EP0318403B1 - Process for continuously anodising strips of aluminium or its alloys which are to be provided with an organic coating - Google Patents
Process for continuously anodising strips of aluminium or its alloys which are to be provided with an organic coating Download PDFInfo
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- EP0318403B1 EP0318403B1 EP88420391A EP88420391A EP0318403B1 EP 0318403 B1 EP0318403 B1 EP 0318403B1 EP 88420391 A EP88420391 A EP 88420391A EP 88420391 A EP88420391 A EP 88420391A EP 0318403 B1 EP0318403 B1 EP 0318403B1
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- Prior art keywords
- strips
- aluminium
- electrolyte
- process according
- anodising
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 6
- 239000000956 alloy Substances 0.000 title claims abstract description 6
- 239000004411 aluminium Substances 0.000 title claims abstract 4
- 238000007743 anodising Methods 0.000 title abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 238000002048 anodisation reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 238000004026 adhesive bonding Methods 0.000 abstract description 2
- 150000001844 chromium Chemical class 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- -1 for example Chemical class 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000009928 pasteurization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
Definitions
- the present invention relates to a process for the continuous anodization of strips of aluminum or one of its alloys intended to be coated with an organic product.
- one of the means consists in coating the surfaces of said elements with organic products such as glues in order to make them integral with one another.
- 4,085,012 claims an anodization process in which an aqueous solution of phosphoric acid with a concentration by weight of between 3 and 20% is used at a temperature between 10 and 30 ° C under a voltage between 3 and 25 volts and which makes it possible to develop an oxide layer in the form of columns.
- This layer constitutes a good bonding base for an epoxy-type resin and makes it possible to produce composite products which, by bonding together, lead to structures having good resistance to humidity.
- the film obtained constitutes a good bonding base for the application of paints or lacquers or for the production of structures based on aluminum.
- the anodization temperatures here are much higher than in the previous patent: 25 to 80 ° C instead of 10 to 30 ° C and this is explained in the application as follows: the oxide film which is formed by anodization is partially redissolved by the acid in particular inside the pores which has the effect of enlarging them and increasing the specific surface of the film. If the temperature of the electrolyte is too low, this dissolution is not sufficient to increase the surface. But, on the other hand, this temperature should not be too high either because the film can then be redissolved completely by the acid.
- the process of this application is only applicable in a range of temperatures recognized as critical by the applicant and this criticality is increased due to the very short contact times of the substrate with the electrolyte which have the effect of causing more dissolution. or less random of the oxide. Hence the obligation to stabilize this dissolution to make very precise temperature, acid concentration, current density, voltage and duration settings, depending on the nature of each of the substrates treated.
- this compound contains an organic radical which is chosen according to the nature of the organic coating. These are in particular the vinyl, acrylic, maleic and fumaric radicals.
- the mineral acid constituting the electrolyte can be chosen from sulfuric and phosphoric acids and their mixtures. It is preferable, for economic reasons, to carry out anodization under alternating current but direct current is also suitable.
- the rinsing be carried out at a temperature of between 70 and 80 ° C. so accelerating the polymerization conditions of the organometallic compound.
- the strip thus treated has an oxide surface covered with a monomolecular layer of organometallic compound chemically grafted with oxide and having organophilic properties with regard to organic coatings.
- a strip of aluminum alloy of the type 5052 according to the standards of the Aluminum Association, of thickness 0.24 mm was anodized with the parade by passage for 5 seconds in an electrolyte containing 100 g / l of phosphoric acid and 0 , 5 g / l of methacrylic chromium chloride.
- the current density being between 8 and 20 A / dm2 and the voltage between 20 and 50 volts, the temperature of the electrolyte has changed between 60 and 70 ° C.
- the strip was rinsed in water at 65 ° C then dried and finally coated with 12 g / m2 of epoxyphenolic organosol varnish used for the interior coating of boxes and lids.
- This strip intended for food packaging showed very good adhesion during the tests constituted by multi-pass stamping and the "feathering" tear tests.
- this last test consisting in subjecting the coated product to a pasteurization operation in demineralized water for 30 minutes at 70 ° C. and then to a tear in the traction bench after a pre-incision of the metal to the back of the coating, it was found that the separation of the coating did not exceed 0.5 mm relative to the location of the rupture of the metal.
- the invention finds its application in obtaining strips of aluminum or aluminum alloy coated with an organic material and intended in particular either for packaging, or for building, or even for making by gluing structural elements composed of several metallic substrates.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
La présente invention est relative à un procédé d'anodisation en continu de bandes en aluminium ou en un de ses alliages destinées à être revêtues d'un produit organique.The present invention relates to a process for the continuous anodization of strips of aluminum or one of its alloys intended to be coated with an organic product.
Bien que l'aluminium et ses alliages offrent une bonne résistance à la corrosion, il est parfois nécessaire pour certaines applications en milieu agressif de protéger leur surface au moyen d'un revêtement organique tel que, par exemple, une peinture, une laque ou un vernis. De même, quand on veut réaliser des ensembles formés de plusieurs éléments à base d'aluminium, un des moyens consiste à revêtir les surfaces desdits éléments de produits organiques tels que des colles afin de les rendre solidaires les uns des autres.Although aluminum and its alloys offer good resistance to corrosion, it is sometimes necessary for certain applications in aggressive medium to protect their surface by means of an organic coating such as, for example, a paint, a lacquer or a varnish. Similarly, when it is desired to produce assemblies formed from several elements based on aluminum, one of the means consists in coating the surfaces of said elements with organic products such as glues in order to make them integral with one another.
L'obtention de tels produits composites pose généralement le problème de l'adhérence du revêtement au substrat métallique tant du point de vue de sa solidité que de sa durabilité sachant que certains facteurs comme l'humidité de l'air peuvent à la longue diminuer cette adhérence et entraîner des décollements du revêtement.Obtaining such composite products generally poses the problem of the adhesion of the coating to the metal substrate both from the point of view of its solidity and of its durability, knowing that certain factors such as the humidity of the air can in the long term decrease this adhesion and cause peeling of the coating.
Ce problème a reçu des solutions plus ou moins satisfaisantes qui consistent généralement à modifier l'état de surface du substrat afin d'augmenter sa surface spécifique et d'y créer un relief favorable à l'accrochage du revêtement.
Cette modification peut être obtenue notamment par anodisation, procédé consistant à soumettre le substrat à un traitement électrochimique dans un électrolyte acide, de façon à développer une couche d'oxyde relativement poreuse, ce qui, suivant les conditions d'obtention permet de former des reliefs qui répondent plus ou moins bien au problème d'adhérence. Ainsi, le brevet US 4 085 012 revendique un procédé d'anodisation dans lequel on met en oeuvre une solution aqueuse d'acide phosphorique de concentration en poids comprise entre 3 et 20 % à une température comprise entre 10 et 30°C sous une tension comprise entre 3 et 25 volts et qui permet de développer une couche d'oxyde en forme de colonnes.This problem has received more or less satisfactory solutions which generally consist in modifying the surface condition of the substrate in order to increase its specific surface and to create a relief favorable to the attachment of the coating.
This modification can be obtained in particular by anodization, a process consisting in subjecting the substrate to an electrochemical treatment in an acid electrolyte, so as to develop a relatively porous oxide layer, which, according to the conditions of obtaining allows to form reliefs which respond more or less well to the adhesion problem. Thus, US Pat. No. 4,085,012 claims an anodization process in which an aqueous solution of phosphoric acid with a concentration by weight of between 3 and 20% is used at a temperature between 10 and 30 ° C under a voltage between 3 and 25 volts and which makes it possible to develop an oxide layer in the form of columns.
La surface de cette couche constitue une bonne base d'accrochage pour une résine du type epoxy et permet de réaliser des produits composites qui, par collage entre eux, conduisent à des structures présentant une bonne résistance à l'humidité.The surface of this layer constitutes a good bonding base for an epoxy-type resin and makes it possible to produce composite products which, by bonding together, lead to structures having good resistance to humidity.
On connaît également la demande de brevet européen no 181 173 qui revendique "un procédé de formation d'un film d'oxyde anodique sur une bande d'aluminium par passage en continu de la bande dans un électrolyte contenant de l'acide phosphorique maintenu à une température comprise entre 25 et 80°C, le temps de contact entre la bande et l'électrolyte étant inférieur à 15 secondes, temps durant lequel la bande est anodisée sous une densité de courant d'au moins 250 A/m²".It is also known the European patent application No. 181 173, which claims a "method of forming an anodic oxide film on an aluminum strip by continuously passing the strip through a phosphoric acid-containing electrolyte maintained at a temperature between 25 and 80 ° C., the contact time between the strip and the electrolyte being less than 15 seconds, time during which the strip is anodized at a current density of at least 250 A / m² ".
Suivant cette demande, le film obtenu constitue une bonne base d'accrochage pour l'application de peintures ou de laques ou pour la réalisation de structures à base d'aluminium.According to this request, the film obtained constitutes a good bonding base for the application of paints or lacquers or for the production of structures based on aluminum.
A la différence du brevet précédent qui s'applique à des pièces traitées en batch, on a dans cette demande, cherché à la fois à rendre le procédé compatible avec les installations de traitement au défilé où la vitesse de déplacement des bandes est de l'ordre de 150 à 250 m/min et à éviter d'utiliser des cuves de traitement trop longues, ce qui suppose des durées d'anodisation très courtes et dans le cas présent inférieures à 15 secondes. Mais, comme il faut néanmoins réaliser des épaisseurs de film suffisantes pour obtenir les propriétés d'adhérence souhaitées, on est obligé de mettre en oeuvre des densités de courant relativement élevées puisqu'elles peuvent atteindre 2000 A/m².Unlike the previous patent which applies to parts treated in batch, we have in this application sought both to make the process compatible with processing installations at the runway where the speed of movement of the strips is range from 150 to 250 m / min and avoid using too long treatment tanks, which implies very short anodization times and in this case less than 15 seconds. However, as it is nevertheless necessary to achieve sufficient film thicknesses to obtain the desired adhesion properties, it is necessary to use relatively high current densities since they can reach 2000 A / m².
De plus, les températures d'anodisation sont ici beaucoup plus élevées que dans le brevet précédent : 25 à 80°C au lieu de 10 à 30°C et cela est expliqué dans la demande de la façon suivante : le film d'oxyde qui se forme par anodisation est redissout partiellement par l'acide notamment à l'intérieur des pores ce qui a pour effet de les agrandir et d'accroître la surface spécifique du film. Si la température de l'électrolyte est trop basse, cette dissolution n'est pas suffisante pour accroître la surface. Mais, par contre, cette température ne doit pas non plus être trop élevée car le film peut alors être redissout complètement par l'acide.In addition, the anodization temperatures here are much higher than in the previous patent: 25 to 80 ° C instead of 10 to 30 ° C and this is explained in the application as follows: the oxide film which is formed by anodization is partially redissolved by the acid in particular inside the pores which has the effect of enlarging them and increasing the specific surface of the film. If the temperature of the electrolyte is too low, this dissolution is not sufficient to increase the surface. But, on the other hand, this temperature should not be too high either because the film can then be redissolved completely by the acid.
Ainsi, le procédé de cette demande n'est applicable que dans une gamme de températures reconnue critique par la demanderesse et cette criticité est accrue en raison des temps de contact très courts du substrat avec l'électrolyte qui ont pour effet de provoquer une dissolution plus ou moins aléatoire de l'oxyde. D'où l'obligation pour stabiliser cette dissolution de procéder à des réglages de température, de concentration d'acide, de densité de courant, de tension et de durée très précis et fonction de la nature de chacun des substrats traités.Thus, the process of this application is only applicable in a range of temperatures recognized as critical by the applicant and this criticality is increased due to the very short contact times of the substrate with the electrolyte which have the effect of causing more dissolution. or less random of the oxide. Hence the obligation to stabilize this dissolution to make very precise temperature, acid concentration, current density, voltage and duration settings, depending on the nature of each of the substrates treated.
Si ce procédé conduit finalement à des surfaces présentant une adhérence convenable vis-à-vis de différents revêtements organiques, on constate cependant que cette adhérence a une durabilité limitée.If this process ultimately leads to surfaces having a suitable adhesion to different organic coatings, it is found, however, that this adhesion has limited durability.
C'est dans le but d'éviter le manque de stabilité de ce procédé et l'insuffisance de la durabilité de l'adhérence, que la demanderesse a mis au point dans le cadre de l'anodisation de bandes en aluminium ou en alliage d'aluminium circulant à grande vitesse dans un électrolyte à base d'acide minéral suivi d'un rinçage à l'eau puis d'un séchage, un nouveau procédé caractérisé en ce que l'on ajoute audit électrolyte au moins un composé organométallique à base de chrome trivalent et d'un radical organique possédant une fonction carboxyle.It is with the aim of avoiding the lack of stability of this process and the insufficiency of the durability of the adhesion, that the applicant has developed in the context of the anodization of aluminum or alloy strips. aluminum circulating at high speed in an electrolyte based on mineral acid followed by rinsing with water and then drying, a new process characterized in that at least one organometallic compound based on said electrolyte is added trivalent chromium and an organic radical having a carboxyl function.
Ainsi, ce qui différencie le procédé du précédent c'est la présence d'un composé organométallique à base de chrome trivalent. En effet, on a eu l'idée puis vérifié qu'un tel composé permettait de stabiliser le procédé et de le rendre moins dépendant des paramètres d'anodisation tels que la température notamment et ce tout en gardant des durées d'anodisation très courtes.Thus, what differentiates the process from the previous one is the presence of an organometallic compound based on trivalent chromium. Indeed, we had the idea then verified that such a compound made it possible to stabilize the process and make it less dependent on anodization parameters such as temperature in particular, while keeping very short anodization times.
Ce composé de formule :
où R correspond au radical organique réagit avec l'oxyde en formant une liaison solide capable de se polymériser par autocondensation quand, lors du rinçage, le pH de l'électrolyte acide qui recouvre la surface tend vers la neutralité. Ce processus confère à l'oxyde des propriété d'adhérence vis-à-vis des revêtements organiques particulièrement bonnes en ce qui concerne à la fois leur solidité et leur durabilité.This compound of formula:
where R corresponds to the organic radical reacts with the oxide forming a solid bond capable of polymerizing by self-condensation when, during rinsing, the pH of the acid electrolyte which covers the surface tends towards neutrality. This process gives the oxide adhesion properties with respect to organic coatings which are particularly good as regards both their solidity and their durability.
De préférence, ce composé renferme un radical organique que l'on choisit en fonction de la nature du revêtement organique. Ce sont en particulier les radicaux vinylique, acrylique, maléique et fumarique.Preferably, this compound contains an organic radical which is chosen according to the nature of the organic coating. These are in particular the vinyl, acrylic, maleic and fumaric radicals.
Par ailleurs, il a été vérifié que les effets du procédé étaient obtenus dès l'instant où le composé organométallique formait un film monomoléculaire à la surface de la bande traitée, ce qui correspond à un film contenant de 1 à 3 mg/m² de Cr³⁺.Furthermore, it was verified that the effects of the process were obtained from the moment the organometallic compound formed a monomolecular film on the surface of the treated strip, which corresponds to a film containing from 1 to 3 mg / m² of Cr³ ⁺.
Quant à l'acide minéral constitutif de l'électrolyte, il peut être choisi parmi les acides sulfurique, phosphorique et leurs mélanges. Il est préférable, pour des questions économiques, d'effectuer l'anodisation sous courant alternatif mais le courant continu convient également.As for the mineral acid constituting the electrolyte, it can be chosen from sulfuric and phosphoric acids and their mixtures. It is preferable, for economic reasons, to carry out anodization under alternating current but direct current is also suitable.
Si les températures, les durées et les densités de courant d'anodisation ainsi que les concentrations des acides peuvent être choisis dans la gamme de valeurs habituelles, il est préférable que le rinçage soit effectué à une température comprise entre 70 et 80°C de façon à accélérer les conditions de polymérisation du composé organométallique.If the temperatures, the durations and the densities of the anodizing current as well as the concentrations of the acids can be chosen within the usual range of values, it is preferable that the rinsing be carried out at a temperature of between 70 and 80 ° C. so accelerating the polymerization conditions of the organometallic compound.
Après séchage, la bande ainsi traitée présente une surface d'oxyde recouverte d'une couche monomoléculaire de composé organométallique greffée chimiquement à l'oxyde et ayant des propriétés organophiles en égard aux revêtements organiques.After drying, the strip thus treated has an oxide surface covered with a monomolecular layer of organometallic compound chemically grafted with oxide and having organophilic properties with regard to organic coatings.
La présente invention peut être illustrée à l'aide de l'exemple d'application suivant :
Une bande en alliage d'aluminium du type 5052 suivant les normes de l'Aluminium Association, d'épaisseur 0,24 mm a été anodisée au défilé par passage pendant 5 secondes dans un électrolyte contenant 100 g/l d'acide phosphorique et 0,5 g/l de chlorure méthacrylique de chrome. La densité de courant étant comprise entre 8 et 20 A/dm² et la tension entre 20 et 50 volts, la température de l'électrolyte a évolué entre 60 et 70°C.
A la sortie de la cuve d'anodisation, la bande a été rincée dans de l'eau à 65°C puis séchée et enfin revêtue de 12 g/m² de vernis organosol epoxyphénolique utilisé pour le revêtement intérieur de boîtes et de couvercles.The present invention can be illustrated using the following example of application:
A strip of aluminum alloy of the type 5052 according to the standards of the Aluminum Association, of thickness 0.24 mm was anodized with the parade by passage for 5 seconds in an electrolyte containing 100 g / l of phosphoric acid and 0 , 5 g / l of methacrylic chromium chloride. The current density being between 8 and 20 A / dm² and the voltage between 20 and 50 volts, the temperature of the electrolyte has changed between 60 and 70 ° C.
At the outlet of the anodization tank, the strip was rinsed in water at 65 ° C then dried and finally coated with 12 g / m² of epoxyphenolic organosol varnish used for the interior coating of boxes and lids.
Cette bande destinée au boîtage alimentaire a montré une très bonne adhérence lors des tests constitués par l'emboutissage multipasses et les essais de déchirure "feathering". Ainsi, au cours de ce dernier test consistant à soumettre le produit revêtu à une opération de pasteurisation dans l'eau déminéralisée pendant 30 minutes à 70°C puis à une déchirure au banc de traction après une pré-incision du métal jusqu'au verso du revêtement, on a constaté que le décollement du revêtement ne dépassait pas 0,5 mm par rapport à l'endroit de la rupture du métal.This strip intended for food packaging showed very good adhesion during the tests constituted by multi-pass stamping and the "feathering" tear tests. Thus, during this last test consisting in subjecting the coated product to a pasteurization operation in demineralized water for 30 minutes at 70 ° C. and then to a tear in the traction bench after a pre-incision of the metal to the back of the coating, it was found that the separation of the coating did not exceed 0.5 mm relative to the location of the rupture of the metal.
D'autre part, les mesures de porosité par la méthode "WACO" effectuées sur les corps de boîtes pasteurisés et stérilisés en milieu agressif a donné des valeurs de courant de fuite < 5 mA ce qui répond parfaitement aux normes imposées par les utilisateurs.
Ces résultats ont été confirmés après une durée de stockage de 6 mois.On the other hand, the porosity measurements by the "WACO" method carried out on the bodies of boxes pasteurized and sterilized in aggressive medium gave values of leakage current <5 mA which perfectly meets the standards imposed by the users.
These results were confirmed after a storage period of 6 months.
L'invention trouve son application dans l'obtention de bandes d'aluminium ou d'alliage d'aluminium revêtues d'un matériau organique et destinées notamment soit à l'emballage, soit au bâtiment, soit encore à la confection par collage d'éléments de structure composés de plusieurs substrats métalliques.The invention finds its application in obtaining strips of aluminum or aluminum alloy coated with an organic material and intended in particular either for packaging, or for building, or even for making by gluing structural elements composed of several metallic substrates.
Claims (7)
- Process for the continuous anodisation of strips of aluminium or of one of its alloys for developing a surface which adheres firmly and durably to an organic coating in which said strips circulate at high speed in a mineral acid-based electrolyte, are then rinsed in water and dried, characterised in that at least one organometallic compound based on trivalent chromium and an organic radical having a carboxyl function is added to said electrolyte.
- Process according to claim 1, characterised in that the organic radical belongs to the group consisting of vinyl, acrylic, maleic and fumaric radicals.
- Process according to claim 1, characterised in that the compound has a concentration in the electrolyte which is such that it forms a monomolecular layer at the surface of the strip after anodisation.
- Process according to claim 1, characterised in that the compound forms a film containing 1 to 3 mg of Cr³⁺ per m² at the surface of the strip after anodisation.
- Process according to claim 1, characterised in that the mineral acid belongs to the group consisting of sulphuric and phosphoric acids and mixtures thereof.
- Process according to claim 1, characterised in that anodisation is carried out in an alternating current.
- Proces according to claim 1, characterised in that rinsing is carried out at a temperature of between 70 and 80°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88420391T ATE83511T1 (en) | 1987-11-23 | 1988-11-21 | PROCESS FOR THE CONTINUOUS ANODISING OF ALUMINUM OR ALUMINUM ALLOYS STRIPS TO BE COATED WITH ORGANIC PRODUCTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8716674 | 1987-11-23 | ||
| FR8716674A FR2623526B1 (en) | 1987-11-23 | 1987-11-23 | PROCESS OF CONTINUOUS ANODIZATION OF ALUMINUM STRIPS OR ONE OF ITS ALLOYS TO BE COATED WITH AN ORGANIC PRODUCT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0318403A1 EP0318403A1 (en) | 1989-05-31 |
| EP0318403B1 true EP0318403B1 (en) | 1992-12-16 |
Family
ID=9357361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88420391A Expired - Lifetime EP0318403B1 (en) | 1987-11-23 | 1988-11-21 | Process for continuously anodising strips of aluminium or its alloys which are to be provided with an organic coating |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0318403B1 (en) |
| AT (1) | ATE83511T1 (en) |
| DE (1) | DE3876763T2 (en) |
| ES (1) | ES2035943T3 (en) |
| FR (1) | FR2623526B1 (en) |
| GR (1) | GR3006569T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH685300A5 (en) * | 1992-08-05 | 1995-05-31 | Alusuisse Lonza Services Ag | Process for the pretreatment of materials made from metals or metal alloys. |
| FR3044329A1 (en) * | 2015-11-27 | 2017-06-02 | Constellium Neuf-Brisach | METHOD FOR ELECTROLYTIC DEPOSITION OF AN ALTERNATING CURRENT CONVERSION LAYER |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3524799A (en) * | 1969-06-13 | 1970-08-18 | Reynolds Metals Co | Anodizing aluminum |
-
1987
- 1987-11-23 FR FR8716674A patent/FR2623526B1/en not_active Expired - Fee Related
-
1988
- 1988-11-21 AT AT88420391T patent/ATE83511T1/en not_active IP Right Cessation
- 1988-11-21 ES ES198888420391T patent/ES2035943T3/en not_active Expired - Lifetime
- 1988-11-21 DE DE8888420391T patent/DE3876763T2/en not_active Expired - Fee Related
- 1988-11-21 EP EP88420391A patent/EP0318403B1/en not_active Expired - Lifetime
-
1992
- 1992-12-17 GR GR920402890T patent/GR3006569T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR3006569T3 (en) | 1993-06-30 |
| ES2035943T3 (en) | 1993-05-01 |
| DE3876763T2 (en) | 1993-06-09 |
| DE3876763D1 (en) | 1993-01-28 |
| ATE83511T1 (en) | 1993-01-15 |
| FR2623526A1 (en) | 1989-05-26 |
| FR2623526B1 (en) | 1990-02-23 |
| EP0318403A1 (en) | 1989-05-31 |
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