EP0990055A1 - Improvements to steel for forming tools - Google Patents

Improvements to steel for forming tools

Info

Publication number
EP0990055A1
EP0990055A1 EP98920603A EP98920603A EP0990055A1 EP 0990055 A1 EP0990055 A1 EP 0990055A1 EP 98920603 A EP98920603 A EP 98920603A EP 98920603 A EP98920603 A EP 98920603A EP 0990055 A1 EP0990055 A1 EP 0990055A1
Authority
EP
European Patent Office
Prior art keywords
steel
niobium
carbon
vanadium
tungsten
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
EP98920603A
Other languages
German (de)
French (fr)
Other versions
EP0990055B1 (en
Inventor
Jacques Adrien
Bertrand Remi
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.)
Thyssen France SA
Original Assignee
Thyssen France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thyssen France SA filed Critical Thyssen France SA
Publication of EP0990055A1 publication Critical patent/EP0990055A1/en
Application granted granted Critical
Publication of EP0990055B1 publication Critical patent/EP0990055B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum

Definitions

  • the present invention relates to a steel obtained by powder metallurgy.
  • This steel obtained from an agglomerated pre-alloyed powder, is characterized in that the alloy has the following weight composition:
  • said steel has a dispersion of Niobium carbides and chromium carbides (Fe-Cr) ⁇ C in preference to (Cr ⁇ -c ⁇ ) obtained by a chromium content of between 6.05 and 6.45%, giving it improved resistance to abrasive wear without affecting the other properties or even improving them.
  • the present invention proposes to provide a semi-hot or even cold forming steel, produced starting from powder metallurgy.
  • the techniques used in mid-hot shaping are generally those of cold shaping but the blanks are preheated to a temperature between 900 ° and room temperature.
  • the main obstacles to the development of mid-hot forming are
  • the tool-part contact time is between 0.5 & 2 seconds. It is mainly on the improvement of the behavior of the material with respect to thermal and mechanical stresses, thermal and mechanical shocks, the increase in abrasion resistance that the shaping steel, object of the 3 present invention, proposes to respond by having a high hardness when cold associated with high characteristics when hot.
  • the new semi-rapid steel produced from powder metallurgy has a dispersion of niobium carbides and chromium carbides (Fe-Cr) 4C in preference to Cr ⁇ C- ⁇ generated by a chromium content of between 6, 05 and 6.45% by weight giving it improved resistance to abrasive wear without reducing the characteristics of the other properties, in particular the toughness.
  • the steel of the present invention complements the ATSI H.11 type steels. H.12 H.13 and M50-M2 etc.
  • niobium carbide 1% niobium for 0.12% carbon.
  • the carbon content of the steel is balanced with its vanadium, niobium, chromium, molybdenum contents to supply sufficient carbon and thus allow the object obtained by powder metallurgy to be heat treated so as to obtain a hardness ⁇ 64 Hrc.
  • the steel for shaping tools according to the invention has a combination of qualities: resistance to abrasive wear, hot hardness characterized by the Mathon cutting capacity test, toughness which could not be obtained. until now.
  • the toughness is determined by a measurement according to the Charpy test defined in standard ASTM 23-92 and 23-93. A 10x10x55mm reference test piece is treated at 1050 ° C, oil stop or isothermal stop at 560 ° C followed three hour returns at 560 °; it then has a toughness greater than 100J / cm2.
  • the cutting capacity is characterized by the Mathon test (defined in standard AFMOR A.03.654).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

The invention concerns steel obtained by powder metallurgy, formed from a sintered and densified high purity pre-alloyed powder. The invention is characterised in that the steel weight composition is as follows: manganese < 1 %; silicon < 1 %; chromium 6.05-6.45 %; molybdenum 2.50-3.50 %; vanadium 0.80-2 %; tungsten < 0.5 %; sulphur < 0.020 %; phosphorus < 0.030 %; niobium 0.60-1.60 %; cobalt 2 to 5 %; nitrogen 0.050 to 0.080 %; aluminium < 0.060 %; carbon 0.75-0.95 %; nickel < 0.50 %; the rest being iron and the standard impurities involved in steel manufacture.

Description

Perfectionnements apportés aux aciers pour outils de mise en formeImprovements to steels for shaping tools
La présente invention a pour objet un acier obtenu par la métallurgie des poudres.The present invention relates to a steel obtained by powder metallurgy.
Cet acier, obtenu à partir d'une poudre pré-alliée agglomérée est caractérisé en ce que l'alliage a la composition pondérale suivante :This steel, obtained from an agglomerated pre-alloyed powder, is characterized in that the alloy has the following weight composition:
Fourchette préférée Fourchette largePreferred range Wide range
Manganèse 0,20-0,40 % < 1%Manganese 0.20-0.40% <1%
Silicium 0,20-0,40 % 1%Silicon 0.20-0.40% 1%
Chrome 6,05-6,45 % 6,05-6,45% Molybdène 2,75-3,25 % 2,50-3,50% Vanadium 0,90-1,30 % 0,80-2% Tungstène 0,50 % 0,50% Soufre 0,020 % < 0,020% Phosphore < 0,030 % *-. 0,030% Niobium 0,70-1,10 % 0,60-1,60% Cobalt 2,60-3,40 % 2 à 5% Azote 0,050-0,080 % 0,050-0,080% Aluminium < 0,060 % -£0,060% Carbone 0,78-0,85 % 0,75-0,95% Nickel <0,30 % έ. 0,50% 2Chromium 6.05-6.45% 6.05-6.45% Molybdenum 2.75-3.25% 2.50-3.50% Vanadium 0.90-1.30% 0.80-2% Tungsten 0.50% 0.50% Sulfur 0.020% <0.020% Phosphorus <0.030% * -. 0.030% Niobium 0.70-1.10% 0.60-1.60% Cobalt 2.60-3.40% 2 to 5% Nitrogen 0.050-0.080% 0.050-0.080% Aluminum <0.060% - £ 0.060% Carbon 0.78-0.85% 0.75-0.95% Nickel <0.30% έ. 0.50% 2
Le complément étant du fer plus les impuretés caractéristiques de la pratique de la fabrication du métal, ledit acier présente une dispersion de carbures de Niobium et de carbures de chrome (Fe-Cr)^ C de préférence au (Cr^-c^) obtenu par une teneur en chrome comprise entre 6,05 et 6,45%, lui conférant une résistance à l'usure abrasive améliorée sans toucher aux autres propriétés voire en les améliorant.The complement being iron plus the impurities characteristic of the practice of metal fabrication, said steel has a dispersion of Niobium carbides and chromium carbides (Fe-Cr) ^ C in preference to (Cr ^ -c ^) obtained by a chromium content of between 6.05 and 6.45%, giving it improved resistance to abrasive wear without affecting the other properties or even improving them.
La présente invention se propose de fournir un acier de formage à mi-chaud, voire à froid, élaboré en partant de la métallurgie des poudres. Les techniques mises en oeuvre dans la mise en forme à mi-chaud sont en général celles de la mise en forme à froid mais les ébauches sont préchauffées à une température comprise entre 900° et la température ambiante. Les principaux obstacles au développement du formage à mi-chaud sontThe present invention proposes to provide a semi-hot or even cold forming steel, produced starting from powder metallurgy. The techniques used in mid-hot shaping are generally those of cold shaping but the blanks are preheated to a temperature between 900 ° and room temperature. The main obstacles to the development of mid-hot forming are
assurer la lubrication de l'opération de formage la tenue des outillages, en grande partie due au matériau de constitution de ceux-ci.ensuring the lubrication of the forming operation the holding of the tools, largely due to the material of which they are made.
L'expérience a prouvé que les meilleurs résultats étaient obtenus avec une température de la matrice de 400 °C environ avant forgeage, après l'opération de formage la température de la matrice est portée superficiellement vers 650 °C. Entre deux opérations de formage la température est ramenée vers 400 °C par un soufflage à l'air comprimé associé à une pulvérisation du lubrifiant.Experience has shown that the best results are obtained with a matrix temperature of approximately 400 ° C before forging, after the forming operation the temperature of the matrix is brought up to 650 ° C. Between two forming operations, the temperature is brought back to around 400 ° C. by blowing with compressed air associated with spraying the lubricant.
Le temps de contact outillage-pièce est compris entre 0,5 & 2 secondes. C'est principalement sur l'amélioration du comportement du matériau vis à vis des contraintes thermiques et mécaniques, des chocs thermiques et mécaniques, de l'augmentation de la résistance à l'abrasion que l'acier de mise en forme, objet de la 3 présente invention, se propose de répondre en présentant une dureté élevée à froid associée à des caractéristiques élevées à chaud.The tool-part contact time is between 0.5 & 2 seconds. It is mainly on the improvement of the behavior of the material with respect to thermal and mechanical stresses, thermal and mechanical shocks, the increase in abrasion resistance that the shaping steel, object of the 3 present invention, proposes to respond by having a high hardness when cold associated with high characteristics when hot.
Le nouvel acier semi-rapide élaboré en partant de la métallurgie des poudres présente une dispersion de carbures de niobium et de carbures de chrome (Fe-Cr)4C de préférence au Cr^C-^ générés par une teneur en chrome comprise entre 6,05 et 6,45% pondérale lui conférant une résistance à l'usure abrasive améliorée sans réduire les caractéristiques des autres propriétés, en particulier la ténacité.The new semi-rapid steel produced from powder metallurgy has a dispersion of niobium carbides and chromium carbides (Fe-Cr) 4C in preference to Cr ^ C- ^ generated by a chromium content of between 6, 05 and 6.45% by weight giving it improved resistance to abrasive wear without reducing the characteristics of the other properties, in particular the toughness.
Cette action est dynamisée si l'acier contient peu ou pas de tungstène, ceci vaut également pour la teneur en cobalt maintenue entre 2,60 et 3,40%, l'acier de la présente invention complète les aciers de type ATSI H.11 H.12 H.13 et M50-M2 etc.This action is energized if the steel contains little or no tungsten, this also applies to the cobalt content maintained between 2.60 and 3.40%, the steel of the present invention complements the ATSI H.11 type steels. H.12 H.13 and M50-M2 etc.
La relation stoechiométrique pour la formation du carbure de niobium est de 1% de niobium pour 0,12% de carbone. La teneur en carbone de l'acier est équilibrée avec ses teneurs en vanadium, niobium, chrome, molybdène pour fournir suffisamment de carbone et permettre ainsi à l'objet obtenu par la métallurgie des poudres d'être traité thermiquement de façon à obtenir une dureté^64 Hrc.The stoichiometric relationship for the formation of niobium carbide is 1% niobium for 0.12% carbon. The carbon content of the steel is balanced with its vanadium, niobium, chromium, molybdenum contents to supply sufficient carbon and thus allow the object obtained by powder metallurgy to be heat treated so as to obtain a hardness ^ 64 Hrc.
L'acier , pour outils de mise en forme, selon l'invention, présente une combinaison de qualités : résistance à l'usure abrasive, dureté à chaud caractérisée par' l'essai de capacité de coupe Mathon, ténacité qui ne pouvait être obtenue jusqu'à présent.The steel for shaping tools according to the invention has a combination of qualities: resistance to abrasive wear, hot hardness characterized by the Mathon cutting capacity test, toughness which could not be obtained. until now.
La ténacité est déterminée par une mesure suivant l'essai Charpy défini dans la norme ASTM 23-92 et 23- 93. Une éprouvette de référence 10x10x55mm est traitée à 1050°C, arrêt à l'huile ou arrêt isotherme à 560°C suivi de trois revenus de une heure à 560°; elle présente alors une ténacité supérieure à 100J/cm2.. La capacité de coupe est caractérisée par l'essai Mathon (défini dans la norme AFMOR A.03.654). The toughness is determined by a measurement according to the Charpy test defined in standard ASTM 23-92 and 23-93. A 10x10x55mm reference test piece is treated at 1050 ° C, oil stop or isothermal stop at 560 ° C followed three hour returns at 560 °; it then has a toughness greater than 100J / cm2. The cutting capacity is characterized by the Mathon test (defined in standard AFMOR A.03.654).

Claims

Revendications. Claims.
1. Acier obtenu par la métallurgie des poudres, formé à partir d'une poudre pré-alliée de haute pureté, agglomérée, densifiée, caractérisé en ce que l'acier a la composition pondérale suivante :1. Steel obtained by powder metallurgy, formed from a pre-alloyed powder of high purity, agglomerated, densified, characterized in that the steel has the following composition by weight:
Manganèse 4 1%Manganese 4 1%
Silicium . 1%Silicon. 1%
Chrome 6,05 - 6,45 %Chrome 6.05 - 6.45%
Molybdène 2,50 - 3,50 %Molybdenum 2.50 - 3.50%
Vanadium 0,80 - 2 %Vanadium 0.80 - 2%
Tungstène έ 0,5 %Tungsten έ 0.5%
Soufre <. 0,020 %Sulfur <. 0.020%
Phosphore 0,030 %Phosphorus 0.030%
Niobium 0,60 - 1,60 %Niobium 0.60 - 1.60%
Cobalt 2 à 5 %Cobalt 2 to 5%
Azote 0,050 à 0,080 %Nitrogen 0.050 to 0.080%
Aluminium 0,060 %Aluminum 0.060%
Carbone 0,75 - 0,95 % Nickel < 0,50 %Carbon 0.75 - 0.95% Nickel <0.50%
Le complément étant du fer, plus les impuretés caractéristiques de la pratique de la fabrication du métal.The complement being iron, plus the impurities characteristic of the practice of metal fabrication.
2. Acier selon la revendication 1, caractérisé en ce que l'alliage a la composition générale suivante :2. Steel according to claim 1, characterized in that the alloy has the following general composition:
Manganèse 0,20 - 0,40 %Manganese 0.20 - 0.40%
Silicium 0,20 - 0,40 %Silicon 0.20 - 0.40%
Chrome 6,05 - 6,45 % - Molybdène 2,75 - 3,25 %Chrome 6.05 - 6.45% - Molybdenum 2.75 - 3.25%
- Vanadium 0,90 - 1,30 %- Vanadium 0.90 - 1.30%
- Tungstène 0,50 %- Tungsten 0.50%
- Soufre . 0,020 %- Sulfur. 0.020%
- Phosphore Δ. 0,030 %- Phosphorus Δ. 0.030%
- Niobium 0,70 - 1,10 %- Niobium 0.70 - 1.10%
- Cobalt 2,60 - 3,40 %- Cobalt 2.60 - 3.40%
- Azote 0,050 - 0,080 %- Nitrogen 0.050 - 0.080%
- Aluminium < 0,060 %- Aluminum <0.060%
- Carbone 0,78 - 0,85 % - Nickel < 0,30 % - Carbon 0.78 - 0.85% - Nickel <0.30%
EP98920603A 1996-10-04 1998-04-09 Improvements to steel for forming tools Expired - Lifetime EP0990055B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9612339A FR2754275B1 (en) 1996-10-04 1996-10-04 IMPROVEMENTS TO STEELS FOR SHAPING TOOLS
PCT/FR1998/000725 WO1999053112A1 (en) 1996-10-04 1998-04-09 Improvements to steel for forming tools

Publications (2)

Publication Number Publication Date
EP0990055A1 true EP0990055A1 (en) 2000-04-05
EP0990055B1 EP0990055B1 (en) 2002-08-07

Family

ID=26233031

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98920603A Expired - Lifetime EP0990055B1 (en) 1996-10-04 1998-04-09 Improvements to steel for forming tools

Country Status (7)

Country Link
EP (1) EP0990055B1 (en)
AT (1) ATE221928T1 (en)
BR (1) BR9815563A (en)
DE (1) DE69807080T2 (en)
ES (1) ES2181215T3 (en)
FR (1) FR2754275B1 (en)
WO (1) WO1999053112A1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3809541A (en) * 1972-10-24 1974-05-07 G Steven Vanadium-containing tool steel article
BR7605089A (en) * 1976-08-03 1976-12-28 Acos Villares Sa HARD ALLOYS
SE457356C (en) * 1986-12-30 1990-01-15 Uddeholm Tooling Ab TOOL STEEL PROVIDED FOR COLD PROCESSING

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9953112A1 *

Also Published As

Publication number Publication date
FR2754275A1 (en) 1998-04-10
EP0990055B1 (en) 2002-08-07
BR9815563A (en) 2006-02-14
ES2181215T3 (en) 2003-02-16
WO1999053112A1 (en) 1999-10-21
ATE221928T1 (en) 2002-08-15
FR2754275B1 (en) 1998-12-24
DE69807080T2 (en) 2003-02-06
DE69807080D1 (en) 2002-09-12

Similar Documents

Publication Publication Date Title
US3410732A (en) Cobalt-base alloys
US5830287A (en) Wear resistant, powder metallurgy cold work tool steel articles having high impact toughness and a method for producing the same
US20090045586A1 (en) Method For Producing Rotary and/or Stationary Seal Rings of a Mechanical Face Seal by Means of Laser Hardening
EP1151146B1 (en) High-hardness powder metallurgy tool steel and article made therefrom
JP5029942B2 (en) Hot work tool steel with excellent toughness
JP4470522B2 (en) Low toughness free-cutting non-tempered steel
JP4523230B2 (en) Strengthened durable tool steel, method for producing the same, method for producing a member made of the steel, and member obtained
US5063116A (en) Wire for dot printer
EP0990055B1 (en) Improvements to steel for forming tools
US2162574A (en) Hard metal alloy
JPH08127831A (en) Synchronizer ring made of copper alloy excellent in wear resistance
JPH0266139A (en) High speed tool steel made of powder reduced in oxygen content
US5361968A (en) Method of manufacturing metallic press die
US1998957A (en) Ferrous alloy
US4671930A (en) High hardness and high toughness nitriding powder metallurgical high-speed steel
EP1070153A1 (en) Steel composition
JPS6310097A (en) Co base alloy for build-up welding
JP4368032B2 (en) Powder for high speed tool steel and powder high speed tool steel
JP2005213630A (en) Powder high speed tool steel for mill roll having excellent wear resistance and toughness
JP2001131683A (en) Die steel for small lot production
Totten Tribology and Wear of tool steels
MXPA00001522A (en) Improvements to steel for forming tools
WO1998003692A1 (en) High-speed steel
FR2722211A1 (en) Wear-resistant tool steel
US2294834A (en) Hard surfacing alloy for ferrous foundation metal

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 CH DE ES GB IT LI

AX Request for extension of the european patent

Free format text: SI PAYMENT 20000120

17P Request for examination filed

Effective date: 20000313

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20011228

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 CH DE ES GB IT LI

AX Request for extension of the european patent

Free format text: SI PAYMENT 20000120

REF Corresponds to:

Ref document number: 221928

Country of ref document: AT

Date of ref document: 20020815

Kind code of ref document: T

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

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

Effective date: 20020807

REF Corresponds to:

Ref document number: 69807080

Country of ref document: DE

Date of ref document: 20020912

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BUGNION S.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2181215

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030508

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050409

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: IT

Effective date: 20091201

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

Ref country code: GB

Payment date: 20100329

Year of fee payment: 13

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

Ref country code: ES

Payment date: 20100406

Year of fee payment: 13

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

Ref country code: IT

Payment date: 20100416

Year of fee payment: 13

Ref country code: DE

Payment date: 20100430

Year of fee payment: 13

Ref country code: AT

Payment date: 20100317

Year of fee payment: 13

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

Ref country code: CH

Payment date: 20100413

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69807080

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69807080

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20110409

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 221928

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110409

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

Ref country code: CH

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

Effective date: 20110430

Ref country code: LI

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

Effective date: 20110430

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: 20110409

Ref country code: GB

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

Effective date: 20110409

Ref country code: IT

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

Effective date: 20110409

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120604

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: 20110410

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

Ref country code: DE

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

Effective date: 20111031