EP1036610B1 - Moulage de précision et en châssis dans des aérogels organiques ou en carbone - Google Patents

Moulage de précision et en châssis dans des aérogels organiques ou en carbone Download PDF

Info

Publication number
EP1036610B1
EP1036610B1 EP00104214A EP00104214A EP1036610B1 EP 1036610 B1 EP1036610 B1 EP 1036610B1 EP 00104214 A EP00104214 A EP 00104214A EP 00104214 A EP00104214 A EP 00104214A EP 1036610 B1 EP1036610 B1 EP 1036610B1
Authority
EP
European Patent Office
Prior art keywords
wax
gel
sol
temperature
plastic
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
EP00104214A
Other languages
German (de)
English (en)
Other versions
EP1036610A1 (fr
Inventor
Lorenz Prof. Ratke
Jochen Prof. Dr. Fricke
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.)
Deutsches Zentrum fuer Luft und Raumfahrt eV
Original Assignee
Deutsches Zentrum fuer Luft und Raumfahrt eV
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 Deutsches Zentrum fuer Luft und Raumfahrt eV filed Critical Deutsches Zentrum fuer Luft und Raumfahrt eV
Publication of EP1036610A1 publication Critical patent/EP1036610A1/fr
Application granted granted Critical
Publication of EP1036610B1 publication Critical patent/EP1036610B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/165—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents in the manufacture of multilayered shell moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds

Definitions

  • the invention relates to a molding material for the fine and casting of metals or metal alloys comprising plastic and / or carbon aerogels and a process for the preparation of corresponding molding materials.
  • Aerogels are highly porous, open-pored oxidic solids, which are usually via sol-gel processes of metal alkoxides by polymerization, polycondensation to gels and subsequent supercritical drying are obtained.
  • plastics via sol-gel processes gelled and by supercritical drying in a highly porous organic Transform solid state. Pyrolysis of such plastic aerogels under inert gas or in vacuum at temperatures above 1000 ° C, this converts into carbon aerogels around.
  • the oxidic aerogels have plastic and carbon aerogels extremely low effective thermal conductivities (order of magnitude some mW / K / m) and are considerably lighter.
  • the airgel mold may consist of silica aerogels or not working under reducing atmosphere of carbon aerogels.
  • a Forming material for the fine and casting of metals or metal alloys comprising highly porous, open-pored plastic and / or carbon aerogels, available by sol-gel polymerization of organic plastic materials optionally followed by partial or complete pyrolysis of the obtained Kunststoffaerogels.
  • the molding material according to the invention is particularly suitable for use in lost wax casting processes and does not have, as in the prior art in oxidic Gels, applied in several steps.
  • the airgel forms produced according to the invention are particularly suitable for the casting of aluminum alloys (with the mold practically unheated must be because there is no heat dissipation by themselves). This increases the economy, because energy costs can be reduced. Magnesium- and titanium alloys also do not react with carbon, so that these carbon aerogels also for these alloys under inert gas or Offer vacuum as molding material.
  • a particular advantage of the molding materials according to the invention is that the Sol-gel formation at room temperature, that is, especially at temperatures completed within a few hours below the pour point of the wax can be.
  • a supercritical drying, as with the purely inorganic Gels are not required. Nevertheless, it is possible to increase the pore size in the micrometer range adjust. For drying in the supercritical temperature range In addition, pore sizes in the nanometer range possible.
  • the molding materials according to the invention can also be inorganic or organic filler materials. These are essentially Under solidification conditions inert inert materials understood.
  • inorganic Filler materials are, for example, selected from alumina, titania and / or quartz, each in an amount of 5 to 30% by volume. used can be. Fillers in the context of the present invention further include Fiber materials containing a fiber reinforcement with organic, inorganic or allow carbon and / or SiC fibers at about equal volume fractions.
  • thermoplastic or thermosetting plastic particles for example polystyrene and / or organic (polyacrylonitrile) fibers.
  • thermoplastic or thermosetting plastic particles for example polystyrene and / or organic (polyacrylonitrile) fibers.
  • the molding material Plastic aerogels based on resorcinol / formaldehyde used in the suitable composition and suitable content of basic catalyst at temperatures between 20 and 50 ° C without supercritical drying in one microstructured plastic airgel can be transferred.
  • the composition of the sol-gel polymerization is adjustable so that, for example First, a highly viscous liquid is formed, which is on a wax mold can be applied. This is also possible in several operations, so that the layer thickness adapted to the needs of the applications in the foundry can be.
  • the temperature of the conversion of the solution into a plastic airgel must be Melting point of the wax can be adjusted. After conversion into one Plastic airgel, the wax can be melted out and at the same time Conversion into a carbon airgel takes place under exclusion of air.
  • the gelation temperature Dependent from the composition of the starting solution, the gelation temperature, The density of the resulting porous body can be used to produce molds both as a plastic and as a carbon airgel, on a micrometer scale are superficially smooth and form sharp contours.
  • the pyrolysis time is determined by the thickness the mold shell; for example, with a wall thickness of 1 cm, the time is less than 24 hours, usually 10 hours.
  • the Kunststoffstöffaerogel was in a cold muffle furnace brought in.
  • the oven was heated slowly (3 hours) to 1050 ° C, whereby continuous nitrogen (argon or another inert gas is possible analogously) was blown to avoid oxidation.
  • the temperature of 1050 ° C was maintained for 24 hours.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (10)

  1. Matière moulée pour la coulée de précision et le moulage en châssis de métaux ou d'alliages métalliques, qui comprend des aérogels de matière plastique et/ou de carbone, très poreux, à pores ouverts, que l'on peut obtenir par polymérisation sol-gel de matières synthétiques organiques, suivie éventuellement d'une pyrolyse partielle ou complète de l'aérogel de matière plastique obtenue.
  2. Matière moulée selon la revendication 1, qui contient des charges minérales ou organiques.
  3. Matière moulée selon la revendication 2, caractérisée en ce que les charges minérales sont choisies parmi l'oxyde d'aluminium, le dioxyde de titane et/ou le quartz, et figurent en particulier en une proportion de 5 à 30 % en volume.
  4. Matière moulée selon la revendication 2, caractérisée en ce que les charges sont choisies parmi des particules de matière plastique thermoplastique ou thermodurcissable, en particulier de polystyrène.
  5. Matière moulée selon la revendication 2, caractérisée en ce que les charges comprennent des fibres organiques, des fibres minérales ou des fibres de carbone et/ou de SiC.
  6. Matière moulée selon l'une quelconque des revendications 1 à 5, qui comprend un sol-gel de résorcinol/formaldéhyde et un catalyseur de polymérisation basique, en particulier de l'hydroxyde d'ammonium et/ou du carbonate de sodium.
  7. Procédé de préparation de moules de coulée pour la coulée de précision et le moulage en châssis de métaux ou d'alliages métalliques, où l'on emploie des aérogels de matière plastique et/ou de carbone, très poreux, à pores ouverts, procédé dans lequel :
    a) on imprègne un moule en cire d'un sol de matière plastique de composition appropriée et d'un catalyseur approprié,
    b) on transforme le sol en un gel à une température inférieure à la température d'écoulement de la cire,
    b') on applique éventuellement une ou plusieurs couches du sol et on met chaque couche partiellement ou totalement sous la forme d'un gel,
    c) on sèche le gel à une température inférieure au point d'écoulement de la cire, et
    d) on sépare la cire du gel solidifié par fusion ou combustion à une température supérieure à la température d'écoulement de la cire.
  8. Procédé de préparation de moules de coulée pour la coulée de précision et le moulage en châssis de métaux ou d'alliages métalliques, où l'on emploie des aérogels de matière plastique et/ou de carbone, très poreux, à pores ouverts, procédé dans lequel :
    a) on introduit une pièce moulée en cire dans un récipient,
    b) on remplit partiellement ou totalement le récipient avec un sol de matière plastique,
    c) on transforme le sol en un gel à une température inférieure à la température d'écoulement de la cire,
    d) on sèche le gel à une température inférieure à la température d'écoulement de la cire, et
    e) on sépare la cire du gel solidifié par fusion ou combustion à une température supérieure à la température d'écoulement de la cire.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que l'on réalise le séchage du gel à une température comprise dans l'intervalle allant de 20 à 50 °C, pendant une durée d'au moins 24 heures.
  10. Procédé selon l'une quelconque des revendications 7 à 9, caractérisé en ce que l'on réalise la pyrolyse du gel solidifié à une température d'au moins 600 °C, en particulier d'au moins 1000 °C, en l'espace de 4 à 24 heures.
EP00104214A 1999-03-17 2000-03-01 Moulage de précision et en châssis dans des aérogels organiques ou en carbone Expired - Lifetime EP1036610B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19911847A DE19911847A1 (de) 1999-03-17 1999-03-17 Fein- und Formguß in Kunststoff/Kohlenstoff-Aerogelen
DE19911847 1999-03-17

Publications (2)

Publication Number Publication Date
EP1036610A1 EP1036610A1 (fr) 2000-09-20
EP1036610B1 true EP1036610B1 (fr) 2005-08-31

Family

ID=7901270

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00104214A Expired - Lifetime EP1036610B1 (fr) 1999-03-17 2000-03-01 Moulage de précision et en châssis dans des aérogels organiques ou en carbone

Country Status (4)

Country Link
US (2) US6599953B1 (fr)
EP (1) EP1036610B1 (fr)
AT (1) ATE303214T1 (fr)
DE (2) DE19911847A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104399446A (zh) * 2014-11-06 2015-03-11 北京化工大学 一种TiO2/RFC复合微球负载型光降解剂及其制备方法
CN107498003A (zh) * 2017-08-10 2017-12-22 合肥市田源精铸有限公司 一种轻质耐磨钢铸件的加工方法

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19911847A1 (de) * 1999-03-17 2000-09-28 Deutsch Zentr Luft & Raumfahrt Fein- und Formguß in Kunststoff/Kohlenstoff-Aerogelen
DE19939062A1 (de) * 1999-08-18 2001-02-22 Deutsch Zentr Luft & Raumfahrt Verwendung von Kunststoff/Kohlenstoff-Aerogelen als Kernwerkstoff
US6806299B2 (en) * 2001-05-18 2004-10-19 The Regents Of The University Of California Preparation of hydrophobic organic aeorgels
DE10216403B4 (de) * 2002-04-12 2004-03-18 Deutsches Zentrum für Luft- und Raumfahrt e.V. Aerogelgebundene Formstoffe mit hoher Wärmeleitfähigkeit
DE10352574A1 (de) * 2003-11-11 2005-06-16 Deutsches Zentrum für Luft- und Raumfahrt e.V. Füllstoff enthaltende Aerogele
DE102004027382B4 (de) * 2004-06-04 2006-03-09 Deutsches Zentrum für Luft- und Raumfahrt e.V. Thermisch zersetzbare Kohlenstoff-Aerogelsande
WO2006010449A2 (fr) * 2004-07-23 2006-02-02 Ceramtec Ag Innovative Ceramic Engineering Noyaux de fonderie en ceramique
US20070089849A1 (en) * 2005-10-24 2007-04-26 Mcnulty Thomas Ceramic molds for manufacturing metal casting and methods of manufacturing thereof
US8851442B2 (en) * 2008-01-22 2014-10-07 Honeywell International Inc. Aerogel-bases mold for MEMS fabrication and formation thereof
DE102008056856A1 (de) * 2008-11-12 2010-05-20 Deutsches Zentrum für Luft- und Raumfahrt e.V. Gießereikerne mit verbesserten Entkernungseigenschaften I
US8293657B2 (en) 2010-11-05 2012-10-23 Honeywell International Inc. Sacrificial layers made from aerogel for microelectromechanical systems (MEMS) device fabrication processes
CN102351506B (zh) * 2011-07-18 2013-04-10 南京工业大学 一种块状耐高温硅-炭复合气凝胶材料的制备方法
CN102343285B (zh) * 2011-07-18 2013-04-10 南京工业大学 一种块状硅-炭复合气凝胶的制备方法
JP5997831B2 (ja) 2012-04-23 2016-09-28 ゼネラル・エレクトリック・カンパニイ 局所的な壁厚さ制御を伴うタービン翼
DE102015225227A1 (de) * 2015-12-15 2017-06-22 Robert Bosch Gmbh Speiser für insbesondere aus Gusseisen bestehende Gussstücke
DE102016223619A1 (de) * 2015-12-15 2017-06-22 Robert Bosch Gmbh Schlichte zum Auftragen auf die poröse Oberfläche von Formen und/oder Kernen für den Metallguss
WO2018078512A1 (fr) * 2016-10-24 2018-05-03 Blueshift International Materials, Inc. Aérogel polymère organique renforcé par des fibres
CA3051470A1 (fr) 2017-01-26 2018-08-02 Blueshift International Materials, Inc. Aerogels polymeres organiques comprenant des microstructures
BG67252B1 (bg) * 2017-06-27 2021-02-15 Е.Миролио ЕАД Метод за получаване на вискозна изкуствена коприна с променяща се дебелина, продукт, получен по този метод и инсталация за реализиране на метода
CN109675620B (zh) * 2017-10-18 2021-07-09 中国石油化工股份有限公司 含钴催化剂及其制备方法和应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4873218A (en) * 1988-05-26 1989-10-10 The United States Department Of Energy Low density, resorcinol-formaldehyde aerogels
US5242647A (en) * 1990-08-23 1993-09-07 Regents Of The University Of California Method of casting aerogels
DE19523382C2 (de) * 1995-06-30 2003-04-30 Jochen Fricke Kohlenstoffaerogele und Verfahren zu deren Herstellung
WO1997017308A1 (fr) * 1995-11-09 1997-05-15 Aspen Systems, Inc. Materiau souple super-isolant a base d'aerogel et procede de fabrication
WO1997043116A1 (fr) * 1996-05-15 1997-11-20 Hyperion Catalysis International, Inc. Structures de carbone poreuses et rigides, leurs procedes de fabrication et d'utilisation et produits les contenant
DE19721600A1 (de) * 1997-05-23 1998-11-26 Hoechst Ag Nanoporöse interpenetrierende organisch-anorganische Netzwerke
DE19738466C1 (de) * 1997-09-03 1998-12-24 Deutsch Zentr Luft & Raumfahrt Stranggußvorrichtung
DE19911847A1 (de) * 1999-03-17 2000-09-28 Deutsch Zentr Luft & Raumfahrt Fein- und Formguß in Kunststoff/Kohlenstoff-Aerogelen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104399446A (zh) * 2014-11-06 2015-03-11 北京化工大学 一种TiO2/RFC复合微球负载型光降解剂及其制备方法
CN107498003A (zh) * 2017-08-10 2017-12-22 合肥市田源精铸有限公司 一种轻质耐磨钢铸件的加工方法

Also Published As

Publication number Publication date
EP1036610A1 (fr) 2000-09-20
US6599953B1 (en) 2003-07-29
US20030212152A1 (en) 2003-11-13
DE50011046D1 (de) 2005-10-06
US6887915B2 (en) 2005-05-03
DE19911847A1 (de) 2000-09-28
ATE303214T1 (de) 2005-09-15

Similar Documents

Publication Publication Date Title
EP1036610B1 (fr) Moulage de précision et en châssis dans des aérogels organiques ou en carbone
EP2244870B1 (fr) Fabrication de parties de moule à des fins de coulée
DE69008419T2 (de) Keramikwerkstoffe für eine Giessform.
AU595567B2 (en) Mold core for investment casting, process for preparing the same and process for preparing mold for investment casting having therewithin said mold core
DE1262515B (de) Thermisch isolierte Giessformen
KR940011096A (ko) 비-다공질성의 탄소 주물사 및 주조 금속의 제조 방법
EP1077097B1 (fr) Utilisation d'aérogels en plastique et/ou en carbone comme matériau de noyeau
DE2219163A1 (de) Feinguß verfahren
DE2520993C3 (de) Feuerfeste Masse auf der Basis von Kieselsäureanhydrid und ihre Verwendung zur Herstellung der Auskleidung eines Gießtrichters sowie Verfahren zur Behandlung einer solchen Auskleidung
DE10357539A1 (de) Herstellung von füllstoffhaltigen Aerogelen
EP1658242A1 (fr) Corps moules en sio sb 2 /sb , leurs procedes de production, et leur utilisation
DE10216403B4 (de) Aerogelgebundene Formstoffe mit hoher Wärmeleitfähigkeit
DE10216464B4 (de) Silica gebundene Kernwerkstoffe, Verfahren zu deren Herstellung und deren Verwendung
EP0143954B1 (fr) Procédé de fabrication de parties de moule, selon le procédé en boîte froide et appareil de moulage utilisé
WO2002064285A2 (fr) Moule
WO2020058393A1 (fr) Noyau de coulée pour moules de coulée et son procédé de fabrication
WO2020058394A1 (fr) Noyau de coulée pour moules de coulée et son procédé de fabrication
CH631096A5 (de) Verfahren zur herstellung von feuerfesten formkoerpern.
DE3629079A1 (de) Verfahren zum vergiessen von gussstuecken nach dem feingussverfahren in eine keramische formschale
DE19703176C2 (de) Verfahren zur Herstellung von keramischen oder pulvermetallurgischen Bauteilen
DE102005053627B4 (de) Verfahren zum Herstellen von keramischen Produkten
WO2020058402A1 (fr) Noyau de coulée pour moules de fonderie et procédé de fabrication
DE2459088C3 (de) Monolithische Form für den Präzisionsguß mit verlorenem Modell
DE102005011019A1 (de) Herstellung und Verwendung eines zerstörbaren Formkerns für den metallischen Guss
DE1583551C (de) Herstellungsverfahren von Gießformen zur Fertigung von Präzisionsguß unter Verwendung von Ausschmelz-Modellen

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 FR GB IT LI

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20001124

AKX Designation fees paid

Free format text: AT CH DE FR GB IT LI

17Q First examination report despatched

Effective date: 20041014

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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 FR GB IT LI

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 50011046

Country of ref document: DE

Date of ref document: 20051006

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & PARTNER AG

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

Effective date: 20051024

ET Fr: translation filed
RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: DEUTSCHES ZENTRUM FUER LUFT- UND RAUMFAHRT E.V.

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: 20060601

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: DEUTSCHES ZENTRUM FUER LUFT- UND RAUMFAHRT E.V.

Free format text: DEUTSCHES ZENTRUM FUER LUFT- UND RAUMFAHRT E.V.# #53175 BONN (DE) -TRANSFER TO- DEUTSCHES ZENTRUM FUER LUFT- UND RAUMFAHRT E.V.#LINDER HOEHE#51147 KOELN (DE)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: RITSCHER & PARTNER AG;RESIRAIN 1;8125 ZOLLIKERBERG (CH)

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

Ref country code: CH

Payment date: 20100325

Year of fee payment: 11

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

Ref country code: IT

Payment date: 20100325

Year of fee payment: 11

Ref country code: FR

Payment date: 20100331

Year of fee payment: 11

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

Ref country code: AT

Payment date: 20100322

Year of fee payment: 11

Ref country code: GB

Payment date: 20100324

Year of fee payment: 11

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: 20110301

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: 20110301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111130

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: 20110331

Ref country code: CH

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

Effective date: 20110331

Ref country code: FR

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

Effective date: 20110331

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

Ref country code: GB

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

Effective date: 20110301

Ref country code: IT

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

Effective date: 20110301

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

Ref country code: DE

Payment date: 20190215

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20190215

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 50011046

Country of ref document: DE