EP0368082B1 - Poudre métallique de molybdène et son procédé de préparation - Google Patents

Poudre métallique de molybdène et son procédé de préparation Download PDF

Info

Publication number
EP0368082B1
EP0368082B1 EP89119866A EP89119866A EP0368082B1 EP 0368082 B1 EP0368082 B1 EP 0368082B1 EP 89119866 A EP89119866 A EP 89119866A EP 89119866 A EP89119866 A EP 89119866A EP 0368082 B1 EP0368082 B1 EP 0368082B1
Authority
EP
European Patent Office
Prior art keywords
metal powder
molybdenum metal
molybdenum
carbon dioxide
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89119866A
Other languages
German (de)
English (en)
Other versions
EP0368082A3 (en
EP0368082A2 (fr
Inventor
Theodor Alexander Dr. Weber
Wolfgang Kummer
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.)
HC Starck GmbH
Original Assignee
HC Starck 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
Application filed by HC Starck GmbH filed Critical HC Starck GmbH
Priority to AT89119866T priority Critical patent/ATE90242T1/de
Publication of EP0368082A2 publication Critical patent/EP0368082A2/fr
Publication of EP0368082A3 publication Critical patent/EP0368082A3/de
Application granted granted Critical
Publication of EP0368082B1 publication Critical patent/EP0368082B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • Y10T428/12181—Composite powder [e.g., coated, etc.]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • the present invention relates to molybdenum metal powder with a shell made of oxides of molybdenum and methods for its production.
  • Molybdenum metal powders with a defined oxygen content are used in plasma spraying in order to achieve particularly hard spray coatings.
  • Flame spraying with an ethine / oxygen mixture is preferably carried out using molybdenum wire as the melting material.
  • the metal droplets are partially oxidized during flame spraying.
  • a method for producing oxygen-containing molybdenum powder by an oxidizing plasma treatment is known from US Pat. No. 4,146,388.
  • EP-A 233 574 describes three processes for producing oxygen-containing molybdenum wettable powders. These are the treatment of molybdenum metal with dilute hydrogen peroxide solution, the thermal treatment of molybdenum metal powder with water vapor under an inert gas atmosphere and the production of agglomerated oxygen-containing molybdenum metal powder using molybdenum oxides.
  • a disadvantage of the molybdenum powders thus produced is that their oxygen content is not precisely defined.
  • these molybdenum metal powders are often inhomogeneous.
  • these molybdenum metal powders often have a MoO3 content, which has a disadvantageous effect on the spray behavior of the powder.
  • the object of the present compound is to provide a molybdenum metal powder with a defined oxygen content which does not have the disadvantages described.
  • the molybdenum metal powder according to the invention has an oxygen content of 1 to 18, preferably 2 to 12,% by weight.
  • the oxygen is in a defined form as MoO2 and is in particular on the surface as a homogeneous layer. This oxide layer adheres firmly to the metallic core, so that the molybdenum metal powder according to the invention has very special structural properties.
  • the powder grains consist of a molybdenum metal core and a uniform, closed MoO2 layer.
  • the average diameter of the molybdenum metal powder individual grains is 5 to 90 microns and the thickness of the MoO2 shell 0.1 to 20 microns.
  • the surface of the partially oxidized molybdenum metal powder according to the invention shows a typical MoO2 color.
  • SEM scanning electron microscope
  • the present invention also relates to a method for producing the molybdenum metal powder according to the invention. Surprisingly, this can be carried out in a very controllable oxidation of the molybdenum metal powder under a carbon dioxide atmosphere at unexpectedly low temperatures.
  • the subject of this invention is thus a process for the production of molybdenum metal powder with a defined oxygen content, whereby molybdenum metal powder is partially oxidized by thermal treatment in a carbon dioxide atmosphere at temperatures below 1200 ° C.
  • the partial oxidation is preferably carried out at temperatures from 700 to 1200 ° C.
  • the oxygen uptake in the molybdenum metal powder is carried out by the process according to the invention exclusively with the formation of MoO2, which can be demonstrated by X-ray diffraction. An equivalent amount of carbon monoxide is released in the reaction.
  • the weight increase in the starting powder is limited to 12% by weight.
  • the increase in the particle diameter of the individual molybdenum metal particles corresponds to the oxygen uptake and the associated change in density.
  • the oxygen loading of the molybdenum metal powder is inversely proportional to its surface. Preselected oxygen levels can be set with great accuracy using the parameters mentioned.
  • the oxygen content of the molybdenum metal powder is set by the choice of the reaction time and / or the reaction temperature and / or the carbon dioxide concentration in the gas atmosphere. This is illustrated in FIGS. 1 to 3.
  • Fig. 2 shows the dependence of the oxygen uptake of a molybdenum metal powder on the carbon dioxide volume flow and the time of constant temperature, measured by the CO2 / CO content in the exhaust gas.
  • a grain coarsening occurs due to the oxygen absorption of the molybdenum metal powder, the density of the powder decreases.
  • This invention therefore also relates to the use of the molybdenum metal powder according to one or more of claims 1 to 6 as molybdenum wettable powder.
  • 800 g of a molybdenum metal powder with a grain size of> 5 ⁇ m and ⁇ 45 ⁇ m are gassed in a tube furnace with 20 l / h of carbon dioxide and heated to 900 ° C.
  • the oxygen content of the metal powder is 3.6% by weight, after 2 hours reaction time 4.6% by weight, after 3 hours reaction time 5.5% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Compounds Of Unknown Constitution (AREA)

Claims (7)

  1. Poudre métallique de molybdène portant une enveloppe d'oxydes de molybdène, caractérisée en ce que l'enveloppe d'oxydes est constituée de MoO₂.
  2. Poudre métallique de molybdène suivant la revendication 1, caractérisée en ce que la teneur en oxygène de la poudre métallique de molybdène s'élève à 1-18, de préférence 2-12 % en poids.
  3. Poudre métallique de molybdène suivant les revendications 1 ou 2, caractérisée en ce que les diamètres moyens des grains individuels de poudre métallique de molybdène ont une valeur de 5 à 90 µm et l'épaisseur de l'enveloppe de MoO₂ a une valeur de 0,1 à 20 µm.
  4. Procédé de production de poudre métallique de molybdène suivant une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'on oxyde partiellement de la poudre métallique de molybdène par traitement thermique dans une atmosphère d'anhydride carbonique à des températures inférieures à 1200°C.
  5. Procédé suivant la revendication 4, caractérisé en ce que l'oxydation partielle est effectuée à des températures de 700 à 1200°C.
  6. Procédé suivant l'une des revendications 4 ou 5, caractérisé en ce que la teneur en oxygène de la poudre métallique de molybdène est ajustée par le choix de la durée de réaction et/ou de la température de réaction et/ou de la concentration en anhydride carbonique dans l'atmosphère gazeuse.
  7. Utilisation de la poudre métallique de molybdène suivant une ou plusieurs des revendications 1 à 6 comme poudre pulvérisable de molybdène.
EP89119866A 1988-11-08 1989-10-26 Poudre métallique de molybdène et son procédé de préparation Expired - Lifetime EP0368082B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89119866T ATE90242T1 (de) 1988-11-08 1989-10-26 Sauerstoffhaltiges molybdaenmetallpulver sowie verfahren zu dessen herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3837782A DE3837782A1 (de) 1988-11-08 1988-11-08 Sauerstoffhaltiges molybdaenmetallpulver sowie verfahren zu dessen herstellung
DE3837782 1988-11-08

Publications (3)

Publication Number Publication Date
EP0368082A2 EP0368082A2 (fr) 1990-05-16
EP0368082A3 EP0368082A3 (en) 1990-07-25
EP0368082B1 true EP0368082B1 (fr) 1993-06-09

Family

ID=6366675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89119866A Expired - Lifetime EP0368082B1 (fr) 1988-11-08 1989-10-26 Poudre métallique de molybdène et son procédé de préparation

Country Status (6)

Country Link
US (2) US4976779A (fr)
EP (1) EP0368082B1 (fr)
JP (1) JPH02185902A (fr)
AT (1) ATE90242T1 (fr)
DE (2) DE3837782A1 (fr)
ES (1) ES2040964T3 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4140900A1 (de) * 1991-12-12 1993-06-17 Basf Ag Als carrier fuer die elektrophotographie geeignete teilchen
US5302450A (en) * 1993-07-06 1994-04-12 Ford Motor Company Metal encapsulated solid lubricant coating system
US5776264A (en) * 1996-04-12 1998-07-07 Rutgers University Method for producing amorphous based metals
US6127654A (en) * 1997-08-01 2000-10-03 Alkron Manufacturing Corporation Method for manufacturing heating element
JP4231990B2 (ja) * 2001-03-21 2009-03-04 信越化学工業株式会社 希土類酸化物溶射用粒子およびその製造方法、溶射部材ならびに耐食性部材
JP4273292B2 (ja) * 2001-04-06 2009-06-03 信越化学工業株式会社 溶射用粒子、および該粒子を用いた溶射部材
US7470307B2 (en) * 2005-03-29 2008-12-30 Climax Engineered Materials, Llc Metal powders and methods for producing the same
US8197885B2 (en) * 2008-01-11 2012-06-12 Climax Engineered Materials, Llc Methods for producing sodium/molybdenum power compacts
US20090181179A1 (en) * 2008-01-11 2009-07-16 Climax Engineered Materials, Llc Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells
EP2636763B1 (fr) * 2012-03-05 2020-09-02 Ansaldo Energia Switzerland AG Procédé pour appliquer une couche de revêtement stable à haute température sur la surface d'un composant et composant avec une telle couche de revêtement
KR102042657B1 (ko) * 2013-08-22 2019-11-28 재단법인대구경북과학기술원 박막 태양전지 및 이의 제조방법

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3407057A (en) * 1965-10-23 1968-10-22 American Metal Climax Inc Molybdenum powder for use in spray coating
US3819384A (en) * 1973-01-18 1974-06-25 Metco Inc Flame spraying with powder blend of ferromolybdenum alloy and self-fluxing alloys
IT1003359B (it) * 1973-03-15 1976-06-10 Goetzewerke Lega rispettivamente miscela di polvere per la produzione di stra ti resistenti all usura mediante saldatura di riporto
DE2332179C2 (de) * 1973-06-25 1978-07-06 Fried. Krupp Huettenwerke Ag, 4630 Bochum Verfahren zur Aktivierung des Sintervorganges von Metallpulvern
US3881911A (en) * 1973-11-01 1975-05-06 Gte Sylvania Inc Free flowing, sintered, refractory agglomerates
US3973948A (en) * 1973-11-12 1976-08-10 Gte Sylvania Incorporated Free flowing powder and process for producing it
US3909241A (en) * 1973-12-17 1975-09-30 Gte Sylvania Inc Process for producing free flowing powder and product
US3907546A (en) * 1974-03-28 1975-09-23 Gte Sylvania Inc Molybdenum flame spray powder and process
US4146388A (en) * 1977-12-08 1979-03-27 Gte Sylvania Incorporated Molybdenum plasma spray powder, process for producing said powder, and coatings made therefrom
US4624700A (en) * 1986-02-20 1986-11-25 Gte Products Corporation Method for controlling the oxygen content in agglomerated molybdenum powders
DE3785775T2 (de) * 1986-02-12 1993-08-12 Gte Prod Corp Verfahren zur ueberwachung des sauerstoffgehaltes in einem agglomerierten molybdaenpulver.
US4684400A (en) * 1986-02-20 1987-08-04 Gte Products Corporation Method for controlling the oxygen content in agglomerated molybdenum powders
US4758406A (en) * 1987-11-25 1988-07-19 Amax Inc. Molybdenum addition agent and process for its production

Also Published As

Publication number Publication date
DE3837782C2 (fr) 1991-02-14
US4976779A (en) 1990-12-11
EP0368082A3 (en) 1990-07-25
US5037705A (en) 1991-08-06
EP0368082A2 (fr) 1990-05-16
JPH02185902A (ja) 1990-07-20
DE3837782A1 (de) 1990-05-10
ES2040964T3 (es) 1993-11-01
DE58904628D1 (de) 1993-07-15
ATE90242T1 (de) 1993-06-15

Similar Documents

Publication Publication Date Title
DE2734529C2 (de) Gegenstand mit verbesserter Oxydations- und Korrosionsbeständigkeit bei hoher Temperatur
EP0368082B1 (fr) Poudre métallique de molybdène et son procédé de préparation
DE3108160C2 (de) Verfahren zur Herstellung von Oxidschichten auf chrom- und/oder nickellegierten Stählen
DE3419638A1 (de) Verfahren zur erzeugung von oxidischen schutzschichten auf der oberflaeche von metallen bzw. metallegierungen
CH647265A5 (de) Verfahren zur herstellung schuetzender oxidschichten.
DE3331927C2 (fr)
EP1140698B1 (fr) Procede de preparation de carbures de tungstene par carburation en phase gazeuse
DE1533344B1 (de) Verfahren zur Herstellung ultrafeiner Legierungspulver
DE3409164C2 (fr)
DE2910596C2 (de) Verfahren zur Herstellung von Titancarbonitrid
EP0063730A2 (fr) Procédé de stabilisation de particules métalliques pyrophores ferromagnétiques aciculaires constituées essentiellement par du fer
DE1558719A1 (de) Verfahren zum pulvermetallurgischen Herstellen chromhaltiger Legierungen
DE2304731A1 (de) Verfahren zur herstellung von sinterkarbiden und die dabei erhaltenen produkte
EP0078950B1 (fr) Procédé de préparation d'oxydes de fer aciculaire, ferrimagnetique
DE4134144A1 (de) Karbidisches spritzpulver
DE3925492A1 (de) Herstellung von urandioxid
DE3830112C2 (fr)
DE2033100A1 (de) Dispersionen von Nitriden in einem Metall oder einer Legierung und Verfahren zu deren Herstellung
EP0512309B1 (fr) Procédé de stabilisation des particules métalliques, aciculaires, ferromagnétiques, constituées essentiellement de fer
DE2032862A1 (de) Verfahren zur Herstellung von wechselseitigen Dispersionen von Carbiden und Metallen oder Legierungen und neue, so erhaltene Produkte
DE4025174A1 (de) Arsenresistenter mischoxidkatalysator und verfahren zu seiner herstellung
DE2352440C2 (de) Verfahren zur Herstellung von γ- Eisen(III)oxid
DE1817495C (de) Verfahren zur pulvermetallur gischen Herstellung einer chrom haltigen Legierung
DE2458623C3 (de) Verfahren zum Verringern des Gehalts an Kohlenstoff und Stickstoff in Ferrochromlegierungen
DE1521443C (de) Verfahren zum Verbessern der Verdich tungseigenschaften von Pulver aus nichtro stendem Stahl

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19891026

AK Designated contracting states

Kind code of ref document: A2

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

17Q First examination report despatched

Effective date: 19920207

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: H.C. STARCK GMBH & CO. KG

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: 90242

Country of ref document: AT

Date of ref document: 19930615

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 58904628

Country of ref document: DE

Date of ref document: 19930715

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930913

Year of fee payment: 5

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

Effective date: 19930816

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

Ref country code: SE

Payment date: 19930916

Year of fee payment: 5

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

Ref country code: AT

Payment date: 19930923

Year of fee payment: 5

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

Ref country code: FR

Payment date: 19930928

Year of fee payment: 5

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

Ref country code: GB

Payment date: 19931018

Year of fee payment: 5

Ref country code: ES

Payment date: 19931018

Year of fee payment: 5

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

Ref country code: BE

Payment date: 19931027

Year of fee payment: 5

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

Ref country code: CH

Payment date: 19931028

Year of fee payment: 5

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

Ref country code: NL

Payment date: 19931031

Year of fee payment: 5

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2040964

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

Ref country code: GB

Effective date: 19941026

Ref country code: AT

Effective date: 19941026

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

Ref country code: SE

Effective date: 19941027

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19941027

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

Ref country code: LI

Effective date: 19941031

Ref country code: CH

Effective date: 19941031

Ref country code: BE

Effective date: 19941031

EAL Se: european patent in force in sweden

Ref document number: 89119866.5

BERE Be: lapsed

Owner name: H.C. STARCK G.M.B.H. & CO. K.G.

Effective date: 19941031

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

Ref country code: NL

Effective date: 19950501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941026

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

Ref country code: FR

Effective date: 19950630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DE

Effective date: 19950701

EUG Se: european patent has lapsed

Ref document number: 89119866.5

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19991007

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: 20051026