EP3126542B1 - Two-stage pre-treatment of aluminum comprising pickling and passivation - Google Patents
Two-stage pre-treatment of aluminum comprising pickling and passivation Download PDFInfo
- Publication number
- EP3126542B1 EP3126542B1 EP15712948.7A EP15712948A EP3126542B1 EP 3126542 B1 EP3126542 B1 EP 3126542B1 EP 15712948 A EP15712948 A EP 15712948A EP 3126542 B1 EP3126542 B1 EP 3126542B1
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- Prior art keywords
- pickling solution
- mmol
- pickling
- points
- solution
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- 238000005554 pickling Methods 0.000 title claims description 56
- 229910052782 aluminium Inorganic materials 0.000 title claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 21
- 238000002203 pretreatment Methods 0.000 title claims description 5
- 238000002161 passivation Methods 0.000 title description 40
- 238000000034 method Methods 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000007591 painting process Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000005233 alkylalcohol group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 235000021110 pickles Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/76—Applying the liquid by spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
- C23G5/02861—Oxygen-containing compounds
- C23G5/02864—Alcohols
Definitions
- the present invention relates to a process for the corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating.
- the passivation of the pretreatment stage involves contacting the components with an acidic aqueous composition based on water-soluble compounds of the elements Zr and / or Ti. Pickling and passivation are coordinated in such a way that a subsequent addition of active components of the passivation solution to substantial parts from the Pickling solution can be done.
- the prior art discloses a multiplicity of pretreatment methods of aluminum-made components, in particular of strip materials, for imparting corrosion protection and as a paint primer based on acidic compositions.
- the aluminum surface is freed in a first step by the natural or caused by the manufacturing process oxide layer by pickling or pickling.
- the pickling not only involves the removal of the oxide layer, but typically includes pickling of the aluminum-made component itself to provide a homogeneous reproducible metallic surface for subsequent passivation.
- pickling not only involves the removal of the oxide layer, but typically includes pickling of the aluminum-made component itself to provide a homogeneous reproducible metallic surface for subsequent passivation.
- the international publication WO 00/68458 A1 describes for the pretreatment of aluminum-made components suitable three-stage process consisting of acidic pickling, a sink and an acidic passivation based on the elements Zr and / or Ti, wherein the sink between pickle and passivation preferably consists of several rinsing steps, within which the rinse water cascade is guided against the transport direction of the component.
- the object of the present invention is now to optimize the pre-treatment stage for aluminum-made components in subsequent painting with respect to the procedural measures to maintain a satisfactory result of the pretreatment in the continuous operation of such a pretreatment stage and beyond the complexity of Reduce pretreatment level.
- This object is achieved in a method for corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating in that the component in the pretreatment stage first with an aqueous pickling solution having a pH of 1 to 3, a free acidity in points of at least 8 and a total fluoride content of at least 40 mmol / L, and then with an aqueous passivating solution having a pH of 1 to 3, a free acid content in points below 8 and a total fluoride content of less as 60 mmol / L, but at least 5 mmol / L and less than 10 mmol / L, but at least 0.1 mmol / L of water-soluble compounds of the elements Zr and / or Ti based on the respective element contains, is brought into contact wherein, in the pretreatment stage, immediately after contacting with the pickling solution, contacting with the passivation oil Solution takes place.
- Components made of aluminum which are treated in accordance with the present invention to be corrosion-protective, are those whose surfaces formed by metallic substrates are at least 80%, preferably at least 90%, more preferably at least 95%, surfaces of the substrate aluminum and / or its alloys in which alloys of the metal aluminum according to the invention consist of more than 50 at.% of the element aluminum. It is furthermore preferred that the surfaces of the substrate aluminum do not contain a conversion layer with a layer weight of more than 10 mg / m.sup.2 relative to such foreign elements whose constituent in the substrate aluminum is below 1 at.%.
- Suitable components made of aluminum in the method according to the invention are selected, for example, from semi-finished products such as sheet metal, strip, coil or wire or from complex three-dimensional production objects, which in turn are formed from strip material or sheets and / or are assembled or produced by die-casting.
- a pretreatment step in the context of the present invention is a process step separate from the application of the paint finish comprising the process steps of pickling and passivation, which are separated in time, with the aid of liquid compositions in the form of pickling and / or pickling respectively independently stored in system tanks. the passivation solution.
- the components made of aluminum are pretreated in series in the pretreatment stage of the process according to the invention.
- pretreatment in series according to the invention is the in-Lontakt Bring a variety of aluminum-made components with each pickled in a system tank pickling and Passivi mecanicswished without after each pretreatment of a single aluminum-made component, a complete replacement with new approach of stocked in the system tanks of the pretreatment stage pickling and passivation takes place.
- the transition of the component from the stain to the passivation takes place "directly". According to the invention, this means that the passivation of the pickle follows, without any wetting of the component with another liquid composition, which is not a passivation solution in the sense of the present invention, interposed. Moreover, in a preferred process according to the invention between pickling and passivation, no such process step takes place in which the provision and use of technical means is intended to dry or remove the aqueous liquid film adhering to the surface of the component, in particular by supplying thermal energy an air flow or by mechanical stripping of the liquid film. In a particularly preferred process according to the invention, the passivation immediately following the pickle is carried out "wet-on-wet", i. in such a way that a wet film adhering to the surface of the component of a liquid composition, which constitutes a pickling solution in the sense of the present invention, is transferred into the passivation solution of the pretreatment stage.
- the ratio of per minute pretreated surface of aluminum-made non-exhaustive components in square meters to vorratetem volume of passivation in cubic meters at least 10, particularly preferred at least 50.
- Non-constituent components are characterized in that they do not transfer more than 1 liter of the pickling solution per square meter of the pickled component surface into the passivation solution, for example flat products such as strips, sheets or wires.
- the free acid content in points is determined in the context of the present invention by diluting 10 ml of the pickling solution to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of milliliters of caustic soda indicates the score.
- the stain has a free acid content of at least 12 points, so that a pickling removal which is largely independent of the type of aluminum material to be treated and sufficient for the subsequent passivation is ensured, for example in the series treatment of each of different aluminum materials Individual components or in the series treatment of individual components made from a mix of different aluminum materials.
- the free acid content in points should preferably not be greater than 16, in order to be able to keep the metal salt load in the pickling still at a moderate level with procedurally acceptable expense.
- the presence of a certain buffer capacity or a certain acidity has proven to be a stable process control in the series treatment.
- the total acid content of importance and this is in the pickling solution of the method according to the invention preferably at least 15 points, but preferably not more than 20 points.
- the total acid content is inventively determined analogously to the free acid with the difference that is titrated to a pH of 8.5.
- the pickling solution preferably has a pH below 2.0 in a process according to the invention. Even then it is regularly ensured that a sufficient stain can take place in the pretreatment stage.
- a further prerequisite for a sufficient pickling effect of the components made of aluminum in the pickling solution of the pretreatment stage of the process according to the invention is the presence of fluorides which, as complexing agents for aluminum ions, on the one hand stain oxidic cover layers and, on the other hand, the high load of aluminum ions in the Stabilize pickling solution.
- the total fluoride content in the pickling solution is at least 60 mmol / L.
- the total fluoride content is determined in the context of the present invention by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1.
- the pickling solution in order to comply with this requirement profile in a preferred process according to the invention has to contain at least 7 mmol / L of water-soluble compounds of the elements Zr and / or Ti relative to the respective element in order to reduce the carryover for the replacement of the the passivation solution used to be able to significantly use shares of these components.
- the proportion of these components in the pickling solution should not exceed values for which a conversion layer formation based on the elements Zr and / or Ti is possible.
- the molar ratio of the total proportion of water-soluble compounds of the elements Zr and / or Ti relative to the respective elements to the total fluoride content in the Pickling solution is less than 0.1.
- Particularly suitable nonionic surfactants are selected from alkoxylated alkyl alcohols, alkoxylated fatty amines and / or alkylpolyglycosides, particularly preferably from alkoxylated alkyl alcohols and / or alkoxylated fatty amines, particularly preferably from alkoxylated alkyl alcohols.
- the alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferably end-capped, more preferably having an alkyl group which in turn preferably has not more than 8 carbon atoms, more preferably not more than 4 carbon atoms.
- the pickling solution in the process according to the invention is preferably set such that for the wrought alloy EN AW-6060 (AlMgSi0.5) at 40 ° C. in an unstirred pickling solution of the process according to the invention a pickling rate of at least 15 mgm -2 s -1 based on the element aluminum results.
- a conversion layer based on the elements Zr and / or Ti is applied in the method according to the invention.
- RFA X-ray fluorescence analysis
- the molar ratio of the total proportion of water-soluble compounds of the elements Zr and / or Ti relative to the respective elements to the total fluoride content in the passivation solution at least 0.1, more preferably at least 0.4.
- the pH of the passivation solution in the pretreatment stage is at least 1.8, more preferably at least 2.0.
- the passivation solution therefore contains a total of less than 10 ppm of water-soluble compounds of the element chromium calculated as Cr.
- the application of the pickling and passivating solution stored in the respective system tanks of the pretreatment stage can be carried out using all methods known in the prior art, with immersion and spraying methods for contacting the components made of aluminum with these solutions being particularly preferred is the spray method as application mode.
- the coating following the pretreatment stage comprises the application of a composition comprising a chemically or physically hardening binder to form a cover layer on the pretreated and made of aluminum component, wherein the coating layer resulting from the coating in the dried or cured state, a layer thickness of preferably at least one micrometer , particularly preferably of at least 10 .mu.m, measured according to the wedge-cut method according to DIN 50986: 1979-03.
- Suitable lacquers are autophoretic lacquers, electrodeposition lacquers, powder lacquers and liquid lacquers which can be applied by conventional means.
- paints based on inorganic binders such as, for example, silicate or lime
- paints based on organic binders can be used according to the invention.
- the following application of lacquers based on organic binders, especially those which are particularly advantageous, is particularly advantageous contain less than 10 wt .-% of organic solvent constituents which have a boiling point below 150 ° C at 1 bar.
- powder coatings are preferred, in particular those with binders based on epoxy resins, carboxyl- and hydroxyl-containing polyester resins and / or acrylate resins, each having an excellent paint adhesion to the pretreated according to the invention made of aluminum components.
- the component made of aluminum can be subjected after pretreatment and before painting to a sink, which serves to remove a wet film of the passivation solution adhering to the surface before the paint is applied. Furthermore, it is customary that the component is dried before the application of the paint. This is especially the case when a powder coating is to be applied.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur korrosionsschützenden Behandlung von aus Aluminium gefertigten Bauteilen umfassend eine Vorbehandlungsstufe und eine nachfolgende Lackierung. Die Passivierung der Vorbehandlungsstufe beinhaltet das In-Kontakt-Bringen der Bauteile mit einer sauren wässrigen Zusammensetzung auf Basis wasserlöslicher Verbindungen der Elemente Zr und/oder Ti. Beize und Passivierung sind derart aufeinander abgestimmt, dass eine Nachdosierung von Aktivkomponenten der Passivierungslösung zu wesentlichen Teilen aus der Beizlösung erfolgen kann.The present invention relates to a process for the corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating. The passivation of the pretreatment stage involves contacting the components with an acidic aqueous composition based on water-soluble compounds of the elements Zr and / or Ti. Pickling and passivation are coordinated in such a way that a subsequent addition of active components of the passivation solution to substantial parts from the Pickling solution can be done.
Im Stand der Technik ist eine Vielzahl an Vorbehandlungsverfahren von aus Aluminium gefertigten Bauteilen, insbesondere von Bandmaterialien, zur Vermittlung eines Korrosionsschutzes und als Lackhaftgrund bekannt, die auf sauren Zusammensetzungen basieren. Üblicherweise wird dabei die Aluminiumoberfläche in einem ersten Schritt von der natürlichen oder durch den Fertigungsprozess bedingten Oxidschicht durch Beizen bzw. Dekapieren befreit. Das Beizen umfasst nicht lediglich die Entfernung der Oxidschicht, sondern schließt üblicherweise auch das Beizen des aus Aluminium gefertigten Bauteils selbst ein, um eine homogene reproduzierbare metallische Oberfläche für eine nachfolgende Passivierung bereitzustellen. In jüngerer Zeit werden verstärkt Vorbehandlungen in der industriellen Serienfertigung von aus Aluminium gefertigten Bauteilen nachgefragt, in denen für eine verbesserte Umweltverträglichkeit und Nachhaltigkeit gänzlich auf den Einsatz von Verbindungen des Elements Chrom verzichtet werden kann.The prior art discloses a multiplicity of pretreatment methods of aluminum-made components, in particular of strip materials, for imparting corrosion protection and as a paint primer based on acidic compositions. Usually, the aluminum surface is freed in a first step by the natural or caused by the manufacturing process oxide layer by pickling or pickling. The pickling not only involves the removal of the oxide layer, but typically includes pickling of the aluminum-made component itself to provide a homogeneous reproducible metallic surface for subsequent passivation. More recently, there has been a growing demand for pretreatments in the industrial mass production of components made of aluminum, in which the use of compounds of the element chromium can be completely dispensed with for improved environmental compatibility and sustainability.
Die internationale Offenlegungsschrift
Ausgehend von diesem Stand der Technik besteht die Aufgabe der vorliegenden Erfindung nun darin, die Vorbehandlungsstufe für aus Aluminium gefertigte Bauteile bei nachfolgender Lackierung hinsichtlich der verfahrenstechnischen Maßnahmen zur Aufrechterhaltung eines zufriedenstellenden Ergebnisses der Vorbehandlung im kontinuierlichen Betrieb einer solchen Vorbehandlungsstufe zu optimieren und darüber hinaus die Komplexität der Vorbehandlungsstufe zu reduzieren.Based on this prior art, the object of the present invention is now to optimize the pre-treatment stage for aluminum-made components in subsequent painting with respect to the procedural measures to maintain a satisfactory result of the pretreatment in the continuous operation of such a pretreatment stage and beyond the complexity of Reduce pretreatment level.
Diese Aufgabe wird in einem Verfahren zur korrosionsschützenden Behandlung von aus Aluminium gefertigten Bauteilen umfassend eine Vorbehandlungsstufe und eine nachfolgende Lackierung dadurch gelöst, dass das das Bauteil in der Vorbehandlungsstufe zunächst mit einer wässrigen Beizlösung, die einen pH-Wert von 1 bis 3, einen freien Säuregehalt in Punkten von zumindest 8 und einen Gesamtfluorid-Gehalt von zumindest 40 mmol/L aufweist, und anschließend mit einer wässrigen Passivierungslösung, die einen pH-Wert von 1 bis 3, einen freien Säuregehalt in Punkten unterhalb von 8 und einen Gesamtfluorid-Gehalt von weniger als 60 mmol/L, aber zumindest 5 mmol/L aufweist und weniger als 10 mmol/L, aber zumindest 0,1 mmol/L an wasserlöslichen Verbindungen der Elemente Zr und/oder Ti bezogen auf das jeweilige Element enthält, in Kontakt gebracht wird, wobei in der Vorbehandlungsstufe unmittelbar nach dem In-Kontakt-Bringen mit der Beizlösung das In-Kontakt-Bringen mit der Passivierungslösung erfolgt.This object is achieved in a method for corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating in that the component in the pretreatment stage first with an aqueous pickling solution having a pH of 1 to 3, a free acidity in points of at least 8 and a total fluoride content of at least 40 mmol / L, and then with an aqueous passivating solution having a pH of 1 to 3, a free acid content in points below 8 and a total fluoride content of less as 60 mmol / L, but at least 5 mmol / L and less than 10 mmol / L, but at least 0.1 mmol / L of water-soluble compounds of the elements Zr and / or Ti based on the respective element contains, is brought into contact wherein, in the pretreatment stage, immediately after contacting with the pickling solution, contacting with the passivation oil Solution takes place.
Aus Aluminium gefertigte Bauteile, die gemäß der vorliegenden Erfindung korrosionsschützend behandelt werden, sind solche, deren von metallischen Substraten gebildete Oberfläche zu zumindest 80%, vorzugsweise zu zumindest 90%, besonders bevorzugt zu zumindest 95% Oberflächen des Substrats Aluminium und/oder seiner Legierungen sind, wobei Legierungen des Metalls Aluminium erfindungsgemäß zu mehr als 50 At.-% aus dem Element Aluminium bestehen. Weiterhin bevorzugt ist, dass die Oberflächen des Substrats Aluminium keine Konversionsschicht mit einem Schichtgewicht von mehr als 10 mg/m2 bezogen auf solche Fremdelemente enthält, deren Bestandteil im Substrat Aluminium unterhalb von 1 At.-% liegt.Components made of aluminum, which are treated in accordance with the present invention to be corrosion-protective, are those whose surfaces formed by metallic substrates are at least 80%, preferably at least 90%, more preferably at least 95%, surfaces of the substrate aluminum and / or its alloys in which alloys of the metal aluminum according to the invention consist of more than 50 at.% of the element aluminum. It is furthermore preferred that the surfaces of the substrate aluminum do not contain a conversion layer with a layer weight of more than 10 mg / m.sup.2 relative to such foreign elements whose constituent in the substrate aluminum is below 1 at.%.
Im erfindungsgemäßen Verfahren geeignete aus Aluminium gefertigte Bauteile sind beispielsweise ausgewählt aus Halbzeugen wie Blech, Band, Coil oder Draht oder aus komplexen dreidimensionalen Fertigungsobjekten, die wiederum aus Bandmaterial oder Blechen geformt und/oder zusammengefügt sind oder im Druckgussverfahren hergestellt wurden.Suitable components made of aluminum in the method according to the invention are selected, for example, from semi-finished products such as sheet metal, strip, coil or wire or from complex three-dimensional production objects, which in turn are formed from strip material or sheets and / or are assembled or produced by die-casting.
Eine Vorbehandlungsstufe im Sinne der vorliegenden Erfindung ist eine von der Aufbringung der Lackierung getrennte Verfahrensstufe umfassend die voneinander zeitlich getrennten Verfahrensschritte Beize und Passivierung unter Zuhilfenahme von jeweils unabhängig voneinander in Systemtanks bevorrateten flüssigen Zusammensetzungen in Form der Beiz-bzw. der Passivierungslösung. In einer bevorzugten Ausführungsform werden die aus Aluminium gefertigten Bauteile in der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens in Serie vorbehandelt. Als Vorbehandlung in Serie gilt erfindungsgemäß das In-Lontakt-Bringen einer Vielzahl von aus Aluminium gefertigten Bauteilen mit der jeweils in einem Systemtank bevorrateten Beiz- und Passivierungslösung, ohne dass nach jeder Vorbehandlung eines einzelnen aus Aluminium gefertigten Bauteils ein vollständiger Austausch mit Neuansatz der in den Systemtanks der Vorbehandlungsstufe bevorrateten Beiz- und Passivierungslösungen erfolgt.A pretreatment step in the context of the present invention is a process step separate from the application of the paint finish comprising the process steps of pickling and passivation, which are separated in time, with the aid of liquid compositions in the form of pickling and / or pickling respectively independently stored in system tanks. the passivation solution. In a preferred embodiment, the components made of aluminum are pretreated in series in the pretreatment stage of the process according to the invention. As pretreatment in series according to the invention is the in-Lontakt Bring a variety of aluminum-made components with each pickled in a system tank pickling and Passivierungslösung without after each pretreatment of a single aluminum-made component, a complete replacement with new approach of stocked in the system tanks of the pretreatment stage pickling and passivation takes place.
Der Übergang des Bauteils von der Beize in die Passivierung erfolgt "unmittelbar". Erfindungsgemäß bedeutet dies, dass die Passivierung der Beize nachfolgt, ohne dass eine Benetzung des Bauteils mit einer anderen flüssigen Zusammensetzung, die keine Passivierungslösung im Sinne der vorliegenden Erfindung darstellt, zwischengeschaltet ist. Zudem findet in einem bevorzugten erfindungsgemäßen Verfahren zwischen Beize und Passivierung kein solcher Verfahrensschritt statt, bei dem durch die Bereitstellung und Nutzung technischer Mittel eine Trocknung oder eine Entfernung des wässrigen, auf der Oberfläche des Bauteils anhaftenden Flüssigfilms beabsichtigt ist, insbesondere durch Zuführung thermischer Energie, Aufprägen einer Luftströmung oder durch mechanisches Abstreifen des Flüssigfilms. In einem besonders bevorzugten erfindungsgemäßen Verfahren erfolgt die der Beize unmittelbar nachfolgende Passivierung "nass-in-nass", d.h. derart, dass ein auf der Oberfläche des Bauteils anhaftender Nassfilm einer flüssigen Zusammensetzung, die eine Beizlösung im Sinne der vorliegenden Erfindung darstellt, mit in die Passivierungslösung der Vorbehandlungsstufe überführt wird.The transition of the component from the stain to the passivation takes place "directly". According to the invention, this means that the passivation of the pickle follows, without any wetting of the component with another liquid composition, which is not a passivation solution in the sense of the present invention, interposed. Moreover, in a preferred process according to the invention between pickling and passivation, no such process step takes place in which the provision and use of technical means is intended to dry or remove the aqueous liquid film adhering to the surface of the component, in particular by supplying thermal energy an air flow or by mechanical stripping of the liquid film. In a particularly preferred process according to the invention, the passivation immediately following the pickle is carried out "wet-on-wet", i. in such a way that a wet film adhering to the surface of the component of a liquid composition, which constitutes a pickling solution in the sense of the present invention, is transferred into the passivation solution of the pretreatment stage.
Im erfindungsgemäßen Verfahren ist bei einer kontinuierlichen Vorbehandlung einer Serie von aus Aluminium gefertigten Bauteilen gewährleistet, dass bei einem Nachschärfen der Beize durch Zudosierung von Säuren und Verbindungen, die eine Quelle für Fluorid-Ionen darstellen, in der unmittelbar nachfolgenden Passivierungsstufe im Wesentlichen lediglich wasserlösliche Verbindungen der Elemente Zr und/oder Ti hinzudosiert werden müssen. Allein die Überschleppung von Aktivkomponenten aus der Beizlösung durch den unvermeidlich am Bauteil anhaftenden Nassfilm bewirkt, dass die gleichen Aktivkomponenten in der Passivierungslösung, die dort sowohl verbraucht als auch ausgeschleppt werden, zumindest teilweise ersetzt werden, ohne dass gleichzeitig signifikante Nachteile hinsichtlich des Vorbehandlungsergebnisses durch die Überschleppung von aus dem Beizprozess stammenden Aluminiumsalzen in die Passivierungslösung resultieren bzw. in Kauf genommen werden. Für eine effektive Nutzung der Überschleppung zum Ausgleich der in der Passivierung verbrauchten Aktivkomponenten ist es vorteilhaft, wenn das Verhältnis von pro Minute vorbehandelter Oberfläche von aus Aluminium gefertigten nichtschöpfenden Bauteilen in Quadratmetern zum bevorratetem Volumen an Passivierungslösung in Kubikmetern zumindest 10, besonders bevorzugt zumindest 50 beträgt. Nichtschöpfende Bauteile sind dadurch gekennzeichnet, dass sie nicht mehr als 1 Liter der Beizlösung pro Quadratmeter der gebeizten Bauteiloberfläche in die Passivierungslösung überschleppen, beispielsweise Flacherzeugnisse wie Bänder, Bleche oder Drähte.In the method according to the invention is ensured in a continuous pretreatment of a series of aluminum-made components that in a resharpening of the stain by addition of acids and compounds which are a source of fluoride ions, in the immediately following passivation step essentially only water-soluble compounds of Elements Zr and / or Ti must be added. The mere entrainment of active components from the pickling solution by the wet film inevitably adheres to the component causes the same active components in the passivation solution, which are both consumed and removed, to be at least partially replaced, without at the same time having significant disadvantages in terms of the pretreatment result due to the carryover resulting from the pickling aluminum salts in the passivation result or be accepted. For effective utilization of the carry-over to compensate for the consumed in the passivation active components, it is advantageous if the ratio of per minute pretreated surface of aluminum-made non-exhaustive components in square meters to vorratetem volume of passivation in cubic meters at least 10, particularly preferred at least 50. Non-constituent components are characterized in that they do not transfer more than 1 liter of the pickling solution per square meter of the pickled component surface into the passivation solution, for example flat products such as strips, sheets or wires.
Der freie Säuregehalt in Punkten wird im Rahmen der vorliegenden Erfindung bestimmt, indem man 10 ml der Beizlösung auf 50 ml verdünnt und mit 0,1 N Natronlauge bis zu einem pH-Wert von 3,6 titriert. Der Verbrauch an Millilitern Natronlauge gibt die Punktzahl an. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens weist die Beize einen freien Säuregehalt von zumindest 12 Punkten auf, so dass eine von der Art des zu behandelnden Aluminiummaterials weitestgehend unabhängige und für die nachfolgende Passivierung hinreichenden Beizabtrag sicherzustellen, beispielsweise in der Serienbehandlung von jeweils aus unterschiedlichen Aluminiummaterialien gefertigten Einzelbauteilen oder in der Serienbehandlung von aus einem Mix unterschiedlicher Aluminiummaterialien gefertigter Einzelbauteile. Umgekehrt sollte der freie Säuregehalt in Punkten vorzugsweise nicht größer als 16 sein, um die Metallsalzfracht in der Beize noch mit verfahrenstechnisch akzeptablen Aufwand auf einem moderaten Niveau halten zu können.The free acid content in points is determined in the context of the present invention by diluting 10 ml of the pickling solution to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of milliliters of caustic soda indicates the score. In a preferred embodiment of the process according to the invention, the stain has a free acid content of at least 12 points, so that a pickling removal which is largely independent of the type of aluminum material to be treated and sufficient for the subsequent passivation is ensured, for example in the series treatment of each of different aluminum materials Individual components or in the series treatment of individual components made from a mix of different aluminum materials. Conversely, the free acid content in points should preferably not be greater than 16, in order to be able to keep the metal salt load in the pickling still at a moderate level with procedurally acceptable expense.
Neben der Einstellung eines freien Säuregehalts in der Beizlösung als Regelungsparameter für die Bereitstellung von im erfindungsgemäßen Verfahren optimal gebeizten Oberflächen der aus Aluminium gefertigten Bauteile, hat sich das Vorliegen einer gewissen Pufferkapazität oder eines gewissen Säurevorrats für eine stabile Prozessführung bei der Serienbehandlung herausgestellt. Hierfür ist der Gesamtsäuregehalt von Bedeutung und dieser liegt in der Beizlösung des erfindungsgemäßen Verfahrens vorzugsweise bei zumindest 15 Punkten, jedoch vorzugsweise bei nicht mehr als 20 Punkten. Der Gesamtsäuregehalt wird erfindungsgemäß analog zur freien Säure bestimmt mit dem Unterschied, dass bis zu einem pH-Wert von 8,5 titriert wird.In addition to the setting of a free acid content in the pickling solution as a control parameter for the provision of optimally pickled in the process according to the invention surfaces of aluminum-made components, the presence of a certain buffer capacity or a certain acidity has proven to be a stable process control in the series treatment. For this purpose, the total acid content of importance and this is in the pickling solution of the method according to the invention preferably at least 15 points, but preferably not more than 20 points. The total acid content is inventively determined analogously to the free acid with the difference that is titrated to a pH of 8.5.
Die Beizlösung weist in einem erfindungsgemäßen Verfahren vorzugsweise einen pH-Wert unterhalb von 2,0 auf. Auch dann ist regelmäßig sichergestellt, dass eine hinreichende Beize in der Vorbehandlungsstufe erfolgen kann.The pickling solution preferably has a pH below 2.0 in a process according to the invention. Even then it is regularly ensured that a sufficient stain can take place in the pretreatment stage.
Bezüglich der in der Beizlösung der Vorbehandlungsstufe für die Einstellung des Säuregehaltes zu verwendenden Säure wurde festgestellt, dass Schwefelsäure zu bevorzugen ist. Dementsprechend ist in erfindungsgemäßen Verfahren die Verwendung von Beizlösungen bevorzugt, deren Gesamtsäuregehalt in Punkten zu 80%, besonders bevorzugt zu 90%, besonders bevorzugt zu 95% durch Schwefelsäure gebildet wird.With respect to the acid to be used in the pickling solution of the pretreatment step for the acidity adjustment, it has been found that sulfuric acid is preferable. Accordingly, preference is given in the process according to the invention to the use of pickling solutions whose total acid content is formed in points of 80%, particularly preferably 90%, particularly preferably 95%, by means of sulfuric acid.
Eine weitere Voraussetzung für eine hinreichende Beizwirkung der aus Aluminium gefertigten Bauteile in der Beizlösung der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens ist die Gegenwart von Fluoriden, die als Komplexbildner für Aluminium-Ionen einerseits oxidische Deckschichten besonders gut beizen und andererseits die hohe Fracht an Aluminium-Ionen in der Beizlösung stabilisieren. Hier ist es bevorzugt, wenn der Gesamtfluorid-Gehalt in der Beizlösung zumindest 60 mmol/L beträgt. Der Gesamtfluorid-Gehalt wird im Rahmen der vorliegenden Erfindung mittels einer Fluorid-Ionensensitiven Elektrode nach der DIN 38 405-D-4-1 bestimmt.A further prerequisite for a sufficient pickling effect of the components made of aluminum in the pickling solution of the pretreatment stage of the process according to the invention is the presence of fluorides which, as complexing agents for aluminum ions, on the one hand stain oxidic cover layers and, on the other hand, the high load of aluminum ions in the Stabilize pickling solution. Here it is preferred if the total fluoride content in the pickling solution is at least 60 mmol / L. The total fluoride content is determined in the context of the present invention by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1.
Überaschenderweise hat sich gezeigt, dass die Anwesenheit von in der Passivierung schichtbildenden wasserlöslichen Verbindungen der Elemente Zr und/oder Ti in der Beize nicht nachteilig ist und daher eine einfache Möglichkeit gegeben ist, die Passivierungslösung in der Vorbehandlungsstufe durch die erfindungsgemäße Verfahrweise, bei der der Übergang der vorzubehandelnden Bauteile von der Beize in die Passivierung "unmittelbar" erfolgt, durch Überschleppung aus der Beizlösung zumindest teilweise ersetzt werden können. Es ist allenfalls darauf zu achten, dass die Aktivkomponenten der Passivierung als zu überschleppende Bestandteile aus der Beizlösung in der Beize keine Schichtbildung herbeiführen. Dies wäre nachteilig für die nachfolgende Passivierung, in der die unter nicht optimalen Schichtbildungsbedingungen in der Beizlösung gebildete Konversionsschicht auf Basis der Elemente Zr und/oder Ti wieder partiell aufgelöst und neu gebildet wird und somit eine weniger effektive Passivierung der Bauteile resultiert. Es hat sich herausgestellt, dass die Beizlösung um diesem Anforderungsprofil zu entsprechen in einem bevorzugten erfindungsgemäßen Verfahren zumindest 7 mmol/L an wasserlöslichen Verbindungen der Elemente Zr und/oder Ti bezogen auf das jeweilige Element zu enthalten hat, um die Überschleppung für den Ersatz der in der Passivierungslösung verbrauchten Anteile dieser Komponenten signifikant nutzen zu können. Andererseits sollte der Anteil an diesen Komponenten in der Beizlösung keine Werte überschreiten, für die eine Konversionsschichtbildung auf Basis der Elemente Zr und/oder Ti möglich wird. Insofern ist erfindungsgemäß bevorzugt, wenn in derartigen Beizlösungen nicht mehr als 30 mmol/L an wasserlöslichen Verbindungen der Elemente Zr und/oder Ti bezogen auf das jeweilige Element enthalten sind. In diesem Zusammenhang ist zur Vermeidung einer partiellen Schichtbildung auf Basis der Elemente Zr und/oder Ti in der Beize weiterhin bevorzugt, wenn das molare Verhältnis des Gesamtanteils wasserlöslicher Verbindungen der Elemente Zr und/oder Ti bezogen auf die jeweiligen Elemente zum Gesamtfluorid-Gehalt in der Beizlösung kleiner als 0,1 ist.Surprisingly, it has been shown that the presence of passivating water-soluble compounds of the elements Zr and / or Ti in the stain is not detrimental and therefore an easy way is given, the passivation in the pretreatment step by the inventive method in which the transition the components to be pretreated from the stain into the passivation "immediately", can be at least partially replaced by Überschleppung from the pickling solution. At most, it must be ensured that the active components of the passivation as constituents to be removed from the pickling solution in the pickling do not cause any layer formation. This would be disadvantageous for the subsequent passivation, in which the conversion layer formed under non-optimal layer formation conditions in the pickling solution is again partially dissolved and newly formed on the basis of the elements Zr and / or Ti, thus resulting in less effective passivation of the components. It has been found that the pickling solution in order to comply with this requirement profile in a preferred process according to the invention has to contain at least 7 mmol / L of water-soluble compounds of the elements Zr and / or Ti relative to the respective element in order to reduce the carryover for the replacement of the the passivation solution used to be able to significantly use shares of these components. On the other hand, the proportion of these components in the pickling solution should not exceed values for which a conversion layer formation based on the elements Zr and / or Ti is possible. In this respect, it is preferred according to the invention if no more than 30 mmol / L of water-soluble compounds of the elements Zr and / or Ti are contained in such pickling solutions, based on the respective element. In this connection, in order to avoid a partial layer formation based on the elements Zr and / or Ti in the stain it is furthermore preferred if the molar ratio of the total proportion of water-soluble compounds of the elements Zr and / or Ti relative to the respective elements to the total fluoride content in the Pickling solution is less than 0.1.
In einem bevorzugten erfindungsgemäßen Verfahren enthält die Beizlösung zusätzlich eine oberflächenaktive organische Verbindung, besonders bevorzugt ein Niotensid, wobei der Anteil an oberflächenaktiven organischen Substanzen in der Beizlösung vorzugsweise zumindest 0,1 mmol/L beträgt. In diesem Zusammenhang sind allgemein solche Niotenside bevorzugt, deren HLB-Wert (Hydrophilic-Lipophilic-Balance) zumindest 8, besonders bevorzugt zumindest 10, insbesondere bevorzugt zumindest 12 ist, jedoch besonders bevorzugt nicht mehr als 18, insbesondere bevorzugt nicht mehr als 16 beträgt. Der HLB-Wert dient zur quantitativen Klassifizierung von Niotensiden entsprechend ihrer inneren molekularen Struktur, wobei eine Aufgliederung des Niotensids in eine lipophile und eine hydrophile Gruppe vorgenommen wird. Der HLB Wert kann auf der willkürlichen Skala Werte von Null bis 20 annehmen und berechnet sich gemäß vorliegender Erfindung wie folgt:
- mit ML: Molmasse der lypophilen Gruppe des Niotensids
- M: Molmasse des Niotensids
- with M L : molar mass of the nonionic surfactant lypophilic group
- M: molecular weight of the nonionic surfactant
Insbesonders geeignete Niotenside sind ausgewählt aus alkoxylierten Alkylalkoholen, alkoxylierten Fettaminen und/oder Alkylpolyglycosiden, besonders bevorzugt aus alkoxylierten Alkylalkoholen und/oder alkoxylierten Fettaminen, insbesondere bevorzugt aus alkoxylierten Alkylalkoholen. Die alkoxylierten Alkylalkohole und/oder alkoxylierten Fettamine sind dabei vorzugsweise endgruppenverschlossen, besonders bevorzugt mit einer AlkylGruppe, die wiederum vorzugsweise nicht mehr als 8 Kohlenstoffatome, besonders bevorzugt nicht mehr als 4 Kohlenstoffatome aufweist.Particularly suitable nonionic surfactants are selected from alkoxylated alkyl alcohols, alkoxylated fatty amines and / or alkylpolyglycosides, particularly preferably from alkoxylated alkyl alcohols and / or alkoxylated fatty amines, particularly preferably from alkoxylated alkyl alcohols. The alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferably end-capped, more preferably having an alkyl group which in turn preferably has not more than 8 carbon atoms, more preferably not more than 4 carbon atoms.
Die Beizlösung im erfindungsgemäßen Verfahren ist vorzugsweise derart eingestellt, dass für die Knetlegierung EN AW- 6060 (AlMgSi0,5) bei 40 °C in einer ungerührten Beizlösung des erfindungsgemäßen Verfahrens eine Beizrate von zumindest 15 mgm-2s-1 bezogen auf das Element Aluminium resultiert.The pickling solution in the process according to the invention is preferably set such that for the wrought alloy EN AW-6060 (AlMgSi0.5) at 40 ° C. in an unstirred pickling solution of the process according to the invention a pickling rate of at least 15 mgm -2 s -1 based on the element aluminum results.
In der der Beize unmittelbar nachfolgenden Passivierung wird im erfindungsgemäßen Verfahren eine Konversionsschicht auf Basis der Elemente Zr und/oder Ti aufgebracht. Für eine hinreichende Passivierung ist bevorzugt, wenn nach der Passivierung eine Schichtauflage von zumindest 5 mg/m2, vorzugsweise zumindest 10 mg/m2, besonders bevorzugt zumindest 20 mg/m2, jedoch vorzugsweise von nicht mehr als 50 mg/2 bestimmt mittels Röntgenfluoreszenzanalyse (RFA) resultiert. Hierfür ist weiterhin bevorzugt, das in der Passivierungslösung des erfindungsgemäßen Verfahrens zumindest 0,5 mmol/L, besonders bevorzugt zumindest 1 mmol/L an wasserlöslichen Verbindungen der Elemente Zr und/oder Ti bezogen auf das jeweilige Element enthalten sind. In diesem Zusammenhang ist für eine effektive Schichtbildung auf Basis der Elemente Zr und/oder Ti in der Passivierung weiterhin bevorzugt, wenn das molare Verhältnis des Gesamtanteils wasserlöslicher Verbindungen der Elemente Zr und/oder Ti bezogen auf die jeweiligen Elemente zum Gesamtfluorid-Gehalt in der Passivierungslösung zumindest 0,1, besonders bevorzugt zumindest 0,4 beträgt.In the passivation immediately following the pickle, a conversion layer based on the elements Zr and / or Ti is applied in the method according to the invention. For a sufficient passivation is preferred if after passivation, a layer of at least 5 mg / m 2 , preferably at least 10 mg / m 2 , more preferably at least 20 mg / m 2 , but preferably determined by not more than 50 mg / 2 X-ray fluorescence analysis (RFA) results. For this purpose, it is further preferred that in the passivation solution of the method according to the invention at least 0.5 mmol / L, more preferably at least 1 mmol / L of water-soluble compounds of the elements Zr and / or Ti are contained based on the respective element. In this connection, for an effective layer formation based on the elements Zr and / or Ti in the passivation it is furthermore preferred if the molar ratio of the total proportion of water-soluble compounds of the elements Zr and / or Ti relative to the respective elements to the total fluoride content in the passivation solution at least 0.1, more preferably at least 0.4.
In einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens liegt der pH-Wert der Passivierungslösung in der Vorbehandlungsstufe bei zumindest 1,8, besonders bevorzugt bei zumindest 2,0.In a preferred embodiment of the method according to the invention, the pH of the passivation solution in the pretreatment stage is at least 1.8, more preferably at least 2.0.
Für eine hinreichende Passivierung in der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens bedarf es nicht der Anwesenheit von wasserlöslichen Verbindungen des Elements Chrom. In einer weiteren bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens enthält die Passivierungslösung daher insgesamt weniger als 10 ppm an wasserlöslichen Verbindungen des Elements Chroms berechnet als Cr.For a sufficient passivation in the pretreatment stage of the process according to the invention does not require the presence of water-soluble compounds of the element chromium. In a further preferred embodiment of the method according to the invention, the passivation solution therefore contains a total of less than 10 ppm of water-soluble compounds of the element chromium calculated as Cr.
Die Applikation der in den jeweiligen Systemtanks der Vorbehandlungsstufe bevorrateten Beiz- und Passivierungslösung kann mit allen im Stand der Technik bekannten Verfahren erfolgen, wobei Tauch- und Sprühverfahren für das In-Kontakt-Bringen der aus Aluminium gefertigten Bauteile mit diesen Lösungen bevorzugt sind, besonders bevorzugt ist das Sprühverfahren als Applikationsart.The application of the pickling and passivating solution stored in the respective system tanks of the pretreatment stage can be carried out using all methods known in the prior art, with immersion and spraying methods for contacting the components made of aluminum with these solutions being particularly preferred is the spray method as application mode.
Die der Vorbehandlungsstufe nachfolgende Lackierung beinhaltet erfindungsgemäß die Aufbringung einer Zusammensetzung enthaltend ein chemisch oder physikalisch aushärtendes Bindemittel zur Ausbildung einer Deckschicht auf dem vorbehandeltem und aus Aluminium gefertigtem Bauteil, wobei die aus der Lackierung resultierende Deckschicht im getrockneten oder ausgehärteten Zustand eine Schichtdicke von vorzugsweise zumindest einem Mikrometer, besonders bevorzugt von zumindest 10 µm, gemessen gemäß Keilschnittverfahren nach der DIN 50986:1979-03 aufweist.According to the invention, the coating following the pretreatment stage comprises the application of a composition comprising a chemically or physically hardening binder to form a cover layer on the pretreated and made of aluminum component, wherein the coating layer resulting from the coating in the dried or cured state, a layer thickness of preferably at least one micrometer , particularly preferably of at least 10 .mu.m, measured according to the wedge-cut method according to DIN 50986: 1979-03.
Geeignete Lacke sind autophorethische Lacke, Elektrotauchlacke, Pulverlacke sowie mit konventionellen Mitteln applizierbare Flüssiglacke. Hinsichtlich der verwendeten Bindemittel können erfindungsgemäß sowohl Lacke, die auf anorganischen Bindemitteln wie beispielsweise Silkat oder Kalk basieren, als auch Lacke basierend auf organischen Bindemittel eingesetzt werden. Besonders vorteilhaft ist erfindungsgemäß die nachfolgende Auftragung von auf organischen Bindemitteln basierten Lacken, insbesondere solchen, die weniger als 10 Gew.-% an organischen Lösemittelbestandteilen enthalten, die einem Siedepunkt unterhalb von 150 °C bei 1 bar aufweisen. In diesem Zusammenhang sind daher Pulverlacke bevorzugt, insbesondere solche mit Bindemitteln auf Basis von Epoxidharzen, carboxy- und hydroxygruppenhaltige Polyesterharzen und/oder Acrylatharzen, die jeweils eine hervorragende Lackhaftung auf den entsprechend der Erfindung vorbehandelten aus Aluminium gefertigten Bauteilen aufweisen.Suitable lacquers are autophoretic lacquers, electrodeposition lacquers, powder lacquers and liquid lacquers which can be applied by conventional means. With regard to the binders used, both paints based on inorganic binders, such as, for example, silicate or lime, and paints based on organic binders can be used according to the invention. According to the invention, the following application of lacquers based on organic binders, especially those which are particularly advantageous, is particularly advantageous contain less than 10 wt .-% of organic solvent constituents which have a boiling point below 150 ° C at 1 bar. In this context, therefore, powder coatings are preferred, in particular those with binders based on epoxy resins, carboxyl- and hydroxyl-containing polyester resins and / or acrylate resins, each having an excellent paint adhesion to the pretreated according to the invention made of aluminum components.
Das aus Aluminium gefertigte Bauteil kann nach der Vorbehandlung und vor der Lackierung einer Spüle unterworfen werden, die dazu dient, einen auf der Oberfläche anhaftenden Nassfilm der Passivierungslösung zu entfernen bevor der Lack aufgetragen wird. Ferner ist es üblich, dass das Bauteil vor der Auftragung des Lackes getrocknet wird. Dies ist insbesondere dann der Fall, wenn ein Pulverlack aufzutragen ist.The component made of aluminum can be subjected after pretreatment and before painting to a sink, which serves to remove a wet film of the passivation solution adhering to the surface before the paint is applied. Furthermore, it is customary that the component is dried before the application of the paint. This is especially the case when a powder coating is to be applied.
Claims (11)
- A method for anti-corrosion treatment of components produced from aluminum, comprising a pretreatment stage and a subsequent painting process, in which the component in the pretreatment stage is brought into contact first with an aqueous pickling solution, which has a pH of from 1 to 3, a free acid content of at least 8 points and a total fluoride content of at least 40 mmol/L, and subsequently with an aqueous passivating solution, which has a pH of from 1 to 3, a free acid content of less than 8 points and a total fluoride content of less than 60 mmol/L, but at least 5 mmol/L and less than 10 mmol/L, but at least 0.1 mmol/L, of water-soluble compounds of the elements Zr and/or Ti based on the particular element, wherein, after the contact with the pickling solution and before the contact with the passivating solution, no rinsing or drying step takes place.
- The method according to claim 1, characterized in that the pickling solution has a free acid content of at least 12 points, but preferably no more than 16 points.
- The method according to one or both of the preceding claims, characterized in that the pickling solution has a pH of less than 2.
- The method according to one or more of the preceding claims, characterized in that the pickling solution has a total acid content of at least 15 points, but preferably no more than 20 points.
- The method according to one or more of the preceding claims, characterized in that the pickling solution additionally contains at least 7 mmol/L, but preferably no more than 30 mmol, of water-soluble compounds of the elements Zr and/or Ti based on the particular element.
- The method according to claim 5, characterized in that the molar ratio of the total amount of water-soluble compounds of the elements Zr and/or Ti, based on the particular element, to the total fluoride content in the pickling solution is less than 0.1.
- The method according to one or more of the preceding claims, characterized in that 80%, preferably 90%, particularly preferably 95%, of the points of the total acid content of the pickling solution is formed by sulfuric acid.
- The method according to one or more of the preceding claims, characterized in that the pickling solution additionally contains a surface-active organic compound, preferably a non-ionic surfactant, the proportion of surface-active organic substances being at least 0.1 mmol/L.
- The method according to one or more of the preceding claims, characterized in that the component is brought into contact with the pickling solution and/or the passivating solution by means of spraying.
- The method according to one or more of the preceding claims, characterized in that, after the passivating process and before the painting process, a rinsing step is carried out.
- The method according to one or more of the preceding claims, characterized in that, after the pre-treatment stage and optionally after the rinsing step according to claim 10, the component is coated with a powder coating.
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PL15712948T PL3126542T3 (en) | 2014-04-03 | 2015-03-31 | Two-stage pre-treatment of aluminum comprising pickling and passivation |
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DE102014206407.4A DE102014206407A1 (en) | 2014-04-03 | 2014-04-03 | Two-stage pre-treatment of aluminum including pickle and passivation |
PCT/EP2015/057035 WO2015150387A1 (en) | 2014-04-03 | 2015-03-31 | Two-stage pre-treatment of aluminum comprising pickling and passivation |
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EP3126542B1 true EP3126542B1 (en) | 2018-03-14 |
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US (1) | US10415140B2 (en) |
EP (1) | EP3126542B1 (en) |
CN (1) | CN106232871B (en) |
DE (1) | DE102014206407A1 (en) |
ES (1) | ES2665193T3 (en) |
MX (1) | MX2016012679A (en) |
PL (1) | PL3126542T3 (en) |
PT (1) | PT3126542T (en) |
TW (1) | TWI665336B (en) |
WO (1) | WO2015150387A1 (en) |
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HUE048447T2 (en) * | 2017-09-18 | 2020-08-28 | Henkel Ag & Co Kgaa | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
CN113699533A (en) * | 2021-08-27 | 2021-11-26 | 海盐卫士标准件有限公司 | Efficient metal surface pickling process and equipment |
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WO1997013005A1 (en) * | 1995-10-06 | 1997-04-10 | Henkel Corporation | Metal cleaning process with improved draining uniformity |
DE19921842A1 (en) | 1999-05-11 | 2000-11-16 | Metallgesellschaft Ag | Pretreatment of aluminum surfaces with chrome-free solutions |
DE10110834B4 (en) * | 2001-03-06 | 2005-03-10 | Chemetall Gmbh | Process for coating metallic surfaces and use of the substrates coated in this way |
DE10322446A1 (en) * | 2003-05-19 | 2004-12-09 | Henkel Kgaa | Pretreatment of metal surfaces before painting |
DE10358310A1 (en) * | 2003-12-11 | 2005-07-21 | Henkel Kgaa | Two-stage conversion treatment |
CN100545308C (en) * | 2007-11-22 | 2009-09-30 | 东北大学 | A kind of chromium-free passivation liquid and using method thereof that is used to handle aluminium alloy |
DE102008038653A1 (en) * | 2008-08-12 | 2010-03-25 | Henkel Ag & Co. Kgaa | Successive anti-corrosive pretreatment of metal surfaces in a multi-stage process |
DE102009047522A1 (en) * | 2009-12-04 | 2011-06-09 | Henkel Ag & Co. Kgaa | Multi-stage pre-treatment process for metallic components with zinc and iron surfaces |
-
2014
- 2014-04-03 DE DE102014206407.4A patent/DE102014206407A1/en not_active Ceased
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2015
- 2015-03-31 PL PL15712948T patent/PL3126542T3/en unknown
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- 2015-03-31 EP EP15712948.7A patent/EP3126542B1/en active Active
- 2015-03-31 ES ES15712948.7T patent/ES2665193T3/en active Active
- 2015-03-31 CN CN201580020911.3A patent/CN106232871B/en active Active
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- 2015-03-31 WO PCT/EP2015/057035 patent/WO2015150387A1/en active Application Filing
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CN106232871A (en) | 2016-12-14 |
PL3126542T3 (en) | 2018-09-28 |
WO2015150387A1 (en) | 2015-10-08 |
ES2665193T3 (en) | 2018-04-24 |
DE102014206407A1 (en) | 2015-10-08 |
PT3126542T (en) | 2018-03-22 |
US20170016119A1 (en) | 2017-01-19 |
US10415140B2 (en) | 2019-09-17 |
TW201602414A (en) | 2016-01-16 |
MX2016012679A (en) | 2016-12-14 |
EP3126542A1 (en) | 2017-02-08 |
TWI665336B (en) | 2019-07-11 |
CN106232871B (en) | 2019-03-01 |
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