EP2489448A1 - Traitement de surface en ligne pour obtenir des extrusions d'aluminium revêtues avec une couche résistante à la corrosion et extrusions ainsi obtenues - Google Patents

Traitement de surface en ligne pour obtenir des extrusions d'aluminium revêtues avec une couche résistante à la corrosion et extrusions ainsi obtenues Download PDF

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Publication number
EP2489448A1
EP2489448A1 EP11001244A EP11001244A EP2489448A1 EP 2489448 A1 EP2489448 A1 EP 2489448A1 EP 11001244 A EP11001244 A EP 11001244A EP 11001244 A EP11001244 A EP 11001244A EP 2489448 A1 EP2489448 A1 EP 2489448A1
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Prior art keywords
profile
solution
corrosion
process according
resistant layer
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EP11001244A
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German (de)
English (en)
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EP2489448B1 (fr
Inventor
Elodie Gazanion
Andreas Afseth
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Constellium Extrusions Deutschland GmbH
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Alcan Centre de Recherches de Voreppe SAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00Extruding metal; Impact extrusion
    • B21C23/002Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00Extruding metal; Impact extrusion
    • B21C23/01Extruding metal; Impact extrusion starting from material of particular form or shape, e.g. mechanically pre-treated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C35/00Removing work or waste from extruding presses; Drawing-off extruded work; Cleaning dies, ducts, containers, or mandrels
    • B21C35/02Removing or drawing-off work
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C35/00Removing work or waste from extruding presses; Drawing-off extruded work; Cleaning dies, ducts, containers, or mandrels
    • B21C35/02Removing or drawing-off work
    • B21C35/023Work treatment directly following extrusion, e.g. further deformation or surface treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229Composition of the substrate
    • C23C18/1241Metallic substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1254Sol or sol-gel processing
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1262Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127Preformed particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/02Processes for applying liquids or other fluent materials performed by spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/20Metallic substrate based on light metals
    • B05D2202/25Metallic substrate based on light metals based on Al
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254After-treatment

Definitions

  • the invention relates to extruded aluminium alloy profiles which are coated with a corrosion resistant layer. It relates more particularly to profiles coated by alternative coating processes which replace expensive batch processes such as anodizing or powder coating.
  • extruded aluminium alloy profiles When they are not coated with a protective layer, extruded aluminium alloy profiles can develop cosmetic corrosion such as staining or discoloration, sometimes within a few days or weeks of natural exposure. As a result, they become unsightly and therefore unsuitable for the application for which they were intended.
  • the anodising process is generally carried out on the profiles after their ageing treatment. This process is preceded by degreasing and etching steps and followed by a sealing step.
  • the protective anodised layer is deposited when the profile is set to an anodic potential in an electrolytic bath, many handlings are required to obtain a good electrical contact ensuring the formation of a regular and homogeneous anodisation layer on the entire profile. Such handlings are very difficult to automate because of the geometric variety of profiles to be treated.
  • the electrical contact areas are not covered and must be then removed, thereby increasing the profile scrap ratio. As a result, it is a long and expensive batch process.
  • the work-piece after being coated, the work-piece must normally be heated either to cure the organic/inorganic coating or to hydrothermally seal an anodic oxide: this heat treatment adds further costs and can also have a negative impact on the mechanical properties of the substrate.
  • the applicant has investigated alternative surface treatment processes which improve the corrosion resistance of the profiles compared to non-treated products and which nevertheless are less expensive than known solutions such as anodising.
  • a first purpose of the present invention is providing a process for manufacturing aluminium alloy extruded profile parts which are resistant to corrosion, comprising the following steps:
  • the process according to the invention basically remains a classical extrusion process, but with an additional coating step occurring simultaneously with the extrusion step.
  • a device is preferably used for depositing the said fluid solution on the freshly formed surface of the profile.
  • the latter is located near the exit of the extrusion press, preferably downstream of the quenching workstation, if any, and upstream of the saw, preferably upstream of the reception table, also called "run out table”. Therefore this surface treatment process can be easily adapted to any common extrusion line.
  • the process according to the invention necessitates low investment. It can be carried out through a shortened fabrication process chain, with a reduced number of process steps.
  • the depositing device works in coordination with the puller in such a manner that there is no coating accumulation when the extrusion press is stopped for removing the container and shearing the butt.
  • the deposit of a protective coating is advantageously achieved by spraying a fluid solution or medium with a viscosity low enough to be able to be sprayed by a nozzle without quick clogging thereof and a viscosity high enough to form a stable and continuous coating on the profile surface.
  • This coating process step is quicker than any batch process of the prior art and makes it possible to obtain a coating thickness of between 0,1 ⁇ m and 20 ⁇ m, preferably between 0,1 ⁇ m and 3 ⁇ m.
  • the corrosion resistant layer may have a thickness between 0,1 ⁇ m and 0,4 ⁇ m or between 0,4 ⁇ m and 3 ⁇ m.
  • the coating obtained is more or less regular and homogeneous. Therefore, the present coating process step is especially recommended for profiles, which should be corrosion resistant, but with undemanding requirements related this corrosion resistance. For example, the present coating process is recommended for profiles, which should be resistant to the cosmetic corrosion which results from their contact with the air and humidity.
  • aluminium alloy extrusions should be cooled or quenched at the exit of the extrusion press to a specific temperature range to ensure adequate mechanical properties after the ageing treatment.
  • the fluid solution contains flammable materials, such as a sol-gel precursor or a varnish
  • the temperature of the profile should be less than a critical value, typically the autoignition temperature of the flammable material and it is therefore recommended to deposit the fluid solution after the profile has been quenched to a temperature less than this critical value.
  • the temperature targeted after quench is advantageously between 80 °C and 250 °C, preferably between 140 °C and 210 °C, more preferably between 150 °C and 200°C.
  • the manufacturing process according to the invention is largely time-saving compared to processes of prior art.
  • the coating obtained by using this process provides significant improvement in corrosion properties in comparison with uncoated profiles. It is significantly less expensive than conventional coating processes due to less handling and treatment process steps.
  • the fluid solution to be applied on the profile at its exit from the extrusion press is a sol-gel precursor. Any other fluid solution able to form a corrosion resistant coating could be used, for example an acrylic, polyester or epoxy-based lacquer or varnish, provided that this fluid solution can be applied with an appropriate device and that the part of the extrusion line located downstream of the extrusion press is not quickly clogged, for example by the fog resulting from spraying the said fluid solution near the fresh surface of the profile.
  • the corrosion resistant layer is a coating obtained by spraying a sol-gel precursor on the freshly formed metal surface of the profile.
  • sol-gel precursor it is to be understood that a coating is produced by the sol-gel technology, which, from application of a liquid solution of organo-metallic precursor chemicals on a substratum (here the profile), forms after curing a hardened protective layer fixed on the said substratum.
  • the protective layer is preferably a transparent curable sol-gel coating, through which the colour tone of the metallic substrate can be detected.
  • the protective layer applied on the fresh surface of the substrate is preferably a sol-gel coating, in particular, a sol-gel coating made of a polysiloxane and advantageously a sol-gel coating made of a polysiloxane prepared from an alcoholic silane solution, especially an alkoxysilane solution, and an aqueous colloidal silica solution.
  • Polysiloxane is the term for polymers of crosslinked siloxanes. The polysiloxane is generated in particular by an acid catalyzed condensation reaction between hydrolyzed silanes, also known as silanols.
  • the condensation reaction between hydrolyzed silanes, especially alkoxysilanes, and colloidal silica results in the formation of an inorganic network of polysiloxanes.
  • organic groups may be built in the inorganic network with carbon bonds.
  • the organic groups for example alkyl groups, such as methyl, ethyl, propyl or butyl, do not participate directly to the polymerization or crosslinking of the siloxanes. They do not serve to form an organic polymer system but only to achieve the functionalization of the said siloxanes.
  • functional properties such as surface energy, hydrophobicity, oleophobicity of flexibility of the final cured coating, may be modified by an appropriate choice of organo-functional silanes.
  • a sol-gel precursor is prepared from two basic solutions A and B.
  • Solution A is an alcoholic solution of one or more different alkoxysilanes, where the alkoxysilanes are present in a non-hydrolyzed form in an anhydrous medium.
  • an alcohol is used as a solvent, such as methyl, ethyl, propyl, or butyl alcohol or, preferably, isopropyl alcohol.
  • the alkoxysilanes are described by the general formula X n Si(OR) 4-n in which "R" is a simple alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl.
  • X is also an alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl.
  • Appropriate alkoxysilanes are for example tetramethoxysilane (TMOS), preferably tetraethoxysilane (TEOS), and methyl trimethoxysilane (MTMOS).
  • the solution A is prepared from a tetraethoxysilane (TEOS) and/or methyl trimethoxysilane (MTMOS) using a methyl, ethyl or propyl alcohol, and in particular an isopropyl alcohol, as a solvent.
  • Solution A can contain for example 25 - 35 wt% (% by weight), preferably 30 wt%, TEOS and 15 - 25 wt%, preferably 20 wt%, MTMOS, both dissolved in 40 - 60 wt%, preferably 50 wt%, isopropyl alcohol.
  • Solution B contains colloidal silica dissolved in water.
  • solution B is set with an acid, preferably with nitric acid (HNO 3 ), to a pH value between 2.0 and 4, preferably between 2.5 and 3.0 and more preferably close to 2.7.
  • the silica used is stabilized in an acid medium, where the pH is advantageously between 2 and 4.
  • the silica has advantageously alkali content as low as possible, preferably less than 0.04 wt % Na 2 O.
  • Solution B contains for example 70-80 wt%, preferably 75 wt%, water as a solvent and 20 - 30 wt%, preferably 25 wt%, colloidal silica.
  • the solution B is set with nitric acid (HNO 3 ) to a pH value between 2.0 and 3.5, preferably between 2.5 and 3.0, more preferably close to 2.7.
  • HNO 3 nitric acid
  • a condensation reaction occurs, where a siloxane bond (Si-O-Si) is formed from two Si-OH groups, accompanied by the formation of water.
  • a network of polysiloxanes affiliated with alkyl groups is formed by progressive polymerization.
  • the resulting mixed solution is in a gel-like state.
  • the two solutions A and B are preferably mixed in a weight ratio of 7:3.
  • the sol-gel precursor is applied in a gel form having appropriate fluidity to be sprayed on the profile fresh surface, and then dried and/or cured.
  • the drying process consists in expelling water and alcohols remaining in the sol-gel coating, whereby the sol-gel coating hardens and a corrosion- and weather-resistant protective layer is formed on the fresh surface of the profile.
  • a sol-gel precursor supplied by company Akzo Nobel under brand name CERAPAINT is used to form the corrosion protection layer.
  • Another purpose of the present invention is providing an aluminium alloy extruded profile part which could have been coated by the coating process step according to the invention, i.e. which is characterised in that it has a corrosion-resistant layer directly deposited on the aluminium alloy of the said extruded profile, except at its sawn ends.
  • the said extruded profile is advantageously made of any of the following alloys: AA 6005, AA 6005A, AA 6008, AA 6014, AA 6060, AA 6061, AA 6063, AA 6063A, AA 6056, AA 6066, AA 6082, AA 6101, AA 6110, AA 6110A, AA 6182, AA 6401 and AA 6463.
  • the said corrosion-resistant layer results from the application of a sol-gel precursor and comprises an inorganic network of polysiloxanes affiliated with alkyl groups attached to the said inorganic network with carbon bonds.
  • Such profiles have a cosmetic corrosion resistance better than uncoated profiles but they do not have to comply with any particularly demanding requirement related to their aesthetic aspect such as profiles for the building industry.
  • Such profiles are preferably structural profiles extruded from an AA6xxx aluminium alloy and heat treated to tempers T6 or T5.
  • Figure 1 illustrates schematically a conventional extrusion process scheme.
  • FIG. 2 illustrates schematically the scheme of the extrusion process according to the invention.
  • the different sol-gel precursor solutions were sprayed using a spray gun the nozzle of which had a diameter of 1.3 mm.
  • the distance between the spray gun and the substrate, the pressure of the air and the dilution of the lacquer are parameters which can be adapted to change the thickness and the appearance of the coatings.
  • Spray coatings were realised on substrates at room temperature and also on substrates pre-heated at 180°C and 230°C.
  • the reference of the spray gun, which was used, is Sata RP 2000.
  • Water-based sol-gel precursors were less easy to be sprayed and to form a regular coating with a smooth surface, whatever the surface temperature of the substrate and consequently gave bad results in the corrosion tests. Therefore, although their autoignition temperature is lower and their shelf-life is shorter, alcohol based sol-gel systems have been preferred: they were easier to be sprayed and presented a lower risk of contamination of the line.
  • the sol-gel precursor chosen for the in-line experiments is an alcohol based sol-gel system, which is prepared by acid catalyzed hydrolysis and condensation of a mixture of a water-free solution A and an aqueous solution B, where the solution A is a solution comprising 30 wt% tetraethoxysilan (TEOS), 20 wt% methyl trimethoxysilane (MTMOS) and 50 wt% isopropyl alcohol.
  • Solution B is a suspension of 25% colloidal silica in 75 wt% deionised water acidified to a pH of 2.7 by nitric acid.
  • a basic solution A as described above in a proportion of 70 wt% of the mixed solution, is added, under mechanical agitation, the solution B in a proportion of 30 wt% of the mixed solution.
  • the pH of the mixed solution is adjusted by means of nitric acid to a value of 2.7.
  • the mixed solution is agitated for around 6 hours, whereby reaction-induced heat is released, and then filtered using a polypropylene filter with pore size of 1 ⁇ m. After filtering the residue is discarded and the filtrate is allowed to rest for a period between 12 and 22 hours before being applied to the substrate to form the protective coating.
  • a solution prepared in this manner has a room temperature dynamic viscosity below 20 cP (i.e. 2 10 -2 Pa.s or Nm -2 .s) and is suitable for spray application by the equipment described above.
  • This coating precursor used for the in-line experiments (See example 3) is also characterized in that no harmful component is released during the formation of the protective layer.
  • Figure 1 illustrates schematically a conventional extrusion line, where aluminium logs are supplied by the log loader (10) and driven to the preheating oven (20).
  • the logs are sheared with a heat shearing device (25) at the exit of the preheating oven to obtain billets at the desired length.
  • the cold logs are sawed to make billets at the wished length which are then preheated, by generally using an induction furnace.
  • the hot billet is then driven towards the extrusion press (30): it is introduced into the central bore of the container (32) thanks to the mandrel (33) attached to the piston (34) which moves towards the press platen (31), where the die set is located.
  • the extrusion starts by moving forward the piston and an extruded profile exits from the die hole.
  • the puller (42) draws the profile (100) during the entire extrusion step with a speed adapted to the speed of the profile so that the profile remains straight and slightly stretched up to the run out table (50).
  • the piston (34) is stopped; the container (32) is removed from the die set so that the butt can be sheared. After the butt is sheared, the final end of the profile is released and the profile can then be drawn again by the puller until that it is fully located on the run out table.
  • a cooling device (41) is used to quench the profile at the exit of the extrusion press. Once on the run out table, the profile is generally slightly plastically stretched by a stretcher (60) and then sawn at the wished length by a sawing machine (70). The profile parts (110) thus obtained are then stacked in a storage area (80) and heat treated, generally in ageing ovens (90).
  • EXAMPLE 3 SPRAYING A SOL-GEL LACQUER AT THE EXIT OF THE EXTRUSION PRESS (FIGURE 2)
  • the extrusion line used in this example is close to the extrusion line described in example 2.
  • the main difference with the conventional extrusion line lies in that a spraying device (45) is introduced at the exit of the extrusion press, downwards of the quenching device (41) and upwards the run out table (50).
  • the profile extruded is a tubular profile having an approximately square section of 80mm*80 mm with 2 mm thick walls. It is extruded from a billet in AA6063 through a porthole die with an exit speed of approximately 30 m/min.
  • the profile is quenched with forced air by the quenching device which is several meters long and begins around 1 meter from the exit of the extrusion die.
  • the temperature of the metal after air quenching is around 180°C.
  • the spraying device is located downwards of the quenching device, typically in an area distant of approximately 6-8 meters from the last end of the bearings. In the present case, it comprises 4 spray guns.
  • the section of the profile used for this test has a quite high size. Smaller extruded profiles, exiting simultaneously from the extrusion press, could also be coated using this spraying device, provided that they are guided to have a stabilised course in the spraying area, which is quite easy to do since this area is far enough from the die exits.
  • the number and the location of the spray guns should be adapted to their shape and spatial configuration. Larger sections could also be coated in a similar way on a larger press.
  • the spraying device (45) works in coordination with the puller (42) in such a manner that there is no coating accumulation when the extrusion press is stopped for shearing the butt.
  • Sol gel coated profiles do not suffer any corrosion. Anodised and untreated profiles are corroded after 240h. The anodisation layer is degraded because of the condensation cycles during the QUV-B testing and not directly because of the QUV irradiation.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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EP20110001244 2011-02-16 2011-02-16 Traitement de surface en ligne pour obtenir des extrusions d'aluminium revêtues avec une couche résistante à la corrosion Active EP2489448B1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015111440A1 (de) * 2015-07-15 2017-01-19 Dura Automotive Body & Glass Systems Gmbh Verfahren zur Behandlung einer anodisch oxidierten Oberfläche aus Aluminium oder einer Aluminiumlegierung
CN106367790A (zh) * 2016-11-11 2017-02-01 佛山市三水雄鹰铝表面技术创新中心有限公司 氧化槽铝离子与硫酸回收及氧化液缓蚀与冷却节能系统
CN107164709A (zh) * 2017-04-26 2017-09-15 西安工程大学 分体式铝合金及轻合金挤压型材柔性在线淬火装置及方法
EP3287211A1 (fr) * 2016-08-24 2018-02-28 Toyota Jidosha Kabushiki Kaisha Procédé d'assemblage de dissipateur de chaleur
IT201800004684A1 (it) * 2018-04-18 2019-10-18 Procedimento ed impianto di rivestimento di un profilato metallico e profilato cosi' ottenuto
CN113263334A (zh) * 2021-07-21 2021-08-17 佛山市通润热能科技有限公司 一种挤压机后部辅机设备
CN115069813A (zh) * 2022-07-27 2022-09-20 广东赛福智能装备有限公司 一种铝型材挤压后部生产线冷却机构
CN118180188A (zh) * 2024-05-17 2024-06-14 广东广源铝业有限公司 一种基于表面处理的铝合金型材成型工艺

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1109248A (en) * 1965-12-29 1968-04-10 Duralumin Improvements relating to the manufacture of metallic section members
US4115607A (en) * 1976-03-29 1978-09-19 Yoshida Kogyo K.K. Process of coating aluminum materials molded by extrusion with polysiloxane coating
JPS58176018A (ja) * 1982-04-10 1983-10-15 Yoshida Kogyo Kk <Ykk> 押出型材の製造方法
JPH0246969A (ja) * 1988-08-09 1990-02-16 Furukawa Alum Co Ltd 熱交換器用ろう付アルミ偏平チューブの製造方法
US4952452A (en) 1988-07-10 1990-08-28 Klil Industries Ltd. Aluminum profile coated with organic resin and non-leafing pigments
EP1306144A1 (fr) * 2001-10-23 2003-05-02 Alcan Technology & Management AG Procédé de traitement en continu de surface d'un profilé en aluminium
EP1457267A1 (fr) * 2003-03-12 2004-09-15 Alcan Technology &amp; Management Ltd. Procédé de fabrication de pièces de tôle d'aluminium formées avec une surface décorative
CN2885613Y (zh) 2005-10-12 2007-04-04 珠海东诚化工有限公司 彩色铝合金型材
CA2625779A1 (fr) 2007-03-16 2008-09-16 Sueddeutsche Aluminium Manufaktur Gmbh Traitement d'une surface d'element d'aluminium ou d'une surface contenant de l'aluminium

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1109248A (en) * 1965-12-29 1968-04-10 Duralumin Improvements relating to the manufacture of metallic section members
US4115607A (en) * 1976-03-29 1978-09-19 Yoshida Kogyo K.K. Process of coating aluminum materials molded by extrusion with polysiloxane coating
JPS58176018A (ja) * 1982-04-10 1983-10-15 Yoshida Kogyo Kk <Ykk> 押出型材の製造方法
US4952452A (en) 1988-07-10 1990-08-28 Klil Industries Ltd. Aluminum profile coated with organic resin and non-leafing pigments
JPH0246969A (ja) * 1988-08-09 1990-02-16 Furukawa Alum Co Ltd 熱交換器用ろう付アルミ偏平チューブの製造方法
EP1306144A1 (fr) * 2001-10-23 2003-05-02 Alcan Technology & Management AG Procédé de traitement en continu de surface d'un profilé en aluminium
EP1457267A1 (fr) * 2003-03-12 2004-09-15 Alcan Technology &amp; Management Ltd. Procédé de fabrication de pièces de tôle d'aluminium formées avec une surface décorative
CN2885613Y (zh) 2005-10-12 2007-04-04 珠海东诚化工有限公司 彩色铝合金型材
CA2625779A1 (fr) 2007-03-16 2008-09-16 Sueddeutsche Aluminium Manufaktur Gmbh Traitement d'une surface d'element d'aluminium ou d'une surface contenant de l'aluminium

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015111440B4 (de) 2015-07-15 2023-07-13 Plasman Europe Ab Verfahren zur Behandlung einer anodisch oxidierten Oberfläche aus Aluminium oder einer Aluminiumlegierung und beschichtete Aluminiumoberfläche, die aus einem derartigen Verfahren erhalten wird
DE102015111440A1 (de) * 2015-07-15 2017-01-19 Dura Automotive Body & Glass Systems Gmbh Verfahren zur Behandlung einer anodisch oxidierten Oberfläche aus Aluminium oder einer Aluminiumlegierung
EP3287211A1 (fr) * 2016-08-24 2018-02-28 Toyota Jidosha Kabushiki Kaisha Procédé d'assemblage de dissipateur de chaleur
JP2018032716A (ja) * 2016-08-24 2018-03-01 トヨタ自動車株式会社 ヒートシンクの製造方法
US20180056363A1 (en) * 2016-08-24 2018-03-01 Toyota Jidosha Kabushiki Kaisha Method for producing heat sink
CN107774963A (zh) * 2016-08-24 2018-03-09 丰田自动车株式会社 散热器的制造方法
US10596618B2 (en) 2016-08-24 2020-03-24 Toyota Jidosha Kabushiki Kaisha Method for producing heat sink
CN107774963B (zh) * 2016-08-24 2020-09-08 丰田自动车株式会社 散热器的制造方法
CN106367790A (zh) * 2016-11-11 2017-02-01 佛山市三水雄鹰铝表面技术创新中心有限公司 氧化槽铝离子与硫酸回收及氧化液缓蚀与冷却节能系统
CN107164709A (zh) * 2017-04-26 2017-09-15 西安工程大学 分体式铝合金及轻合金挤压型材柔性在线淬火装置及方法
CN107164709B (zh) * 2017-04-26 2018-10-30 西安工程大学 分体式铝合金挤压型材柔性在线淬火装置及方法
IT201800004684A1 (it) * 2018-04-18 2019-10-18 Procedimento ed impianto di rivestimento di un profilato metallico e profilato cosi' ottenuto
CN113263334A (zh) * 2021-07-21 2021-08-17 佛山市通润热能科技有限公司 一种挤压机后部辅机设备
CN115069813A (zh) * 2022-07-27 2022-09-20 广东赛福智能装备有限公司 一种铝型材挤压后部生产线冷却机构
CN118180188A (zh) * 2024-05-17 2024-06-14 广东广源铝业有限公司 一种基于表面处理的铝合金型材成型工艺
CN118180188B (zh) * 2024-05-17 2024-09-10 广东广源铝业有限公司 一种基于表面处理的铝合金型材成型工艺

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