EP0882811A1 - Method of carburizing metallic workpieces in a vacuum furnace - Google Patents

Method of carburizing metallic workpieces in a vacuum furnace Download PDF

Info

Publication number
EP0882811A1
EP0882811A1 EP97108860A EP97108860A EP0882811A1 EP 0882811 A1 EP0882811 A1 EP 0882811A1 EP 97108860 A EP97108860 A EP 97108860A EP 97108860 A EP97108860 A EP 97108860A EP 0882811 A1 EP0882811 A1 EP 0882811A1
Authority
EP
European Patent Office
Prior art keywords
carbon
carbon carrier
carburizing
partial pressure
carrier
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
EP97108860A
Other languages
German (de)
French (fr)
Other versions
EP0882811B1 (en
EP0882811B2 (en
Inventor
Bernd Dr. Edenhofer
Hansjakob Drissen
Winfried Gräfen
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.)
Ipsen International GmbH
Original Assignee
Ipsen International 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=8226864&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0882811(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ipsen International GmbH filed Critical Ipsen International GmbH
Priority to DE59704123T priority Critical patent/DE59704123D1/en
Priority to AT97108860T priority patent/ATE203572T1/en
Priority to EP97108860A priority patent/EP0882811B2/en
Priority to ES97108860T priority patent/ES2161398T5/en
Publication of EP0882811A1 publication Critical patent/EP0882811A1/en
Publication of EP0882811B1 publication Critical patent/EP0882811B1/en
Application granted granted Critical
Publication of EP0882811B2 publication Critical patent/EP0882811B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • C23C8/06Solid 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
    • C23C8/36Solid 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 using ionised gases, e.g. ionitriding
    • C23C8/38Treatment of ferrous surfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • C23C8/06Solid 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
    • C23C8/08Solid 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
    • C23C8/20Carburising
    • C23C8/22Carburising of ferrous surfaces

Definitions

  • the invention relates to a method for carburizing metallic workpieces in a vacuum furnace, the furnace atmosphere being a carbon carrier contains, under the process conditions of carburization with the release of pure carbon is split.
  • thermochemical case hardening treatments metallic workpieces have been in addition to the conventional gas carburizing is increasingly the carburizing processes in Vacuum systems enforced, because only with these procedures Carburization free of edge oxidation is feasible.
  • these Carburizing processes in vacuum plants are the vacuum and plasma carburizing. Since in these carburizing processes without oxygen-containing reaction gases is working, no C level control respectively; the key parameter for the carbon transition is at this method the carbon mass flow density, which as The amount of carbon is defined per unit of time and area in the Material passes over.
  • This carbon required for carburization is from a carbon carrier in the furnace atmosphere - usually one Hydrocarbon - provided at the given Process conditions with the release of pure carbon is split.
  • propane C 3 H 8
  • propane C 3 H 8
  • propane C 3 H 8
  • propane pyrolysis methane (CH 4 ) is mostly used as the carbon carrier, which is obtained by methane pyrolysis according to the equation CH 4 ⁇ C + 2H 2 is split.
  • propane instead of methane.
  • methane or propane as a carbon carrier is in each case associated with various advantages and disadvantages.
  • propane due to its larger number of carbon atoms - 3 carbon atoms for propane versus 1 carbon atom for methane - a more effective carbon carrier as methane.
  • propane has the disadvantage that it is already thermally split in the temperature range above 600 ° C, which leads to Sooting of the oven and tar formation in the oven can result.
  • methane only has one carbon atom, but it is the methane molecule so stable that it is not already necessary Carburizing temperature is split. Rather, the split takes place only in Plasma and therefore really only on the workpiece surface. Since the Carbon mass flow density is low when splitting methane, For large batches, large quantities of process gas must be sent to the furnace be fed.
  • Partial pressure of the carbon carrier pulsates towards higher partial pressures vary so that the increasing the carbon mass flow density Partial pressure of the carbon carrier only briefly to increase the Carburizing effect is available, but then decreases again, so that the soot formation can be kept within limits. Because of the partial high partial pressure of the carbon carrier of up to 100 mbar however, even in this method operated with pressure pulses gradual sooting of the furnace so that it still closes Cleaning purposes must be switched off.
  • the invention has for its object to provide a method for carburizing metallic workpieces in a vacuum furnace, which ensures a constant carburization with a high carbon mass flow density, without the risk of sooting the furnace .
  • the carbon carrier is a hydrocarbon with a carbon-hydrogen ratio of 1: 1 is used, preferably acetylene.
  • a partial pressure of the carbon carrier of less than 20 mbar, preferably 10 mbar, observed in order to achieve a high without soot formation Carbon mass flow density or carbon transfer rate achieve.
  • Carburizing the partial pressure of the carbon carrier pulsating can be varied, the partial pressure of the carbon carrier values from to reached to 50 mbar.
  • the furnace atmosphere can also contain other gases, in particular Contain hydrogen and / or argon, which additionally as the inert gases Prevent oxidation of the workpieces.
  • the Splitting of the carbon carrier can be supported by a plasma.
  • Vacuum carburization with the carbon carriers propane and ethane took place at 860 ° C and with a partial pressure of the carbon carrier of 10 mbar.
  • the vacuum carburization with the carbon carrier acetylene was carried out at 930 ° C and a partial pressure of the carbon carrier of 10 mbar a carburizing and diffusion phase period of 260 min.
  • the above-described uniform carburization on the outer and The inner surface of the test workpiece is also shown in the illustrations 2 to 4, in which the surface hardness and the case hardening depth (HV 1.0) is shown at different measuring points.
  • a comparison of the graphics 3 and 4 shows that when using acetylene as a carbon carrier not just an almost constant surface hardness along the inner and outer workpiece surface is achieved, but also the Case hardening depth (HV 1.0) on the inner and outer Workpiece surface coincides almost at all measuring points.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Furnace Details (AREA)

Abstract

The method concerns carburisation of metal workpieces in a vacuum furnace, according to which the furnace atmosphere contains a carbon carrier which under the process conditions is split for delivery of pure carbon. The carbon carrier used is a hydrocarbon with a carbon to hydrogen ratio of 1:1, preferably acetylene.

Description

Die Erfindung betrifft ein Verfahren zur Aufkohlung metallischer Werkstücke in einem Vakuum-Ofen, wobei die Ofenatmosphäre einen Kohlenstoff-Träger enthält, der unter den Prozeßbedingungen der Aufkohlung unter Abgabe von reinem Kohlenstoff gespalten wird.The invention relates to a method for carburizing metallic workpieces in a vacuum furnace, the furnace atmosphere being a carbon carrier contains, under the process conditions of carburization with the release of pure carbon is split.

Unter den thermochemischen Behandlungsverfahren zur Einsatzhärtung metallischer Werkstücke haben sich in den letzten Jahren neben der konventionellen Gasaufkohlung immer mehr die Aufkohlungsprozesse in Vakuumanlagen durchgesetzt, da nur mit diesen Verfahren eine randoxidationsfreie Aufkohlung realisierbar ist. Bei diesen Aufkohlungsprozessen in Vakuumanlagen handelt es sich um die Unterdruck- und die Plasmaaufkohlung. Da bei diesen Aufkohlungsverfahren ohne sauerstoffhaltige Reaktionsgase gearbeitet wird, kann keine C-Pegelregelung erfolgen; die entscheidende Kenngröße für den Kohlenstoffübergang ist bei diesen Verfahren die Kohlenstoff-Massenstromdichte, die als Kohlenstoffmenge definiert ist, die pro Zeit- und Flächeneinheit in den Werkstoff übergeht. Dieser zur Aufkohlung benötigte Kohlenstoff wird von einem in der Ofenatmosphäre befindlichen Kohlenstoff-Träger - meist einem Kohlenwasserstoff - zur Verfügung gestellt, der bei den gegebenen Prozeßbedingungen unter Abgabe von reinem Kohlenstoff gespalten wird.Among thermochemical case hardening treatments metallic workpieces have been in addition to the conventional gas carburizing is increasingly the carburizing processes in Vacuum systems enforced, because only with these procedures Carburization free of edge oxidation is feasible. With these Carburizing processes in vacuum plants are the vacuum and plasma carburizing. Since in these carburizing processes without oxygen-containing reaction gases is working, no C level control respectively; the key parameter for the carbon transition is at this method the carbon mass flow density, which as The amount of carbon is defined per unit of time and area in the Material passes over. This carbon required for carburization is from a carbon carrier in the furnace atmosphere - usually one Hydrocarbon - provided at the given Process conditions with the release of pure carbon is split.

Bei den bekannten Unterdruck-Aufkohlungsverfahren wird als Kohlenstoff-Träger in der Regel Propan (C3H8) verwendet, welches im Laufe der sogenannten Propanpyrolyse nach folgenden Reaktionsgleichungen gespalten wird: C3H8 → CH4 + C2H4 C2H4 → 2C + 2H2 CH4 → C + 2H2 Bei der Plasmaaufkohlung wird als Kohlenstoff-Träger meist Methan (CH4) verwendet, welches im Wege der Methanpyrolyse nach der Gleichung CH4 → C + 2H2 gespalten wird. Bei der Plasmaaufkohlung ist es jedoch auch möglich, anstelle von Methan Propan zu verwenden.In the known vacuum carburizing processes, propane (C 3 H 8 ) is generally used as the carbon carrier, which is split in the course of the so-called propane pyrolysis according to the following reaction equations: C 3 H 8 → CH 4 + C 2 H 4 C 2 H 4 → 2C + 2H 2 CH 4 → C + 2H 2 In plasma carburizing, methane (CH 4 ) is mostly used as the carbon carrier, which is obtained by methane pyrolysis according to the equation CH 4 → C + 2H 2 is split. In plasma carburizing, however, it is also possible to use propane instead of methane.

Die Verwendung von Methan oder Propan als Kohlenstoff-Träger ist jeweils mit verschiedenen Vor- und Nachteilen verbunden. So ist beispielsweise Propan aufgrund seiner größeren Anzahl von Kohlenstoffatomen - 3 C-Atome bei Propan gegenüber 1 C-Atom bei Methan - ein wirksamerer Kohlenstoff-Träger als Methan. Andererseits weist Propan jedoch den Nachteil auf, daß es bereits im Temperaturbereich über 600°C thermisch gespalten wird, was zum Verrußen des Ofens sowie zur Teerbildung im Ofen führen kann. Die frühe Dissoziation des Propan schon bei niedrigen Temperaturen hat darüber hinaus zur Folge, daß bei der Behandlung dicht gepackter Chargen sowie von Werkstücken mit schwierig zugängigen Oberflächen, wie beispielsweise Sacklochbohrungen, der dissoziierte Kohlenstoff überwiegend außen an der Charge abgegeben wird, so daß die Aufkohlungswirkung in der Chargenmitte geringer ist. Dasselbe gilt nicht nur für dicht gepackte Chargen, sondern auch für Bohrungen, insbesondere Sacklochbohrungen, bei denen der Kohlenstoff überwiegend an der Bohrungsöffnung abgegeben wird und im Inneren der Bohrung kaum noch eine Aufkohlungswirkung nachzuweisen ist.The use of methane or propane as a carbon carrier is in each case associated with various advantages and disadvantages. For example Propane due to its larger number of carbon atoms - 3 carbon atoms for propane versus 1 carbon atom for methane - a more effective carbon carrier as methane. On the other hand, however, propane has the disadvantage that it is already thermally split in the temperature range above 600 ° C, which leads to Sooting of the oven and tar formation in the oven can result. The early one Dissociation of the propane even at low temperatures has beyond that as a result that in the treatment of tightly packed batches and of Workpieces with difficult to access surfaces, such as Blind holes, the dissociated carbon predominantly on the outside of the Batch is released so that the carburizing effect in the middle of the batch is less. The same applies not only to tightly packed batches, but also for bores, in particular blind holes, in which the carbon is predominantly dispensed at the bore opening and inside the There is hardly any carburizing effect in the bore.

Methan hingegen weist zwar nur ein C-Atom auf, jedoch ist das Methan-Molekül so stabil, daß es nicht bereits bei der notwendigen Aufkohlungstemperatur gespalten wird. Die Spaltung erfolgt vielmehr erst im Plasma und somit wirklich nur an der Werkstückoberfläche. Da die Kohlenstoff-Massenstromdichte bei der Spaltung von Methan gering ist, müssen bei großflächigen Chargen große Mengen an Prozeßgas dem Ofen zugeführt werden.In contrast, methane only has one carbon atom, but it is the methane molecule so stable that it is not already necessary Carburizing temperature is split. Rather, the split takes place only in Plasma and therefore really only on the workpiece surface. Since the Carbon mass flow density is low when splitting methane, For large batches, large quantities of process gas must be sent to the furnace be fed.

Wie bereits voranstehend angedeutet, liegt ein weiteres Problem bei den aus dem Stand der Technik bekannten Aufkohlungsverfahren darin, daß mit zunehmendem Kohlenstoff-Wasserstoff-Verhältnis (C/H) des Kohlenstoff-Trägers die Rußbildung im Ofen zunimmt. Bei Methan, CH4 (C/H = 0,25), ist der Rußanfall gering, bei Ethan, C2H6 (C/H = 0,33), ist der Rußanfall mittelgroß, bei Propan, C3H8 (C/H = 0,375) groß und bei Butan, C4H10 (C/H = 0,4) sehr hoch. Somit stehen sich bei der Optimierung der Aufkohlungsverfahren in Vakuum-Öfen zwei widerstreitende Forderungen bzw. Prozesse gegenüber, nämlich einerseits die Forderung nach einer Erhöhung des Kohlenstoff-Wasserstoff-Verhältnisses beim Kohlenstoff-Träger zur Erhöhung der Kohlenstoff-Massenstromdichte zur Erzielung einer besseren Aufkohlungswirkung und andererseits die zunehmende Rußbildung bei der Erhöhung des Kohlenstoff-Wasserstoff-Verhältnisses beim Kohlenstoff-Träger. Eine zur Erhöhung der Kohlenstoff-Massenstromdichte angestrebte Erhöhung des Partialdruckes des Kohlenstoff-Trägers erhöht dabei zusätzlich die Rußbildung im Ofen.As already indicated above, a further problem with the carburizing processes known from the prior art is that with increasing carbon-hydrogen ratio (C / H) of the carbon carrier, the soot formation in the furnace increases. With methane, CH 4 (C / H = 0.25), the soot accumulation is low, with ethane, C 2 H 6 (C / H = 0.33), the soot accumulation is medium, with propane, C 3 H 8 ( C / H = 0.375) large and very high for butane, C 4 H 10 (C / H = 0.4). Thus, when optimizing the carburizing processes in vacuum furnaces, there are two conflicting demands or processes, namely on the one hand the demand for an increase in the carbon-hydrogen ratio in the carbon carrier to increase the carbon mass flow density to achieve a better carburizing effect and on the other hand the increasing soot formation with the increase in the carbon-hydrogen ratio in the carbon carrier. An increase in the partial pressure of the carbon support aimed at increasing the carbon mass flow density additionally increases the soot formation in the furnace.

Zur Reduzierung der Rußbildung bei steigendem Partialdruck des Kohlenstoff-Trägers ist es beispielsweise aus der US-PS 3 796 615 bekannt, den Partialdruck des Kohlenstoff-Trägers pulsierend auf höhere Partialdrücke zu variieren, so daß der die Kohlenstoff-Massenstromdichte erhöhende Partialdruck des Kohlenstoff-Trägers nur kurzzeitig zur Erhöhung der Aufkohlungswirkung zur Verfügung steht, danach jedoch wieder absinkt, so daß die Rußbildung in Grenzen gehalten werden kann. Aufgrund des teilweise hohen Partialdruckes des Kohlenstoff-Trägers von bis zu 100 mbar liegt jedoch selbst bei diesem mit Druckpulsen betriebenen Verfahren eine allmähliche Verrußung des Ofens vor, so daß dieser immer noch zu Reinigungszwecken abgeschaltet werden muß.To reduce soot formation with increasing partial pressure of the carbon carrier it is known, for example, from US Pat. No. 3,796,615 Partial pressure of the carbon carrier pulsates towards higher partial pressures vary so that the increasing the carbon mass flow density Partial pressure of the carbon carrier only briefly to increase the Carburizing effect is available, but then decreases again, so that the soot formation can be kept within limits. Because of the partial high partial pressure of the carbon carrier of up to 100 mbar however, even in this method operated with pressure pulses gradual sooting of the furnace so that it still closes Cleaning purposes must be switched off.

In Anbetracht des voranstehend geschilderten Standes der Technik liegt der Erfindung die Aufgabe zugrunde, ein Verfahren zur Aufkohlung metallischer Werkstücke in einem Vakuum-Ofen bereitzustellen, das eine gleichbleibende Aufkohlung mit einer hohen Kohlenstoff-Massenstromdichte gewährleistet, ohne daß gleichzeitig die Gefahr der Verrußung des Ofens besteht.In view of the above-described prior art, the invention has for its object to provide a method for carburizing metallic workpieces in a vacuum furnace, which ensures a constant carburization with a high carbon mass flow density, without the risk of sooting the furnace .

Überraschenderweise hat sich herausgestellt, daß diese Aufgabe erfindungsgemäß dadurch gelöst wird, daß als Kohlenstoff-Träger ein Kohlenwasserstoff mit einem Kohlenstoff-Wasserstoff-Verhältnis von 1:1, vorzugsweise Acetylen, verwendet wird.Surprisingly, it has been found that this object is achieved in that as the carbon carrier is a hydrocarbon with a carbon-hydrogen ratio of 1: 1 is used, preferably acetylene.

Überraschend bei der Verwendung von Acetylen als Kohlenstoff-Träger ist nicht nur die sehr gute und gleichmäßige Aufkohlungswirkung auch bei schwierig zugänglichen Werkstücken, sondern insbesondere die Tatsache, daß trotz des hohen Kohlenstoff-Wasserstoff-Verhältnisses von 1:1 so gut wie keine Ruß- und Teerbildung auftritt. Die gute Aufkohlungswirkung bei der Verwendung von Acetylen als Kohlenstoff-Träger läßt sich damit erklären, daß aufgrund des hohen Kohlenstoff-Wasserstoff-Verhältnisses auch schon bei geringen Partialdrücken des Kohlenstoff-Trägers eine ausreichende Kohlenstoff-Massenstromdichte zur Verfügung steht, um eine gleichbleibende und ausreichende Aufkohlung zu erzielen.Is surprising when using acetylene as a carbon carrier not only the very good and even carburizing effect difficult to access workpieces, but especially the fact that despite the high carbon-hydrogen ratio of 1: 1 as good as no soot and tar formation occurs. The good carburizing effect at Use of acetylene as a carbon carrier can be explained by the fact that due to the high carbon-hydrogen ratio low partial pressures of the carbon carrier an adequate Carbon mass flow density is available to a constant and to achieve sufficient carburization.

Gemäß einer ersten bevorzugten erfindungsgemäßen Verfahrensweise wird mit Vorteil ein Partialdruck des Kohlenstoff-Trägers von unter 20 mbar, vorzugsweise 10 mbar, eingehalten, um ohne Rußbildung eine hohe Kohlenstoff-Massenstromdichte bzw. Kohlenstoff-Übertragungsrate zu erzielen. Dabei kann gemäß einer Verfahrensvariante des erfindungsgemäßen Aufkohlungsverfahrens der Partialdruck des Kohlenstoff-Trägers pulsierend variiert werden, wobei der Partialdruck des Kohlenstoff-Trägers Werte von bis zu 50 mbar erreicht.According to a first preferred procedure according to the invention advantageously a partial pressure of the carbon carrier of less than 20 mbar, preferably 10 mbar, observed in order to achieve a high without soot formation Carbon mass flow density or carbon transfer rate achieve. According to a variant of the method according to the invention Carburizing the partial pressure of the carbon carrier pulsating can be varied, the partial pressure of the carbon carrier values from to reached to 50 mbar.

Neben dem Kohlenwasserstoff mit einem Kohlenstoff-Wasserstoff-Verhältnis von 1:1 kann die Ofenatmosphäre zusätzlich noch weitere Gase, insbesondere Wasserstoff und/oder Argon enthalten, welche als Inertgase zusätzlich die Oxydation der Werkstücke verhindern sollen.In addition to the hydrocarbon with a carbon-hydrogen ratio 1: 1, the furnace atmosphere can also contain other gases, in particular Contain hydrogen and / or argon, which additionally as the inert gases Prevent oxidation of the workpieces.

Bei einer erfindungsgemäßen Weiterbildung des Verfahrens kann die Aufspaltung des Kohlenstoff-Trägers durch ein Plasma unterstützt werden. In a further development of the method according to the invention, the Splitting of the carbon carrier can be supported by a plasma.

Weitere Merkmale und Vorteile des erfindungsgemäßen Verfahrens ergeben sich aus den nachfolgenden Erläuterungen, die auf die beigefügten Zeichnungen Bezug nehmen. In der Zeichnung zeigt:

Fig. 1
einen schematischen Längsschnitt durch ein Probewerkstück mit zugehörigem Tabellenwerk, die Oberflächenhärtewerte auf der Innenseite des Probewerkstücks bei verschiedenen Kohlenstoff-Trägern wiedergebend;
Fig. 2
eine Seitenansicht des Probewerkstücks gemäß Fig. 1 mit der Angabe verschiedener Meßpunkte für den Härteverlauf an der Außen- und Innenseite des Probewerkstücks;
Fig. 3
eine graphische Darstellung des Härteverlaufs an den Meßpunkten A, C und E gemäß Fig. 2 an der Außenseite des Probewerkstücks nach der Einsatzhärtung mit Acetylen und
Fig. 4
eine graphische Darstellung des Härteverlaufs an den Meßpunkten B, D, F und H gemäß Fig. 2 an der Innenseite des Probewerkstück nach der Einsatzhärtung mit Acetylen.
Further features and advantages of the method according to the invention result from the following explanations, which refer to the accompanying drawings. The drawing shows:
Fig. 1
a schematic longitudinal section through a test workpiece with associated tables, showing the surface hardness values on the inside of the test workpiece with different carbon carriers;
Fig. 2
a side view of the sample workpiece according to FIG 1 with the specification of various measuring points for the hardness curve on the outside and inside of the sample workpiece.
Fig. 3
a graphical representation of the hardness curve at the measuring points A, C and E according to FIG. 2 on the outside of the test workpiece after case hardening with acetylene and
Fig. 4
a graphical representation of the hardness curve at the measuring points B, D, F and H according to FIG. 2 on the inside of the test workpiece after case hardening with acetylene.

In der Zeichnung mit dem zugehörigen Tabellenwerk ist für ein Rohr aus dem Werkstoff 16 MnCr 5 mit einer abgestuften Durchgangsbohrung der Verlauf der Oberflächenhärte auf der Innenseite des Rohres nach dem Unterdruckaufkohlen mit den Kohlenstoff-Trägern Acetylen, Propan und Ethan vergleichend dargestellt.In the drawing with the associated tables is for a pipe from the Material 16 MnCr 5 with a graduated through hole of the course the surface hardness on the inside of the pipe after the Vacuum carburizing with the carbon carriers acetylene, propane and ethane presented comparably.

Die Unterdruckaufkohlung mit den Kohlenstoff-Trägern Propan und Ethan erfolgte bei 860°C und mit einem Partialdruck des Kohlenstoff-Trägers von 10 mbar. Die Unterdruckaufkohlung mit dem Kohlenstoff-Träger Acetylen erfolgte bei 930°C und einem Partialdruck des Kohlenstoff-Trägers von 10 mbar über einen Zeitraum für die Aufkohlungs- und Diffusionsphase von 260 min.Vacuum carburization with the carbon carriers propane and ethane took place at 860 ° C and with a partial pressure of the carbon carrier of 10 mbar. The vacuum carburization with the carbon carrier acetylene was carried out at 930 ° C and a partial pressure of the carbon carrier of 10 mbar a carburizing and diffusion phase period of 260 min.

Wie aus der Abbildung sowie dem zugehörigen Tabellenwerk ersichtlich ist, wurden mit den aus dem Stand der Technik bekannten Kohlenstoff-Trägern Propan und Ethan Oberflächenhärten von etwa 60 HRC und mehr nur in den Randbereichen der Bohrungen, das heißt bis zu einer Bohrungstiefe von etwa 50 mm von beiden Bohrungsöffnungen her gesehen, erzielt. Dahingegen lag bei der Verwendung von Propan als Kohlenstoff-Träger der Wert der Oberflächenhärte in der Mitte der Durchgangsbohrung bei einer Bohrtiefe von 110 mm bei nur 36,0 HRC. Hier fand also so gut wie keine Aufkohlung statt. Bei der Verwendung von Ethan als Kohlenstoff-Träger, welches aufgrund seines geringeren Kohlenstoff-Wasserstoff-Verhältnisses bei gleichem Partialdruck des Kohlenstoff-Trägers auch nur eine geringere Kohlenstoff-Massendichte erzielen kann, lag der Wert für die Oberflächenhärte in der Mitte der Durchgangsbohrung sogar bei nur 25,9 HRC.As can be seen from the figure and the associated tables, with the carbon carriers known from the prior art Propane and ethane surface hardness of about 60 HRC and more only in the Edge areas of the holes, that is up to a hole depth of about 50 mm seen from both holes, achieved. In contrast, lay the value of when using propane as a carbon carrier Surface hardness in the middle of the through hole at a drilling depth of 110 mm at only 36.0 HRC. There was practically no carburization here. When using ethane as a carbon carrier, which due to its lower carbon-hydrogen ratio at the same Partial pressure of the carbon carrier also only a lower carbon mass density the surface hardness was in the middle the through hole even at only 25.9 HRC.

Im Vergleich mit diesen bekannten Kohlenstoff-Trägern Propan und Ethan wurde mit dem neuen Kohlenstoff-Träger Acetylen eine nahezu gleichbleibend gute Aufkohlung über die gesamte Durchgangsbohrung erzielt. Wie aus der Tabelle ersichtlich ist, liegt der Wert für die Oberflächenhärte an der inneren Oberfläche der Durchgangsbohrung fast durchgehend bei einem Wert von 60 HRC und mehr.In comparison with these known carbon carriers propane and ethane became almost constant with the new carbon carrier acetylene good carburization achieved over the entire through hole. As from the As can be seen in the table, the value for the surface hardness lies on the inner one Surface of the through hole almost continuously at a value of 60 HRC and more.

Die voranstehend beschriebene gleichmäßige Aufkohlung an der äußeren und inneren Oberfläche des Probewerkstücks verdeutlichen auch die Abbildungen Fig. 2 bis 4, in denen die Oberflächenhärte sowie die Einsatzhärtungstiefe (HV 1,0) an verschiedenen Meßpunkten dargestellt ist. Ein Vergleich der Graphiken in Fig. 3 und 4 zeigt, daß bei der Verwendung von Acetylen als Kohlenstoff-Träger nicht nur eine nahezu gleichbleibende Oberflächenhärte entlang der inneren und äußeren Werkstückoberfläche erzielt wird, sondern auch die Einsatzhärtungstiefe (HV 1,0) an der inneren und äußeren Werkstückoberfläche fast an allen Meßpunkten übereinstimmt.The above-described uniform carburization on the outer and The inner surface of the test workpiece is also shown in the illustrations 2 to 4, in which the surface hardness and the case hardening depth (HV 1.0) is shown at different measuring points. A comparison of the graphics 3 and 4 shows that when using acetylene as a carbon carrier not just an almost constant surface hardness along the inner and outer workpiece surface is achieved, but also the Case hardening depth (HV 1.0) on the inner and outer Workpiece surface coincides almost at all measuring points.

Mit dem voranstehend dargestellten Verfahren ist es somit möglich, durch die Verwendung eines Kohlenwasserstoffes mit einem Kohlenstoff-Wasserstoff-Verhältnis von 1:1, vorzugsweise Acetylen, als Kohlenstoff-Träger die Aufkohlungswirkung bei der Aufkohlung von metallischen Werkstücken in einem Vakuum-Ofen auch bei Werkstücken mit schwer zugänglichen Oberflächen deutlich zu erhöhen, ohne daß die Gefahr der Verrußung des Ofens besteht.With the method described above, it is thus possible to Use of a hydrocarbon with a carbon-hydrogen ratio of 1: 1, preferably acetylene, as the carbon carrier Carburizing effect when carburizing metallic workpieces in a vacuum oven even for workpieces with difficult to access Surfaces to increase significantly without the risk of sooting the Oven exists.

Claims (7)

Verfahren zur Aufkohlung metallischer Werkstücke in einem Vakuum-Ofen, wobei die Ofenatmosphäre einen Kohlenstoff-Träger enthält, der unter den Prozeßbedingungen der Aufkohlung unter Abgabe von reinem Kohlenstoff gespalten wird,
dadurch gekennzeichnet,
daß als Kohlenstoff-Träger ein Kohlenwasserstoff mit einem Kohlenstoff-Wasserstoff-Verhältnis von 1:1, vorzugsweise Acetylen, verwendet wird.
Process for carburizing metallic workpieces in a vacuum furnace, the furnace atmosphere containing a carbon carrier which is split under the process conditions of carburization with the release of pure carbon,
characterized,
that a hydrocarbon with a carbon-hydrogen ratio of 1: 1, preferably acetylene, is used as the carbon carrier.
Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Partialdruck des Kohlenstoff-Trägers unter 20 mbar, vorzugsweise 10 mbar, beträgt.A method according to claim 1, characterized in that the Partial pressure of the carbon carrier below 20 mbar, preferably 10 mbar. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Partialdruck des Kohlenstoff-Trägers pulsierend variiert wird.A method according to claim 1 or 2, characterized in that the Partial pressure of the carbon carrier is varied pulsating. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Partialdruck des Kohlenstoff-Trägers bei den Druckpulsen bis auf 50 mbar angehoben wird.A method according to claim 3, characterized in that the Partial pressure of the carbon carrier in the pressure pulses up to 50 mbar is raised. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß in der Ofenatmosphäre neben dem Kohlenstoff-Träger noch andere Gase enthalten sind.Method according to at least one of claims 1 to 4, characterized characterized in that in the furnace atmosphere next to the carbon carrier other gases are included. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Ofenatmosphäre zusätzlich noch Wasserstoff und/oder Argon enthält.A method according to claim 5, characterized in that the Furnace atmosphere also contains hydrogen and / or argon. Verfahren nach einem der Ansprüche 1, 2, 5 oder 6, dadurch gekennzeichnet, daß die Aufspaltung des Kohlenstoff-Trägers durch ein Plasma unterstützt wird.Method according to one of claims 1, 2, 5 or 6, characterized characterized in that the splitting of the carbon carrier by a Plasma is supported.
EP97108860A 1997-06-03 1997-06-03 Method of carburizing metallic workpieces in a vacuum furnace Expired - Lifetime EP0882811B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE59704123T DE59704123D1 (en) 1997-06-03 1997-06-03 Process for carburizing metallic workpieces in a vacuum furnace
AT97108860T ATE203572T1 (en) 1997-06-03 1997-06-03 METHOD FOR CARBURING METAL WORKPIECES IN A VACUUM FURNACE
EP97108860A EP0882811B2 (en) 1997-06-03 1997-06-03 Method of carburizing metallic workpieces in a vacuum furnace
ES97108860T ES2161398T5 (en) 1997-06-03 1997-06-03 PROCEDURE FOR CARBURATION OF METAL PARTS IN A VACUUM OVEN.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP97108860A EP0882811B2 (en) 1997-06-03 1997-06-03 Method of carburizing metallic workpieces in a vacuum furnace

Publications (3)

Publication Number Publication Date
EP0882811A1 true EP0882811A1 (en) 1998-12-09
EP0882811B1 EP0882811B1 (en) 2001-07-25
EP0882811B2 EP0882811B2 (en) 2010-12-15

Family

ID=8226864

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97108860A Expired - Lifetime EP0882811B2 (en) 1997-06-03 1997-06-03 Method of carburizing metallic workpieces in a vacuum furnace

Country Status (4)

Country Link
EP (1) EP0882811B2 (en)
AT (1) ATE203572T1 (en)
DE (1) DE59704123D1 (en)
ES (1) ES2161398T5 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0818555A1 (en) 1995-03-29 1998-01-14 JH Corporation Method and equipment for vacuum carburization and products of carburization
FR2821362A1 (en) * 2001-02-23 2002-08-30 Etudes Const Mecaniques LOW PRESSURE CEMENTING PROCESS
WO2003097893A1 (en) * 2002-05-15 2003-11-27 Linde Aktiengesellschaft Method and device for heat treatment of metallic work pieces
EP1391525A1 (en) * 2002-08-01 2004-02-25 Ipsen International GmbH Process and apparatus for blackening components
FR2847591A1 (en) * 2002-11-25 2004-05-28 Bosch Gmbh Robert Cementation of hot working steel components by low pressure or vacuum carburation involves fixing the peripheral carbon content by thermodynamic simulation
US6846366B2 (en) 2001-01-19 2005-01-25 Oriental Engineering Co., Ltd. Carburizing method and carburizing apparatus

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10209382B4 (en) * 2002-03-02 2011-04-07 Robert Bosch Gmbh Method of carburizing components
PL204202B1 (en) 2002-10-21 2009-12-31 Politechnika & Lstrok Odzka Mixture for negative pressure carburization
DE10322563B3 (en) * 2003-05-20 2004-11-11 Ipsen International Gmbh Vacuum carburizing or vacuum case hardening of steel components at low absolute pressure with addition of hydrogen, nitrogen, or argon
DE102009041927B4 (en) 2009-09-17 2015-08-06 Hanomag Härtecenter GmbH Process for low-pressure carburizing of metallic workpieces
PT2886668T (en) 2013-12-19 2019-02-04 Groz Beckert Kg Textile tool and manufacturing method for the same
PL422596A1 (en) 2017-08-21 2019-02-25 Seco/Warwick Spółka Akcyjna Method for low pressure carburizing (LPC) of elements made from iron and other metals alloys

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU668978A1 (en) * 1977-06-02 1979-06-28 Предприятие П/Я А-7697 Method of carburisation of steel articles
GB2261227A (en) * 1991-11-08 1993-05-12 Univ Hull Surface treatment of metals at low pressure
WO1996030556A1 (en) * 1995-03-29 1996-10-03 Jh Corporation Method and equipment for vacuum carburization and products of carburization

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3796615A (en) 1971-06-23 1974-03-12 Hayes Inc C I Method of vacuum carburizing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU668978A1 (en) * 1977-06-02 1979-06-28 Предприятие П/Я А-7697 Method of carburisation of steel articles
GB2261227A (en) * 1991-11-08 1993-05-12 Univ Hull Surface treatment of metals at low pressure
WO1996030556A1 (en) * 1995-03-29 1996-10-03 Jh Corporation Method and equipment for vacuum carburization and products of carburization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8010, Derwent World Patents Index; Class M13, AN 80-17823C, XP002046310 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0818555A1 (en) 1995-03-29 1998-01-14 JH Corporation Method and equipment for vacuum carburization and products of carburization
EP0818555B2 (en) 1995-03-29 2007-08-15 JH Corporation Method for vacuum carburization
US6846366B2 (en) 2001-01-19 2005-01-25 Oriental Engineering Co., Ltd. Carburizing method and carburizing apparatus
FR2821362A1 (en) * 2001-02-23 2002-08-30 Etudes Const Mecaniques LOW PRESSURE CEMENTING PROCESS
WO2002068707A1 (en) * 2001-02-23 2002-09-06 Etudes Et Constructions Mecaniques Low-pressure carburising method
US7118634B2 (en) 2001-02-23 2006-10-10 Bnp Parlbas Low-pressure cementation method
WO2003097893A1 (en) * 2002-05-15 2003-11-27 Linde Aktiengesellschaft Method and device for heat treatment of metallic work pieces
EP1391525A1 (en) * 2002-08-01 2004-02-25 Ipsen International GmbH Process and apparatus for blackening components
US7160576B2 (en) 2002-08-01 2007-01-09 Ipsen International Gmbh Method and device for blacking components
FR2847591A1 (en) * 2002-11-25 2004-05-28 Bosch Gmbh Robert Cementation of hot working steel components by low pressure or vacuum carburation involves fixing the peripheral carbon content by thermodynamic simulation

Also Published As

Publication number Publication date
ES2161398T3 (en) 2001-12-01
EP0882811B1 (en) 2001-07-25
EP0882811B2 (en) 2010-12-15
ES2161398T5 (en) 2011-04-05
DE59704123D1 (en) 2001-08-30
ATE203572T1 (en) 2001-08-15

Similar Documents

Publication Publication Date Title
EP0882811B1 (en) Method of carburizing metallic workpieces in a vacuum furnace
EP2203575B1 (en) Method for carburising workpieces and associated use
DE3841731C1 (en) Process for coating a tool base, and tool produced by this process
DE4420262A1 (en) Amorphous hard carbon film and process for its production
DE19526387A1 (en) Steel components with wear and oxidation resistant double coating
DE60223202T2 (en) PROCESS FOR LOW PRESSURE RECYCLING
EP1333105B1 (en) Process for heat treating metallic articles and heat treated article
DE3019830C2 (en) Process for carburizing and heating workpieces made of steel in a controlled furnace atmosphere
DE19909694A1 (en) Production of carbonitrided edge layers in a low pressure carburization process comprises enriching the edge layers with nitrogen at the end of the process using molecular nitrogen as donor gas
DE102013213897A1 (en) Method and apparatus for forming amorphous hard carbon coatings
EP1160349B1 (en) Process and apparatus for heat treating of metallic workpieces
EP0779376B2 (en) Plasma carburizing of metallic workpieces
EP1122331A1 (en) Process of nitriding and/or carbonitriding of high-alloyed steel
EP1044289B1 (en) Plasma boronizing
AT404139B (en) METHOD FOR THE HEAT TREATMENT OF WORKPIECES UNDER TREATMENT GAS
DE19822928C2 (en) Process for the adhesive application of a coating to a tribologically stressed surface of a chain link and chain link
DE2109997A1 (en) Process for metallic cementing animals
DE2802445B2 (en) Process for the continuous production of a steel strip from steel powder
DE2435026A1 (en) PROCESS FOR PRODUCING A PROTECTIVE GAS WITH DEFINED CARBON EFFECT
EP0318998B1 (en) Process for the production of thermally stable layers with a great hardness and/or low-friction properties
DE692080C (en) Process for casting metal objects in gas or vapor form
DE3540282A1 (en) ACCELERATED CARBURETOR PROCESS WITH DISCRETE MEDIA
DE3512825A1 (en) METHOD FOR THE PRODUCTION OF WEAR-RESISTANT COMPOSITES
DE10209382B4 (en) Method of carburizing components
DE1167152B (en) Process for carburizing steel using methyl alcohol and gas mixtures containing it

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): AT BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19990609

AKX Designation fees paid

Free format text: AT BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 20000331

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 203572

Country of ref document: AT

Date of ref document: 20010815

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

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

Effective date: 20010726

REF Corresponds to:

Ref document number: 59704123

Country of ref document: DE

Date of ref document: 20010830

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: ALD VACUUM TECHNOLOGIES AG

Effective date: 20010921

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2161398

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

NLR1 Nl: opposition has been filed with the epo

Opponent name: ALD VACUUM TECHNOLOGIES AG

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: AICHELIN GESMBH

Effective date: 20020402

Opponent name: ALD VACUUM TECHNOLOGIES AG

Effective date: 20010921

NLR1 Nl: opposition has been filed with the epo

Opponent name: AICHELIN GESMBH

Opponent name: ALD VACUUM TECHNOLOGIES AG

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

Free format text: ORIGINAL CODE: EPIDOS OBSO

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APAA Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOS REFN

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: IPSEN INTERNATIONAL GMBH

Free format text: IPSEN INTERNATIONAL GMBH#FLUTSTRASSE 78#47533 KLEVE (DE) -TRANSFER TO- IPSEN INTERNATIONAL GMBH#FLUTSTRASSE 78#47533 KLEVE (DE)

PLBP Opposition withdrawn

Free format text: ORIGINAL CODE: 0009264

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

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

Free format text: ORIGINAL CODE: 0009299OPPO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20101215

AK Designated contracting states

Kind code of ref document: B2

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

REG Reference to a national code

Ref country code: SE

Ref legal event code: RPEO

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2161398

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20110405

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

Ref country code: GB

Payment date: 20140618

Year of fee payment: 18

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

Ref country code: IT

Payment date: 20140627

Year of fee payment: 18

Ref country code: SE

Payment date: 20140618

Year of fee payment: 18

Ref country code: ES

Payment date: 20140627

Year of fee payment: 18

Ref country code: DE

Payment date: 20140619

Year of fee payment: 18

Ref country code: CH

Payment date: 20140618

Year of fee payment: 18

Ref country code: NL

Payment date: 20140618

Year of fee payment: 18

Ref country code: AT

Payment date: 20140611

Year of fee payment: 18

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

Ref country code: BE

Payment date: 20140620

Year of fee payment: 18

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

Ref country code: FR

Payment date: 20140619

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59704123

Country of ref document: DE

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 NON-PAYMENT OF DUE FEES

Effective date: 20150603

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 203572

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150603

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

Effective date: 20150603

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

Ref country code: SE

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

Effective date: 20150604

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20150701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160229

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: 20150630

Ref country code: DE

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

Effective date: 20160101

Ref country code: GB

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

Effective date: 20150603

Ref country code: CH

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

Effective date: 20150630

Ref country code: NL

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

Effective date: 20150701

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

Ref country code: AT

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

Effective date: 20150603

Ref country code: FR

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

Effective date: 20150630

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160728

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

Ref country code: ES

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

Effective date: 20150604

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

Ref country code: BE

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

Effective date: 20150630