EP0842309A1 - Process for dep tsols into microporous coating layers - Google Patents
Process for dep tsols into microporous coating layersInfo
- Publication number
- EP0842309A1 EP0842309A1 EP96922737A EP96922737A EP0842309A1 EP 0842309 A1 EP0842309 A1 EP 0842309A1 EP 96922737 A EP96922737 A EP 96922737A EP 96922737 A EP96922737 A EP 96922737A EP 0842309 A1 EP0842309 A1 EP 0842309A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lyosol
- silica
- microporous
- pores
- capillaries
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Definitions
- aluminum is relatively corrosion-resistant because the metal surface in the air is immediately covered with a 5 to 20 nm thick, firmly adhering and very dense oxide layer which prevents further oxygen access.
- Magnesium and titanium and their alloys are also protected against further oxidation by a thin oxide layer at normal temperature.
- the anodically produced coating consists, for example, of a coherent sub-layer (barrier layer) about 0.15 ⁇ m thick and a microporous cover layer, which consists of capillaries perpendicular to the metal of 0.01 to 0.05 ⁇ m (10 - 50 nm) is penetrated at a distance of about 0.3 ⁇ m.
- the microporous cover layer has an inner surface of about 100 m / g after its production and is very chemically reactive. This high chemical reactivity is caused by active centers, which are formed by OH groups in the near-surface area of the microporous cover layer (see Peri, J.B .: J.Phsy.Chem. 69 (1965), p. 220). With newer methods of anodic oxidation, microporous cover layers down to about 200 ⁇ m can be created on Al materials.
- Anodic oxidation of magnesium can also be used to produce microporous cover layers which are oxidic in nature and, if appropriate
- Anodic oxidation of titanium also forms microporous cover layers with different oxidic compositions
- the pores are of different sizes. They range in size from 10 nm to 30 ⁇ m.
- Coating film on the corrosion-resistant anodized surface film of aluminum products in which this includes subjected to a sealing treatment of the micropores in the oxide film by immersing them in an aqueous sealing liquid containing dispersed silica and then coating them with a thermosetting acrylic resin.
- the purpose of this process is to be able to use coating agents with a drying or curing temperature of 140 ° C. or above due to the sealing treatment, in which problems of cracking and insufficient adhesion previously occurred.
- Oxide films by immersing the aluminum objects in the aqueous sealing liquid containing silica or silicate should also close the micropores so that, for example, sulfuric acid remaining therein can no longer escape; but it was not possible or intends to fill the vertical capillaries with the silica.
- the aim of the invention is to avoid the corrosion caused by the pores and to produce a stable bond between the microporous oxide cover layer and at least one compound forming an inorganic network.
- the invention relates to a process for the treatment of microporous top layers produced by anodic oxidation or by plasma-chemical anodic oxidation on objects made of aluminum, magnesium, titanium or their alloys, in the form of silica in the pores or capillaries of the microporous top layer a lyosol is introduced in which the colloidally distributed Si0 2 particles are at least one dimension smaller than the diameter of the pores or capillaries and the introduced and applied silica lyosol is then coagulated or reacted with the cover layer.
- a lyosol is a colloidal solution in which a solid substance is dispersed in a finely divided form in a liquid.
- Organosols and hydrosols can also be used for the purposes of the invention, depending on whether it is a suspension of the silica in organic liquids, such as alcohols, preferably C 1 -C 6 -alcohols, or water.
- organic liquids such as alcohols, preferably C 1 -C 6 -alcohols, or water.
- the silica lyosol is a silica sol (see Römpp, chemistry lexicon, key words brine and silica sol).
- the sol In order to achieve an incorporation of the sol into the pores or capillaries, it is introduced according to the invention in a form in which the SiO 2 particles are at least one dimension smaller than that
- the size of the particles of colloidal silica in the sol is accordingly about 1 to 50 nm, preferably 1 to 10 nm.
- the particles of the colloidal silica to be introduced are Appropriately as an aqueous and / or organic dispersion.
- the film formers such as alcohols and / or silanes and / or salts of organic acids, which tend to polymerize or polycondense, are added to the SiO 2 sols.
- Silica sols suitable for the purposes of the invention are known. They are produced by in situ growth of Si0 2 micro-nuclei and are then present as a concentrated aqueous dispersion of colloidally distributed pore-free amorphous Si0 2 particles. These Si0 2 dispersions generally contain minor amounts of alkali, which negatively charge the surface of the Si0 2 particles. As a result, the particles repel each other and bring about the stability of the solution. Silica sols which are suitable for the purposes of the invention are commercially available, for example, under the name KLEBOSOL. These can also be modified by other film-forming oxides of the third to eighth group of the periodic system of the elements, for example aluminum, indium, zirconium, titanium, iron, nickel and rare earths. Modification with mono- or polyhydric alcohols, eg diethylene glycol, is also possible. The silica lyosols can be produced by in situ growth of Si0 2 micro-nuclei and are then present as a concentrated aqueous dispersion
- Substances especially alcohols and silanes, are added which form films with the silica.
- the sols can also contain fillers, corrosion inhibitors, dyes, lubricants, surface-active substances, UV stabilizers in amounts which do not affect the reactivity of the sol with the microporous top layer.
- Solids concentration of the silica sol is advantageously 15 to 60%, preferably 30 to 50%.
- Objects with such oxide cover layers are immersed in the lyosol, in particular silica sol, sprayed or painted with them.
- the introduction can be improved in that the object provided with the oxide layer and immersed in the lyosol changes Exposed to pressure conditions.
- An impregnation system is suitable for this, in which the air is first removed from the pores or capillaries using a vacuum. Under the action of the vacuum, the lyosol penetrates into the pores and, after the vacuum is released, is pressed into the pores by atmospheric pressure and thus also reaches the bottom of the vertical capillaries of the anodically produced coatings of aluminum or the finest branches of the microporous cover layers on magnesium or titanium materials or on the oxide ceramic layers produced by plasma chemical oxidation.
- the change from vacuum and pressure, which can also exceed atmospheric pressure, is repeated one or more times if necessary.
- Devices suitable for introducing the particles into the microporous cover layer of the objects are available, for example, in the form of the Maldaner impregnation system.
- microporous cover layers such as hard anodized layers or oxide ceramic layers, which are less than 24 hours old, accelerate the incorporation of the silica sol to the bottom of the capillaries and pores by anodic oxidation or by plasma-chemical anodic oxidation.
- Coagulation of the silica lyosol according to the sol-gel process known per se for the film formation of such brine (Sol-Gel Technology for thin Films, Fibers, Preforms, Electronics, and Specialty Shapes, edited by Lisa Klein, Noyes Publications, S. 50 ff., Sect. 4, Helmut Dislich, Thin Films from the Sol-Gel Process). Coagulation takes place by withdrawing the liquid from the lyosol, in particular the silica sol.
- This silicate glass layer formed on the surface of the microporous cover layer from the Si0 2 particles is provided with pins protruding vertically into the capillaries of the anodized layer and having a diameter of 10 to 50 nm or in the manner of roots which penetrate the capillaries of other oxide layers, in particular ceramic layers. protrude, firmly anchored in the microporous top layer. That is probably the reason for the high corrosion and scratch resistance.
- the invention also relates to components made of aluminum,
- the surface of the microporous cover layer is preferably also covered with a film of these gels and connected to the gels in the pores or capillaries.
- magnesium casting alloys of the ASTM designation are also suitable for the purposes of the invention.
- EP-B-333 084 were treated according to the ORMOCER process in order to fill the capillaries and pores and to seal the surface of the microporous cover layer.
- a scanning electron micrograph on a cross-section shows that the pores and capillaries are filled with the silicon dioxide formed after the thermal treatment or its reaction products.
- the outer sealing layer has a thickness of approximately 5 ⁇ m.
- plates After immersion in soda water glass and subsequent silicification in a CO 2 atmosphere, plates likewise had an approximately 5 ⁇ m thick sealing layer and in the neutral salt spray test mentioned only a service life of approx. 200 hours.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19527688 | 1995-07-28 | ||
DE19527688 | 1995-07-28 | ||
PCT/DE1996/001188 WO1997005302A1 (en) | 1995-07-28 | 1996-07-02 | Process for depôtsols into microporous coating layers |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0842309A4 EP0842309A4 (en) | 1996-09-30 |
EP0842309A1 true EP0842309A1 (en) | 1998-05-20 |
EP0842309B1 EP0842309B1 (en) | 2002-01-16 |
Family
ID=7768067
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96922737A Expired - Lifetime EP0842309B1 (en) | 1995-07-28 | 1996-07-02 | Process for deposition of sols into microporous coating layers |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0842309B1 (en) |
AT (1) | ATE212075T1 (en) |
AU (1) | AU6352796A (en) |
DE (3) | DE59608600D1 (en) |
ES (1) | ES2168491T3 (en) |
PT (1) | PT842309E (en) |
WO (1) | WO1997005302A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8747641B2 (en) | 2007-03-16 | 2014-06-10 | Suddeutsche Aluminium Manufaktur Gmbh | Partial pigmentation of a coating layer to prevent interference on aluminum components or components comprising aluminum |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19741580A1 (en) * | 1997-09-20 | 1999-04-01 | Bosch Gmbh Robert | Composite |
CZ2002572A3 (en) * | 1999-08-17 | 2002-08-14 | Isle Coat Limited | Protective polyfunctional mixed coating based on light alloys and process for producing thereof |
DE102006045617B4 (en) * | 2006-09-22 | 2010-06-10 | Innovent E.V. Technologieentwicklung | Process for producing an inorganic-inorganic gradient composite layer |
DE102007027628B3 (en) * | 2007-06-12 | 2008-10-30 | Siemens Ag | Method of introducing nanoparticles into anodized aluminum surface |
EP2166200A1 (en) | 2008-09-23 | 2010-03-24 | Franz Rübig & Söhne GmbH & Co. KG | Valve spring disc and method for its manufacture |
GB2469115B (en) * | 2009-04-03 | 2013-08-21 | Keronite Internat Ltd | Process for the enhanced corrosion protection of valve metals |
CN102199785B (en) * | 2011-06-29 | 2012-12-12 | 上海理工大学 | Microarc oxidation solution of titanium alloy wear-resistant coating and application thereof |
GB2513575B (en) | 2013-04-29 | 2017-05-31 | Keronite Int Ltd | Corrosion and erosion-resistant mixed oxide coatings for the protection of chemical and plasma process chamber components |
CN106435685B (en) * | 2016-09-18 | 2018-09-07 | 佛山科学技术学院 | The method that aluminium surface electro-deposition prepares low absorptivity and high hemispherical emissivity oxidation film |
DE102017207589A1 (en) * | 2017-05-05 | 2018-11-08 | Federal-Mogul Nürnberg GmbH | Thermally insulating coating for an aluminum piston |
US11312107B2 (en) * | 2018-09-27 | 2022-04-26 | Apple Inc. | Plugging anodic oxides for increased corrosion resistance |
FR3101361B1 (en) * | 2019-09-27 | 2022-01-14 | Liebherr Aerospace Toulouse Sas | METHOD FOR MANUFACTURING A FIRE-RESISTANT PART OF AN AIR CONDITIONING SYSTEM AND PART OBTAINED BY SUCH A PROCESS |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR802421A (en) * | 1936-02-26 | 1936-09-04 | Protection of magnesium against corrosion by vitrification | |
JPS582596A (en) * | 1981-06-30 | 1983-01-08 | Nippon Parkerizing Co Ltd | Surface treatment for heat exchanger made of aluminum |
JPS5959896A (en) * | 1982-09-28 | 1984-04-05 | Nippon Light Metal Co Ltd | Sealing of anodic oxidized film of aluminum |
JPS59179798A (en) * | 1983-03-30 | 1984-10-12 | Mitsubishi Heavy Ind Ltd | Aluminum and its alloy member |
JPS61250193A (en) * | 1985-04-26 | 1986-11-07 | Pentel Kk | Surface treatment of formed aluminum or aluminum alloy body to provide antislipping property |
DE3808610A1 (en) * | 1988-03-15 | 1989-09-28 | Electro Chem Eng Gmbh | PROCESS FOR SURFACE FINISHING OF MAGNESIUM AND MAGNESIUM ALLOYS |
WO1990009670A1 (en) * | 1989-02-14 | 1990-08-23 | Sumitomo Electric Industries, Ltd. | Insulated electric wire |
JPH0327043A (en) * | 1989-06-23 | 1991-02-05 | Fuji Photo Film Co Ltd | Photosensitive planographic printing plate requiring no dampening water |
JPH04311595A (en) * | 1991-04-08 | 1992-11-04 | Nippon Parkerizing Co Ltd | Ceramic coating method for aluminium |
JPH06316787A (en) * | 1993-04-28 | 1994-11-15 | Kojundo Chem Lab Co Ltd | Treatment of surface of anodized alminum layer |
-
1996
- 1996-07-02 AT AT96922737T patent/ATE212075T1/en not_active IP Right Cessation
- 1996-07-02 DE DE59608600T patent/DE59608600D1/en not_active Expired - Fee Related
- 1996-07-02 EP EP96922737A patent/EP0842309B1/en not_active Expired - Lifetime
- 1996-07-02 DE DE29680628U patent/DE29680628U1/en not_active Expired - Lifetime
- 1996-07-02 PT PT96922737T patent/PT842309E/en unknown
- 1996-07-02 WO PCT/DE1996/001188 patent/WO1997005302A1/en active IP Right Grant
- 1996-07-02 DE DE19680596A patent/DE19680596C1/en not_active Expired - Fee Related
- 1996-07-02 ES ES96922737T patent/ES2168491T3/en not_active Expired - Lifetime
- 1996-07-02 AU AU63527/96A patent/AU6352796A/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO9705302A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8747641B2 (en) | 2007-03-16 | 2014-06-10 | Suddeutsche Aluminium Manufaktur Gmbh | Partial pigmentation of a coating layer to prevent interference on aluminum components or components comprising aluminum |
Also Published As
Publication number | Publication date |
---|---|
DE29680628U1 (en) | 1998-11-05 |
AU6352796A (en) | 1997-02-26 |
ATE212075T1 (en) | 2002-02-15 |
PT842309E (en) | 2002-07-31 |
ES2168491T3 (en) | 2002-06-16 |
DE19680596C1 (en) | 2001-08-23 |
EP0842309B1 (en) | 2002-01-16 |
DE59608600D1 (en) | 2002-02-21 |
EP0842309A4 (en) | 1996-09-30 |
WO1997005302A1 (en) | 1997-02-13 |
DE19680596D2 (en) | 1997-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102007057777B4 (en) | Method for producing a component from aluminum and / or an aluminum alloy and use of the method | |
EP0842309A1 (en) | Process for dep tsols into microporous coating layers | |
EP0545230A1 (en) | Process for preparing modified oxide ceramic coatings on barrier-layer metals and products obtained | |
DE4311772A1 (en) | Biocompatible implants comprising titanium@ for bone surgery - are prepd. by anodic oxidation of etched surface treated with phosphate-contg. soln., and then heat treating | |
Kiele et al. | Methyl–modified hybrid organic-inorganic coatings for the conservation of copper | |
DE102008062881A1 (en) | Process for producing a hollow glass molded body | |
EP3019644B1 (en) | Method for producing a corrosion-resistant, wear-resistant aluminium substrate | |
WO2000044305A1 (en) | Osteophilic implants | |
Lee et al. | Simple fabrication of superoleophobic titanium surfaces via hierarchical microhorn/nanoporous structure growth by chemical acid etching and anodization | |
DE102009041248A1 (en) | Bioactively coated metal implants and process for their preparation | |
DE102014110922A1 (en) | Metallic workpiece with a porous surface, method for its production and use of the metallic workpiece with a porous surface | |
Csokan | Some observations on the growth mechanism of hard anodic oxide coatings on aluminium | |
EP0347663B1 (en) | Method for sealing-in anodised films on aluminium and aluminium alloys | |
Menchaca-Campos et al. | Smart protection of polymer-inhibitor doped systems | |
EP2151481A1 (en) | Aqueous solution and method for coating metallic surfaces and use of modified silicic acids and concentrate compound for preparing an aqueous coating solution | |
EP2729604B1 (en) | Method for producing a bonding layer on a surface of a titanium workpiece | |
EP2236163A2 (en) | Implant made of biocorrodible metallic material with a silane coating containing nanoparticles and accompanying production method | |
DE112008002441B4 (en) | Metal materials with hybrid-stabilized oxide layer, process for the production and their use | |
DE10127494A1 (en) | Production of inorganic layers on metallic, enameled and/or glass substrates used as a scratch resistant coating comprises mixing boron nitride with solvent and inorganic binder, applying substrate, drying and sealing | |
JPS62129110A (en) | Production of microfilter | |
DE102006011348B4 (en) | A process for producing a physiological environment corrosion inhibiting layer on a molding | |
CN105648431A (en) | Method for preparing super-hydrophobic corrosion-resistant film layers on magnesium alloy surfaces | |
DE10241494A1 (en) | Porous material used for water purification and treatment has crystal-analogous overstructure formed by regular structure of particles and regular pores and consists (partly) of titanium (di)oxide | |
DE102011055644A1 (en) | Production of black ceramic oxide surface layer on component, involves forming surface layer by plasma chemical anodic oxidation using aqueous electrolyte of aqueous ammonia, citric acid, cobalt acetate and nickel acetate on component | |
EP2271792A1 (en) | Method for compressing a component made of aluminum and/or an aluminum alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A4 | Supplementary search report drawn up and despatched | ||
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
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: 19980117 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
17Q | First examination report despatched |
Effective date: 19980708 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
RTI1 | Title (correction) |
Free format text: PROCESS FOR DEPOSITION OF SOLS INTO MICROPOROUS COATING LAYERS |
|
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 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020116 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020116 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020116 |
|
REF | Corresponds to: |
Ref document number: 212075 Country of ref document: AT Date of ref document: 20020215 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: KELLER & PARTNER PATENTANWAELTE AG |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
REF | Corresponds to: |
Ref document number: 59608600 Country of ref document: DE Date of ref document: 20020221 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020416 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020416 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20020406 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2168491 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020702 |
|
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: 20020703 |
|
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: 20020731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20020415 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
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 | ||
BERE | Be: lapsed |
Owner name: *ELECTRO CHEMICAL ENGINEERING G.M.B.H. Effective date: 20020731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030201 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030630 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20030703 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030704 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030711 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040131 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20040131 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030811 |
|
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: 20040702 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050331 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20050201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
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: 20050702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020702 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20090106 Year of fee payment: 13 |
|
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: 20100202 |