EP2499272A1 - 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

Info

Publication number
EP2499272A1
EP2499272A1 EP10830248A EP10830248A EP2499272A1 EP 2499272 A1 EP2499272 A1 EP 2499272A1 EP 10830248 A EP10830248 A EP 10830248A EP 10830248 A EP10830248 A EP 10830248A EP 2499272 A1 EP2499272 A1 EP 2499272A1
Authority
EP
European Patent Office
Prior art keywords
aluminium
web
process according
degreasing
magnesium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10830248A
Other languages
German (de)
French (fr)
Other versions
EP2499272B1 (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

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)
  • 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.
  • 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: I. Rolling to final thickness of the aluminium web
  • 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, prefrablyl .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)

Abstract

Process for the production of magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or sheet material, The process is characterized by the following steps: E. rolling to final thickness of the aluminium web F. levelling of the aluminium web G. electrochemical degreasing of the aluminium web H. soft annealing of the aluminium web. The electrochemical degreasing is done by alternating current (AC) processing of the aluminium sheet material in hot sulphuric acid resulting in a thin aluminium oxide layer on the surface of between 10 - 20nm. The hereby degreased material give excellent adhesion since there is no magnesium oxide on the surface.

Description

Process for production of magnesium containing aluminium strip or web material with improved adhesion
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. With the present invention is provided a process for the production of magnesium containing aluminium alloys, in particular magnesium containing 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. Dependent claims 2 - 8 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: I. Rolling to final thickness of the aluminium web
II. Levelling of the aluminium web
III. Electrochemical degreasing of the aluminium web
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, prefrablyl .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

Claims
1. . Process for the production of magnesium containing aluminium alloys, in particular magnesium containing rolled aluminium strip or sheet material, characterised by the following steps:
A. rolling to final thickness of the aluminium web
B. levelling of the aluminium web
C. electrochemical degreasing of the aluminium web
D. soft annealing of the aluminium web.
2. Process according to claim 1 ,
characterised in that
the electrochemical degreasing is done by alternating current (AC) processing of the aluminium sheet material in hot sulphuric acid resulting in a thin aluminium oxide layer on the surface of between 10 - 30nm.
3. Process according to claims 1 and 2,
characterised in that
the concentration of the sulphuric acid is between 100 - 200 g /litre
4. Process according to claims 1 -3,
characterised in that
the applied AC current density is between 200 - 500 A/m2
5. Process according to claims 1 -4,
characterised in that
the electrochemical degreasing takes place at a temperature between 60 - 90 °C
6. Process according to claims 5,
characterised in that the electrochemical degreasing takes place at a temperature between 75 - 85 °C.
7. Process according to claims 1-6
characterised in that
the contact time under degreasing is between 1.-10 seconds.
Process according to claims 7,
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 true EP2499272A1 (en) 2012-09-19
EP2499272A4 EP2499272A4 (en) 2016-03-23
EP2499272B1 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)

Cited By (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
See references of WO2011059341A1 *

Cited By (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

Also Published As

Publication number Publication date
EP2499272B1 (en) 2017-08-16
NO2499272T3 (en) 2018-01-13
WO2011059341A1 (en) 2011-05-19
EP2499272A4 (en) 2016-03-23

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