv. The procedure of Example 4 was repeated analogously with a spray material of the composition, in percent by weight, 20.0 TiC in a matrix alloy of 0.5 C, 14.0 Cr, 0.5 Cu, 14.0 Mo, 5.0 W, Rest Co. The hardness of the heat-treated part reached 530 Hv.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Verfahren zur Herstellung einer verschleiεsfeεten Schicht aud einem metallischen Grundkörper, bei dem ein Werkstoff, der 10-50 Gewichtεprozent gesinterte, agglomerierte Partikel oder Legierungspartikel aus .TiC und aus einer Fe- und/oder Ni-Legierung oder einer Co-Legierung aufweist, thermisch aufgespritzt wird und die aufgespritzte Schicht eine Wärmebehandlung im Temperaturbereich von 400-650°C erfährt, dadurch gekennzeichnet, dass die Werkstoff-Partikel eine Korngrösεe von -150/+37 jum beεitzen und die Schicht durch autogenes Flammspritzen in einer Dicke von mindestenε 1 mm aufgeεpritzt wird.1. Process for the production of a wear-resistant layer on a metallic base body, in which a material consisting of 10-50% by weight sintered, agglomerated particles or alloy particles . TiC and from an Fe and / or Ni alloy or a Co alloy, is thermally sprayed and the sprayed layer undergoes a heat treatment in the temperature range of 400-650 ° C, characterized in that the material particles have a grain size of - 150 / + 37 j um and the layer is sprayed on by autogenous flame spraying in a thickness of at least 1 mm.
2. Verfahren nach Patentanεpruch 1, dadurch gekennzeichnet, daεs die Fe- und/oder Ni-Legierung mindestenε zwei Legierungszusätze aus den folgenden Elementen und in den angegebenen Gewichtεprozentbereichen enthält :2. The method according to claim 1, characterized in that the Fe and / or Ni alloy contains at least two alloy additions from the following elements and in the stated weight percent ranges:
0-1 C, 0-25 Cr, 0-20 Mo, 0-15 Co, 0-2 Cu, 0-0,5 V, 0-2 AI, 0-1,5 Nb, 0-1 V, 0-2 Ti, 0-4 W, 0-2 Si.0-1 C, 0-25 Cr, 0-20 Mo, 0-15 Co, 0-2 Cu, 0-0.5 V, 0-2 AI, 0-1.5 Nb, 0-1 V, 0 -2 Ti, 0-4 W, 0-2 Si.
3. Verfahren nach Patentanεpruch 2, dadurch gekennzeichnet, daεε die Partikel 30-35 Gewichtεprozent TiC enthalten und im übrigen auε einer Fe-Legierung beεtehen, die Legierungszusätze aus den folgenden Elementen und in den angegebenen Gewichtεprozentbereichen enthält : 0,1-0,8 C, 2-22 Cr, 0,1-4 Mo, 0,5-2 Cu, 0-0,5 V, 0-1 AI, 0-1 Ni, 0-1 Ti, 0-2 Mn, 0-1,5 Si.3. The method according to claim 2, characterized in that the particles contain 30-35 percent by weight TiC and otherwise consist of an Fe alloy that contains alloy additions from the following elements and in the given percentages by weight range: 0.1-0.8 ° C , 2-22 Cr, 0.1-4 Mo, 0.5-2 Cu, 0-0.5 V, 0-1 AI, 0-1 Ni, 0-1 Ti, 0-2 Mn, 0-1 , 5 Si.
4. Verfahren nach Patentanspruch 2, dadurch gekennzeichnet, daεε die Partikel 20-35 Gewichtsprozent TiC enthalten und im übrigen aus einer Fe-Legierung bestehen, die Legierungszuεätze auε den folgenden Elementen und in den angegebenen Gewichtsprozentbereichen enthält :4. The method according to claim 2, characterized in that the particles contain 20-35 percent by weight of TiC and moreover consist of an Fe alloy that contains alloy additions from the following elements and in the stated percentages by weight:
0-0,8 C, 0-20 Cr, 2-15 Mo, 0,5-1 Cu, 0-1,5 AI, 5-16 Ni, 0-16 Co, 0-1 Ti, 0-1 Nb. 5. Verfahren nach Patentanεpruch 2, dadurch gekennzeichnet, daεs die Partikel 15-33 Gewichtsprozent TiC enthalten und im übrigen aus einer Ni-Legierung bestehen, die Legierungszusätze aus den folgenden Elementen und in den angegebenen Gewichtsprozentbereichen enthält :0-0.8 C, 0-20 Cr, 2-15 Mo, 0.5-1 Cu, 0-1.5 AI, 5-16 Ni, 0-16 Co, 0-1 Ti, 0-1 Nb . 5. The method according to claim 2, characterized in that the particles contain 15-33 percent by weight of TiC and moreover consist of a Ni alloy that contains alloy additives from the following elements and in the stated percentages by weight:
14-25 Cr, 2-16 Mo, 0-1 Cu, 0-1 AI, 0-2,5 Ti, 0-1 Nb, 0-0,5 C, 0-3,14-25 Cr, 2-16 Mo, 0-1 Cu, 0-1 AI, 0-2.5 Ti, 0-1 Nb, 0-0.5 C, 0-3,
5 W.5 W.
6. Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass die Co-Legierung mindestens zwei Legierungszusätze aus den folgenden Elementen und in den angegebenen Gewjchtsprozentbereichen enthält :6. The method according to claim 1, characterized in that the co-alloy contains at least two alloy additions from the following elements and in the specified percentages by weight:
0-1 C, 0-25 Cr, 0-20 Mo, 0-2 Mn, 0-2 Cu, 0-2 AI, 0-1,5 Nb, 0-1 V, 0-2 Ti, 0-5 W, 0-2 Si.0-1 C, 0-25 Cr, 0-20 Mo, 0-2 Mn, 0-2 Cu, 0-2 AI, 0-1.5 Nb, 0-1 V, 0-2 Ti, 0-5 W, 0-2 Si.
7. Verfahren nach Patentanspruch 6, dadurch gekennzeichnet, dasε die Partikel 15-33 Gewichtεprozent TiC enthalten und im übrigen aus einer Co-Legierung bestehen, die Legierungszuεätze auε den folgenden Elementen und in den angegebenen Gewichtsprozentbereichen enthält :7. The method according to claim 6, characterized in that the particles contain 15-33 percent by weight of TiC and, moreover, consist of a Co alloy that contains alloy additions from the following elements and in the stated percentages by weight:
14-25 Cr, 2-16 Mo, 0-1 Cu, 0-1 AI, 0-2,5 Ti, 0-1 Nb, 0-1 C, 0-5 W.14-25 Cr, 2-16 Mo, 0-1 Cu, 0-1 AI, 0-2.5 Ti, 0-1 Nb, 0-1 C, 0-5 W.
8. Verfahren nach einem der Patentansprüche 1 bis 7, dadurch gekennzeichnet, dasε die Legierung einen Zuεatz von weniger als 3, vorzugsweiεe weniger alε 1 Gewichtεprozent Zr02 enthält.8. The method according to any one of claims 1 to 7, characterized in that the alloy contains an addition of less than 3, preferably less than 1% by weight of Zr0 2 .
9. Verfahren nach einem der Patentanεprüche 1 bis 8, dadurch gekennzeichnet, dass die Wärmebehandlung im Temperaturbereich von 400-600°C während einer Behandlungsdauer von 1-10 Stunden durchgeführt wird.9. The method according to any one of claims 1 to 8, characterized in that the heat treatment in the temperature range of 400-600 ° C is carried out for a treatment period of 1-10 hours.
10. Verfahren nach Patentanεpruch 9, dadurch gekennzeichnet, daεε die Wärmebehandlung im Temperaturbereich von 450-550°C während einer Behandlungεdauer von 1-5 Stunden durchgeführt wird. 10. The method according to claim 9, characterized in that the heat treatment is carried out in the temperature range of 450-550 ° C for a treatment period of 1-5 hours.
EP87900795A 1986-02-04 1987-02-04 Process for producing a titanium-carbide containing wear-resistant coating on a metal base Revoked EP0256049B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH425/86A CH670103A5 (en) 1986-02-04 1986-02-04
CH425/86 1986-02-04

Publications (2)

Publication Number Publication Date
EP0256049A1 true EP0256049A1 (en) 1988-02-24
EP0256049B1 EP0256049B1 (en) 1991-12-04

Family

ID=4186733

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87900795A Revoked EP0256049B1 (en) 1986-02-04 1987-02-04 Process for producing a titanium-carbide containing wear-resistant coating on a metal base

Country Status (5)

Country Link
US (1) US4806394A (en)
EP (1) EP0256049B1 (en)
CH (1) CH670103A5 (en)
DE (1) DE3774956D1 (en)
WO (1) WO1987004732A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5035957A (en) * 1981-11-27 1991-07-30 Sri International Coated metal product and precursor for forming same
JPH0778242B2 (en) * 1993-02-12 1995-08-23 日本ユテク株式会社 Method for manufacturing wear resistant composite metal member
US6048586A (en) * 1996-06-05 2000-04-11 Caterpillar Inc. Process for applying a functional gradient material coating to a component for improved performance
US6087022A (en) * 1996-06-05 2000-07-11 Caterpillar Inc. Component having a functionally graded material coating for improved performance
DE19640787C1 (en) * 1996-10-02 1998-04-16 Fraunhofer Ges Forschung Wear-resistant parts for process valves
DE19640788C1 (en) * 1996-10-02 1997-11-20 Fraunhofer Ges Forschung Coating powder used e.g. in thermal spraying
US5798002A (en) * 1996-12-02 1998-08-25 Gugel; Saveliy M. Method of and device for producing carbide and carbon solid solution containing surface layers
DE60210660T2 (en) 2001-12-04 2007-02-22 Magotteaux International S.A. FOUNDRY WITH IMPROVED WEAR RESISTANCE
JP2004359998A (en) * 2003-06-04 2004-12-24 Hitachi Ltd Method for manufacturing metallic member having compound-particle-dispersed alloy layer, and slide member
EP1711642B1 (en) * 2004-01-28 2010-07-07 Ford Global Technologies, LLC, A subsidary of Ford Motor Company Ferrous layer for a sliding surface, in particular for cylinder running surfaces on engine blocks, applied by means of thermal spraying
CA2861581C (en) 2011-12-30 2021-05-04 Scoperta, Inc. Coating compositions
WO2015167769A1 (en) * 2014-04-30 2015-11-05 Oerlikon Metco (Us) Inc. Titanium carbide overlay and method of making
US10465267B2 (en) * 2014-07-24 2019-11-05 Scoperta, Inc. Hardfacing alloys resistant to hot tearing and cracking
MX2018002635A (en) 2015-09-04 2019-02-07 Scoperta Inc Chromium free and low-chromium wear resistant alloys.
CN113195759B (en) 2018-10-26 2023-09-19 欧瑞康美科（美国）公司 Corrosion and wear resistant nickel base alloy

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA659644A (en) * 1963-03-19 J. Dittrich Ferdinand Production of carbide-containing sprayweld coatings
FR1357986A (en) * 1963-05-21 1964-04-10 Soudure Electr Autogene Method of applying a covering of materials to a part by spraying
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US3896244A (en) * 1971-11-17 1975-07-22 Chromalloy American Corp Method of producing plasma sprayed titanium carbide tool steel coatings
US3779720A (en) * 1971-11-17 1973-12-18 Chromalloy American Corp Plasma sprayed titanium carbide tool steel coating
US3941903A (en) * 1972-11-17 1976-03-02 Union Carbide Corporation Wear-resistant bearing material and a process for making it
GB2050424B (en) * 1979-05-09 1983-06-15 Special Metals Corp Nickel-cobalt-chromium base alloy
GB2076019B (en) * 1980-05-16 1984-03-28 Metallurg Ind Inc Erosion-resistant alloys
US4395279A (en) * 1981-11-27 1983-07-26 Gte Products Corporation Plasma spray powder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8704732A1 *

Also Published As

Publication number Publication date
WO1987004732A1 (en) 1987-08-13
DE3774956D1 (en) 1992-01-16
US4806394A (en) 1989-02-21
EP0256049B1 (en) 1991-12-04
CH670103A5 (en) 1989-05-12

Similar Documents

Publication Publication Date Title
EP0256049A1 (en) Process for producing a titanium-carbide containing wear-resistant coating on a metal base.
DE3937526C2 (en) Wear-resistant titanium alloy, process for its production and its use
DE19780253C2 (en) Cast iron and piston ring
DE2829369A1 (en) PROCESS FOR DESIGNING HARD, WEAR-RESISTANT COVERS AND OBJECTS PROVIDED WITH SUCH A COVER
DE1198568B (en) Process for the production of pore-free spray-weld coatings
DE2801016A1 (en) ITEM MADE OF A SUPER ALLOY THAT IS PROVIDED WITH AN OXIDATION AND CORROSION-RESISTANT COATING BY FLAME SPRAYING, AND THE PROCESS FOR THE PRODUCTION OF IT
DE2208070C2 (en) Composite body and process for its manufacture
DE2853724A1 (en) Sputtered or wire explosion formed hard wear resistant metal coating - has finely dispersed metal oxide particles in metal matrix
WO1982001897A1 (en) Material allowing the stratification of machining parts,the latter having then an improved resistance to abrasion and hammering
DE4203869C2 (en) Heavy-duty, coated components made of a material that consists of the intermetallic phase titanium aluminide
DE3137752C2 (en)
DE2210935A1 (en) MEASURES MADE FROM TITANIUM CARBIDE AND A STEEL BASE MEASUREMENT FOR THE SURFACE HARDENING OF METAL SUBSTRATES
EP0438971A1 (en) Coated metallic substrate
DE19508947A1 (en) New wear resistant iron@-molybdenum@-tungsten@ alloy
EP0948659B1 (en) Coating powder and method for its production
DE1246352B (en) Powder mixture for aluminizing workpieces made of high-alloy steels or alloys based on at least one of the metals cobalt, nickel or chromium
DE2919478A1 (en) COPPER-ZINC ALLOY AND THEIR USE
DE3241377A1 (en) FLAME INJECTION MATERIAL
CH668776A5 (en) METHOD FOR PRODUCING AN EROSION-RESISTANT SURFACE LAYER ON A METAL WORKPIECE.
WO2002048422A1 (en) Wear protection layer for piston rings, containing wolfram carbide and chromium carbide
DE60310283T3 (en) High temperature element for a gas turbine
CH663219A5 (en) FLAME INJECTION MATERIAL.
EP0386618A1 (en) Element with wear-resisting layer comprising nickel or cobalt
DE2743841C2 (en) Use of an Fe-Ni-Si alloy as a material for producing a working surface for valve rocker arms
DE10061749C2 (en) Piston ring for internal combustion engines

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19880125

17Q First examination report despatched

Effective date: 19890717

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3774956

Country of ref document: DE

Date of ref document: 19920116

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: THYSSEN EDELSTAHLWERKE AG

Effective date: 19920606

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: FRIED. KRUPP AG

Effective date: 19920825

Opponent name: THYSSEN EDELSTAHLWERKE AG

Effective date: 19920606

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

Ref country code: GB

Payment date: 19930112

Year of fee payment: 7

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

Ref country code: FR

Payment date: 19930204

Year of fee payment: 7

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

Ref country code: DE

Payment date: 19930304

Year of fee payment: 7

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

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: THYSSEN EDELSTAHLWERKE AG * 920825 FRIED. KRUPP A

Effective date: 19920606

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

Ref country code: GB

Effective date: 19940204

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940204

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19941021