EP2499272B1 - Process for production of magnesium containing aluminium strip or web material with improved adhesion - Google Patents

Process for production of magnesium containing aluminium strip or web material with improved adhesion Download PDF

Info

Publication number
EP2499272B1
EP2499272B1 EP10830248.0A EP10830248A EP2499272B1 EP 2499272 B1 EP2499272 B1 EP 2499272B1 EP 10830248 A EP10830248 A EP 10830248A EP 2499272 B1 EP2499272 B1 EP 2499272B1
Authority
EP
European Patent Office
Prior art keywords
aluminium
degreasing
magnesium
sheet material
process according
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.)
Active
Application number
EP10830248.0A
Other languages
German (de)
French (fr)
Other versions
EP2499272A1 (en
EP2499272A4 (en
Inventor
Merete Hallenstvet
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.)
Norsk Hydro ASA
Original Assignee
Norsk Hydro ASA
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 Norsk Hydro ASA filed Critical Norsk Hydro ASA
Publication of EP2499272A1 publication Critical patent/EP2499272A1/en
Publication of EP2499272A4 publication Critical patent/EP2499272A4/en
Application granted granted Critical
Publication of EP2499272B1 publication Critical patent/EP2499272B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • 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
    • C25D11/04—Anodisation of aluminium 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids

Definitions

  • the present invention relates to a process for the production of magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or web material.
  • the surface of rolled aluminium strip has excess rolling lubricants and therefore needs to be thoroughly cleaned to provide sufficient adhesion for different types of adhesives or coatings needed to withstand specified use under different and often aggressive environmental conditions.
  • Multi Layer Tube/pipe A standard design of these products comprises an inner tube of a poly ethylene (PE / PEX) or other polymer and where tie resin or adhesive is provided on the polymer tube.
  • PE / PEX poly ethylene
  • An aluminium tube is roll formed around the inner polymer tube and welded. The adhesive secures the roll formed aluminium tube to the polymer tube.
  • the aluminium tube is in turn provided with a new layer of tie resin or adhesive prior to the extrusion of the outer polymer (PE or PEX and others).
  • the adhesion of the polymer to the aluminium is of outmost importance for the performance of the final product.
  • Aluminium for this application is supplied as degreased material.
  • the standard process steps related to the production of aluminium sheet materials are by rolling and annealing thereafter chemical degreasing prior to subsequent coating with a lacquer or other organic or inorganic coating.
  • magnesium oxide on the surface of aluminium in MLT and other applications give bad adhesion for the adhesive on the aluminium surface.
  • the magnesium oxide when exposed to moisture, the magnesium oxide is converted to magnesium hydroxide which is a mild alkali and which can attack the metal underneath a coating, resulting in the loss of adhesion.
  • document WO 2008/058708A1 discloses a method of producing a low-creep aluminium alloy product, comprising the processing steps of: a) casting an ingot; b) homogenizing and/or preheating the ingot after casting; c) hot rolling the ingot into a pre-worked product, d) cold rolling the pre-worked product to a final gauge; e) annealing the cold-rolled product at a temperature of 250°C to 550°C.
  • the cold-rolled products were subjected to alcalic (alkaline) degreasing before final annealing.
  • document US5997721A relates to cleaning aluminium workpieces
  • document US 2008/035488A1 relates to a manufacturing process to produce litho sheet
  • document US3718547 A relates to continuous electrolytic treatment for cleaning and conditioning aluminium surfaces
  • document GB1235661A relates to production of lacquered aluminium or aluminium alloy strip or sheet
  • document GB1539341A relates to a process for the pre-treatment of aluminium or aluminium alloy ribbons prior to lacquering.
  • magnesium containing aluminium alloys in particular magnesium containing rolled aluminium strip or aluminium sheet material, which is not encumbered with the above disadvantages, but which has excellent surface adhesion properties.
  • the invention is characterized by the features as defined in the independent claim 1.
  • Magnesium containing aluminium alloys in particular magnesium containing rolled aluminium strip or web material forming basis for the process according to the invention have high strenght and at the same time give excellent forming properties.
  • the skilled person would have to choose higher alloyed aluminium if he wants to down gauge the metal and maintain the strength of the product.
  • the process according to the invention is based on production of magnesium containing aluminium alloy sheet material of the above kind including the following steps:
  • Rolling and levelling is performed in conventional aluminium rolling mill. After levelling, the aluminium sheet is passed to a degreasing unit where it is subjected to electrochemical degreasing including following rinsing and drying.
  • the electrochemical degreasing is done by alternating current (AC) in hot sulphuric acid resulting in a very thin aluminium oxide on the surface, typical 10 - 30nm.
  • AC alternating current
  • aluminium oxide is built at the aluminium - aluminium oxide interface.
  • the aluminium web is generating hydrogen gas on the surface and debris and lubricants are flushed off and at the same time the aluminium oxide on the surface is chemically dissolved in the hot sulphuric acid.
  • Thin oxide layer is obtained by using sulphuric acid at a concentration of 150 +/- 50 g /litre, current density of preferably 300 - 430 A/m 2 , with a contact time of 1 - 10 seconds, prefrably1.5 - 3.5 seconds and at a temperature of 60 - 90 °C, preferably 75 - 85 °C.
  • This oxide is thick enough to stop magnesium from migrating to the surface during soft annealing, but will in stead concentrate at the interface between aluminium oxide layer and aluminium metal.
  • the hereby degreased material give excellent adhesion since there is no magnesium oxide on the surface
  • Tests were performed with aluminium 3005 alloy sheet substrates with typically 0,5% Mg, comparing chemical degreasing with electrochemical degreasing according to the present invention prior to annealing.
  • the chemical degreasing was accomplished by dipping the specimen of the sheet substrate in acid degreasing bath of sulphuric acid and hydrofluoric acid with addition of surfactants.
  • electrochemical degreasing according to the invention was done by production equipment with the following parameters, current density 346 A/m2, contact time 6,4 seconds and 150g/ litre sulphuric acid with a temperature of 80°C.
  • the surface of electrochemical degreased AA3005 is aluminium oxide (Oxygen peaks at the surface) and the magnesium peak is at the interface between the aluminium oxide and the aluminium metal.
  • the surface of the chemically degreased material has magnesium oxide on the outer surface seen by the magnesium peak at the outermost surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

  • The present invention relates to a process for the production of magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or web material.
  • The surface of rolled aluminium strip has excess rolling lubricants and therefore needs to be thoroughly cleaned to provide sufficient adhesion for different types of adhesives or coatings needed to withstand specified use under different and often aggressive environmental conditions.
  • As an example, soft annealed aluminium strip is applied as an oxygen and water barrier in plastic pipes and tubes called Multi Layer Tube/pipe (MLT). A standard design of these products comprises an inner tube of a poly ethylene (PE / PEX) or other polymer and where tie resin or adhesive is provided on the polymer tube. An aluminium tube is roll formed around the inner polymer tube and welded. The adhesive secures the roll formed aluminium tube to the polymer tube. The aluminium tube is in turn provided with a new layer of tie resin or adhesive prior to the extrusion of the outer polymer (PE or PEX and others).
  • The adhesion of the polymer to the aluminium is of outmost importance for the performance of the final product. Aluminium for this application is supplied as degreased material.
  • The standard process steps related to the production of aluminium sheet materials are by rolling and annealing thereafter chemical degreasing prior to subsequent coating with a lacquer or other organic or inorganic coating.
  • Normally, chemical degreasing will give a surface free from organic material (lubricant and kerosene). Soft annealing is done in an inert atmosphere. Magnesium in the alloy will migrate to the surface during the annealing step and oxidize on the surface. When magnesium oxidizes on the surface, more magnesium metal will in turn migrate to the surface. This phenomenon will take place for all concentration of magnesium in the alloy down to ppm level.
  • However, magnesium oxide on the surface of aluminium in MLT and other applications give bad adhesion for the adhesive on the aluminium surface. Thus, when exposed to moisture, the magnesium oxide is converted to magnesium hydroxide which is a mild alkali and which can attack the metal underneath a coating, resulting in the loss of adhesion.
  • As an alternative to avoiding migration of magnesium to the surface of a rolled aluminium strip, It is commonly known in the market a clad product with a core alloy with high magnesium content typical 1.5%, but which is provided with a 99,5 - 99.7 aluminium sheet material on both surfaces. By using the low magnesium material on each side the above-mentioned migration is reduced. However, this represents an expensive process route resulting in an expensive strip material product.
  • In this respect, document WO 2008/058708A1 discloses a method of producing a low-creep aluminium alloy product, comprising the processing steps of: a) casting an ingot; b) homogenizing and/or preheating the ingot after casting; c) hot rolling the ingot into a pre-worked product, d) cold rolling the pre-worked product to a final gauge; e) annealing the cold-rolled product at a temperature of 250°C to 550°C. According to said document, the cold-rolled products were subjected to alcalic (alkaline) degreasing before final annealing.
  • Further, document US5997721A relates to cleaning aluminium workpieces, document US 2008/035488A1 relates to a manufacturing process to produce litho sheet, document US3718547 A relates to continuous electrolytic treatment for cleaning and conditioning aluminium surfaces, document GB1235661A relates to production of lacquered aluminium or aluminium alloy strip or sheet, and document GB1539341A relates to a process for the pre-treatment of aluminium or aluminium alloy ribbons prior to lacquering.
  • With the present invention there is provided a process for the production of magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or aluminium sheet material, which is not encumbered with the above disadvantages, but which has excellent surface adhesion properties.
  • The invention is characterized by the features as defined in the independent claim 1.
  • The dependent claims define preferred embodiments of the invention.
  • The present invention will be further described in the following by means of examples and with reference to the figures, where:
    • Fig. 1
    show XPS = X-ray Photon Spectroscopy diagrams of a magnesium (0,5%) containing alloy which has been chemically degreased, respectively electrochemical degreased according to the invention,
  • Magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or web material forming basis for the process according to the invention have high strenght and at the same time give excellent forming properties. The skilled person would have to choose higher alloyed aluminium if he wants to down gauge the metal and maintain the strength of the product.
  • The process according to the invention is based on production of magnesium containing aluminium alloy sheet material of the above kind including the following steps:
    1. I. Rolling to final thickness of the aluminium web
    2. II. Levelling of the aluminium web
    3. III. Electrochemical degreasing of the aluminium web
    4. IV. Soft annealing of the aluminium web
  • Rolling and levelling is performed in conventional aluminium rolling mill. After levelling, the aluminium sheet is passed to a degreasing unit where it is subjected to electrochemical degreasing including following rinsing and drying. The electrochemical degreasing is done by alternating current (AC) in hot sulphuric acid resulting in a very thin aluminium oxide on the surface, typical 10 - 30nm. When the aluminium web is the anode, aluminium oxide is built at the aluminium - aluminium oxide interface. In the cathodic phase the aluminium web is generating hydrogen gas on the surface and debris and lubricants are flushed off and at the same time the aluminium oxide on the surface is chemically dissolved in the hot sulphuric acid. Thin oxide layer is obtained by using sulphuric acid at a concentration of 150 +/- 50 g /litre, current density of preferably 300 - 430 A/m2, with a contact time of 1 - 10 seconds, prefrably1.5 - 3.5 seconds and at a temperature of 60 - 90 °C, preferably 75 - 85 °C. This oxide is thick enough to stop magnesium from migrating to the surface during soft annealing, but will in stead concentrate at the interface between aluminium oxide layer and aluminium metal. The hereby degreased material give excellent adhesion since there is no magnesium oxide on the surface
    • Experiments.
  • Tests were performed with aluminium 3005 alloy sheet substrates with typically 0,5% Mg, comparing chemical degreasing with electrochemical degreasing according to the present invention prior to annealing.
  • The chemical degreasing was accomplished by dipping the specimen of the sheet substrate in acid degreasing bath of sulphuric acid and hydrofluoric acid with addition of surfactants.
  • Further, electrochemical degreasing according to the invention was done by production equipment with the following parameters, current density 346 A/m2, contact time 6,4 seconds and 150g/ litre sulphuric acid with a temperature of 80°C.
  • Surface analysis of specimen from the test were performed with XPS = X-ray Photon Spectroscopy equipment, and the results of these analysis are shown in Fig. 1.
    The surface of electrochemical degreased AA3005 is aluminium oxide (Oxygen peaks at the surface) and the magnesium peak is at the interface between the aluminium oxide and the aluminium metal. The surface of the chemically degreased material has magnesium oxide on the outer surface seen by the magnesium peak at the outermost surface.

Claims (6)

  1. Process for the production of magnesium containing aluminium alloys with the following steps:
    A. rolling to final thickness of an aluminium sheet material
    B. levelling of the aluminium sheet material
    C. electrochemical degreasing of the aluminium sheet material
    D. soft annealing of the aluminium sheet material,
    wherein step C is carried out before step D, wherein the electrochemical degreasing is done by alternating current (AC) processing of the aluminium sheet material in sulphuric acid resulting in an aluminium oxide layer on the surface of up to 30 nm, and wherein the electrochemical degreasing takes place at a temperature between 60 - 90 °C.
  2. Process according to claims 1,
    characterised in that
    a concentration of the sulphuric acid is between 100 - 200 g /litre.
  3. Process according to claims 1 or 2,
    characterised in that
    an applied AC current density is between 200 - 500 A/m2.
  4. Process according to claims 1,
    characterised in that
    the electrochemical degreasing takes place at a temperature between 75 - 85 °C.
  5. Process according to claims 1- 4
    characterised in that
    a contact time under degreasing is between 1. - 10 seconds.
  6. Process according to claims 5,
    characterised in that
    the contact time under degreasing is between 1.5 - 3.5 seconds.
EP10830248.0A 2009-11-13 2010-11-11 Process for production of magnesium containing aluminium strip or web material with improved adhesion Active EP2499272B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20093346 2009-11-13
PCT/NO2010/000410 WO2011059341A1 (en) 2009-11-13 2010-11-11 Process for production of magnesium containing aluminium strip or web material with improved adhesion

Publications (3)

Publication Number Publication Date
EP2499272A1 EP2499272A1 (en) 2012-09-19
EP2499272A4 EP2499272A4 (en) 2016-03-23
EP2499272B1 true EP2499272B1 (en) 2017-08-16

Family

ID=43991814

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10830248.0A Active EP2499272B1 (en) 2009-11-13 2010-11-11 Process for production of magnesium containing aluminium strip or web material with improved adhesion

Country Status (3)

Country Link
EP (1) EP2499272B1 (en)
NO (1) NO2499272T3 (en)
WO (1) WO2011059341A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018108529A1 (en) * 2016-12-12 2018-06-21 Norsk Hydro Asa Composite product

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1235661A (en) * 1967-03-30 1971-06-16 Alcan Res & Dev Production of lacquered aluminium or aluminium alloy strip or sheet
US3718547A (en) * 1970-11-16 1973-02-27 Alcan Res & Dev Continuous electrolytic treatment for cleaning and conditioning aluminum surfaces
NO143804C (en) * 1976-03-09 1981-04-15 Nordisk Aluminium As PROCEDURE FOR PRE-TREATMENT OF ALUMINUM BANDS FOR PAINTING
EP0795048B1 (en) * 1994-12-19 2000-03-15 Alcan International Limited Cleaning aluminium workpieces
CN1802716A (en) * 2003-06-03 2006-07-12 昭和电工株式会社 Method for producing aluminum material for electrolytic capacitor electrode, aluminum material for electrolytic capacitor electrode, method for producing electrode material for electrolytic capacitor,
BRPI0709691A2 (en) * 2006-03-31 2011-07-19 Alcoa Inc lithographic sheet
US8241719B2 (en) * 2006-11-14 2012-08-14 Aleris Aluminum Duffell BVBA Creep resistant aluminium alloy for multilayer tubes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
NO2499272T3 (en) 2018-01-13
WO2011059341A1 (en) 2011-05-19
EP2499272A1 (en) 2012-09-19
EP2499272A4 (en) 2016-03-23

Similar Documents

Publication Publication Date Title
JP5015239B2 (en) Plated steel sheet for can and manufacturing method thereof
JP4920800B2 (en) Manufacturing method of steel plate for containers
JP5304000B2 (en) Steel plate for containers with excellent weldability, appearance, and can manufacturing process adhesion
JP6286821B2 (en) Flexible device substrate and manufacturing method thereof
CN103097582B (en) Steel plate for container and manufacture method thereof
WO1997035716A1 (en) Thermoplastic resin-coated aluminum alloy plate, and process and apparatus for producing the same
CN102822387B (en) Steel sheet for vessel having excellent corrosion resistance
WO2015174190A1 (en) Steel plate for container
MX2010011889A (en) Process for production of tin-plated steel sheets, tin-plated steel sheets and chemical conversion treatment fluid.
JP2009001854A (en) Steel plate for containers
JP4869976B2 (en) Plated steel sheet for can and manufacturing method thereof
KR19980080435A (en) Galvanized Steel Sheet and Manufacturing Method
TWI424098B (en) Can-making steel sheet with excellent corrosion resistance
JP5594443B1 (en) Steel plate for container and method for producing the same
JP4626532B2 (en) Surface-treated steel sheet and method for producing the same, resin-coated steel sheet, can and can lid
JP5994960B1 (en) Steel plate for container and method for producing steel plate for container
EP2499272A1 (en) Process for production of magnesium containing aluminium strip or web material with improved adhesion
Moffitt et al. Improved corrosion protection of al alloys by system approach interface engineering: part 3—AA7075-T6
JP2004018906A (en) Surface-treated aluminum material, manufacturing method therefor, formed aluminum article, and aluminum can
CN102245794A (en) Titanium material and method for producing titanium material
JP2008230117A (en) Resin coating tin plated steel sheet, can, and can lid
JP4376475B2 (en) Surface-treated aluminum material excellent in adhesiveness and method for producing the same
JP2007321212A (en) Ni-plated steel sheet excellent in slidability and contact resistance and method for producing the same
WO2016111350A1 (en) Steel sheet for container and method for producing steel sheet for container
JP2005350775A (en) Surface-treated aluminum material and production method therefor

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: 20120613

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20160223

RIC1 Information provided on ipc code assigned before grant

Ipc: C22F 1/04 20060101AFI20160217BHEP

Ipc: C25D 11/04 20060101ALI20160217BHEP

Ipc: C25F 1/00 20060101ALI20160217BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170309

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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 919105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170915

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010044519

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170816

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 919105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170816

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20170816

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: 20170816

Ref country code: LT

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: 20170816

Ref country code: NL

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: 20170816

Ref country code: AT

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: 20170816

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: 20170816

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

Ref country code: LV

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: 20170816

Ref country code: ES

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: 20170816

Ref country code: PL

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: 20170816

Ref country code: RS

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: 20170816

Ref country code: IS

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: 20171216

Ref country code: BG

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: 20171116

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20170403027

Country of ref document: GR

Effective date: 20180330

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

Ref country code: RO

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: 20170816

Ref country code: CZ

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: 20170816

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: 20170816

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010044519

Country of ref document: DE

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

Ref country code: SK

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: 20170816

Ref country code: SM

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: 20170816

Ref country code: EE

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: 20170816

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

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170816

26N No opposition filed

Effective date: 20180517

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

Effective date: 20171116

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: 20171111

Ref country code: SI

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: 20170816

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: MT

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

Effective date: 20171111

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 NON-PAYMENT OF DUE FEES

Effective date: 20171111

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: 20171116

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20101111

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

Ref country code: CY

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

Effective date: 20170816

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

Ref country code: MK

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: 20170816

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

Ref country code: TR

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: 20170816

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170816

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

Ref country code: HR

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: 20170816

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

Ref country code: AL

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: 20170816

REG Reference to a national code

Ref country code: NO

Ref legal event code: CREP

Representative=s name: ZACCO NORWAY AS, POSTBOKS 488, 0213 OSLO, NORGE

REG Reference to a national code

Ref country code: NO

Ref legal event code: CHAD

Owner name: SPEIRA GMBH, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602010044519

Country of ref document: DE

Owner name: SPEIRA GMBH, DE

Free format text: FORMER OWNER: NORSK HYDRO ASA, OSLO, NO

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: SPEIRA GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: NORSK HYDRO ASA

Effective date: 20230417

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230519

REG Reference to a national code

Ref country code: CH

Ref legal event code: U11

Free format text: ST27 STATUS EVENT CODE: U-0-0-U10-U11 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20251201

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

Ref country code: DE

Payment date: 20251120

Year of fee payment: 16

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

Ref country code: NO

Payment date: 20251124

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20251124

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20251120

Year of fee payment: 16

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

Ref country code: BE

Payment date: 20251120

Year of fee payment: 16

Ref country code: GR

Payment date: 20251023

Year of fee payment: 16

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

Ref country code: CH

Payment date: 20251201

Year of fee payment: 16