EP3456864B1 - Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion - Google Patents

Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion Download PDF

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Publication number
EP3456864B1
EP3456864B1 EP17191578.8A EP17191578A EP3456864B1 EP 3456864 B1 EP3456864 B1 EP 3456864B1 EP 17191578 A EP17191578 A EP 17191578A EP 3456864 B1 EP3456864 B1 EP 3456864B1
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EP
European Patent Office
Prior art keywords
pickling solution
brought
contact
solution
water
Prior art date
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EP17191578.8A
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German (de)
English (en)
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EP3456864A1 (fr
Inventor
Volker GEICK
Kathrin SCHÄUBLE
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to HUE17191578A priority Critical patent/HUE048447T2/hu
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to ES17191578T priority patent/ES2767852T3/es
Priority to PL17191578T priority patent/PL3456864T3/pl
Priority to EP17191578.8A priority patent/EP3456864B1/fr
Priority to MX2020001673A priority patent/MX2020001673A/es
Priority to CN201880060188.5A priority patent/CN111094624B/zh
Priority to KR1020207007534A priority patent/KR102538202B1/ko
Priority to PCT/EP2018/067027 priority patent/WO2019052701A1/fr
Publication of EP3456864A1 publication Critical patent/EP3456864A1/fr
Application granted granted Critical
Publication of EP3456864B1 publication Critical patent/EP3456864B1/fr
Priority to US16/817,044 priority patent/US11499237B2/en
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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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/82—After-treatment
    • 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
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • 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
    • C23C24/00—Coating starting from inorganic powder

Definitions

  • the present invention relates to a process for the corrosion-protective treatment of components made of aluminum, in particular castings such as automobile rims, comprising a pretreatment stage and a subsequent coating.
  • the pretreatment step again includes a pickle based on sulfuric acid and phosphate-free aqueous solutions containing water-soluble compounds of the element Ti and at least one polybasic ⁇ -hydroxycarboxylic acid and a source of fluoride ions, the conversion treatment based on an acidic aqueous solution containing water-soluble compounds of the elements Zr and / or Ti is upstream.
  • the prior art discloses a multiplicity of pretreatment methods of components made of aluminum, in particular of aluminum casting, for imparting corrosion protection and as a paint adhesion base, which are based on a plurality of successive wet-chemical process steps.
  • the component is first subjected to a cleaning, which is a combination of surface-active and etching substances both for removing superficial contaminants originating from upstream fabrication stages, for example mold release agents, as well as for producing a reproducible component surface, which is necessary for the application of a homogeneous adhesion-promoting conversion layer , contains.
  • a cleaning which is a combination of surface-active and etching substances both for removing superficial contaminants originating from upstream fabrication stages, for example mold release agents, as well as for producing a reproducible component surface, which is necessary for the application of a homogeneous adhesion-promoting conversion layer , contains.
  • additional process steps may be required in order to obtain a substrate surface optimally conditioned for the conversion layer formation.
  • WO 94/28193 A1 It is known that a preservation of the aluminum surface produced after the cleaning and acid pickling or dewetting can be achieved for a subsequent permanent corrosion-protective pretreatment if the pickling already has passivating active components selected from water-soluble compounds of the elements Zr and / or Ti.
  • active components in the acidic pickling polyhydroxycarboxylic acids, such as gluconic acid, or polymers based on acrylates or derivatized vinylphenols are optional.
  • the after the WO 94/28193 A1 obtained passivation is intended to protect the surface against partial oxidation until the application of the permanent corrosion-protecting pretreatment and to preserve the largely homogenous chemical nature of the aluminum surface.
  • the semifinished product treated in this way can be subjected to further component production such as chipless machining, welding or forming without the occurrence of adverse effects on the immediately following applied permanent corrosion protection until the application of the permanent corrosion protection.
  • the object of the present invention is now to provide the operators of coating equipment for components made of aluminum and its alloys, in particular castings, a pretreatment stage based on the established process sequence of an acid pickling followed by a chromium-free conversion treatment based on the elements Zr and / or Ti built in the continuous operation of such a system, the bath life and maintenance intervals are extended over the prior art and ideally no caused by sludge maintenance of the pretreatment stage of the coating plant is required.
  • every measure suitable for avoiding sludge formation should be taken at the same time exerts no negative influence on the corrosion protection and the paint adhesion of the pre-treated in such a coating system components.
  • This object is achieved in a method for corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating, wherein the component in the pretreatment stage first with an aqueous sulfuric acid and phosphate-free pickling solution, the pH of 1 to 2.5, has a free acidity in points of at least 5 and at least one water-soluble compound of the element Ti; a source of fluoride ions and at least one polybasic ⁇ -hydroxycarboxylic acid, and then contacted with an aqueous conversion treatment solution having a pH of 1 to 3.5 and at least one water-soluble compound of the elements Zr and / or Ti becomes.
  • the pH denotes the negative decadic logarithm of the activity of the hydronium ions.
  • the pH is determined potentiometrically at 20 ° C. directly in the solution by means of pH-sensitive electrodes after two-point calibration with buffer solutions for the pH values of 4.01 and 7.01.
  • a compound is water soluble if its solubility in deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and at a temperature of 20 ° C is at least 1g / kg. All quantities in "g / kg" refer to the proportion of the respective component per kilogram of the respectively indicated reference solution.
  • an excellent paint adhesion is achieved which, surprisingly, also in the absence of phosphates and with high tolerance to aluminum ions in the stain, is based on the combination of the Ti and Zr coating applied in the multistage process.
  • the absence of phosphates and high tolerance to aluminum ions in the stain enable the pretreatment stage to produce no precipitates and therefore no sludge in continuous operation. This requires the presence of the polybasic ⁇ -hydroxycarboxylic acid.
  • Polybasic ⁇ -hydroxycarboxylic acids in the context of the present invention have at least two carboxylic acid groups and at least one hydroxyl group in ⁇ position to one of the carboxylic acid groups.
  • the at least one polybasic ⁇ -hydroxycarboxylic acid is selected from those compounds in which each carboxyl group has a hydroxyl group in the ⁇ - or ⁇ -position, and which furthermore preferably has not more than 8 carbon atoms.
  • Particularly preferred representatives of the polybasic ⁇ -hydroxycarboxylic acid are tartaric acid and / or citric acid, particularly preferably citric acid.
  • the proportion of polybasic ⁇ -hydroxycarboxylic acids in the pickling solution at least 0.1 g / kg, especially preferably at least 0.5 g / kg, especially
  • the proportion of polybasic ⁇ - Hydroxycarboxylic acids in the pickling solution therefore in a preferred process according to the invention not greater than 4 g / kg, more preferably not greater than 2 g / kg.
  • the positive effect of the mordant-containing water-soluble compounds of the element titanium in the presence of the source of fluoride ions on the subordinate conversion treatment is usually already achieved with small amounts in the range of a few milligrams of Ti per kilogram of mordant.
  • the proportion of water-soluble compounds of the element Ti in the pickling solution is preferably at least 0.04 g / kg, more preferably at least 0.1 g / kg. Above one gram of Ti per kilogram of pickling solution, no significant improvement in paint adhesion is obtained after the conversion treatment.
  • the pickling solution is preferably not more than 0.6 g / kg, more preferably not more than 0.3 g / kg in each case based on the element Ti of water-soluble compounds of the element Ti.
  • water-soluble compounds of the element Ti titanyl sulfate (TiO (SO 4 )), titanyl nitrate (TiO (NO 3 ) 2 ) and / or hexafluorotitanic (H 2 TiF 6 ) and their salts are well suited and therefore preferred in the pickling solution of the process according to the invention , particularly preferred is hexafluorotitanic acid and its salts.
  • a source of fluoride ions according to the invention is required for a sufficient stain of the aluminum-made component without a reproducible largely oxide-free surface can not be adjusted and the positive effect of containing in the stain water-soluble compounds of the element titanium on the paint adhesion does not apply can.
  • a source of fluoride ions in the context of the present invention is any water-soluble inorganic compound containing fluorine containing at least 100 mg / kg of fluoride ions as 0.1% by weight aqueous solution after TISAB buffering with an aliquot of the buffer. determined potentiometrically at 20 ° C by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1, released. An aliquot of the buffer results in a volume mixing ratio of buffer to aqueous solution containing the source of fluoride of 1: 1.
  • the TISAB Buffer (Total Lonic Strength Adjustment Buffer) is manufactured with a resolution of 58 g NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and setting a pH of 5.3 by means of 5 N NaOH and filling to a total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
  • the total fluoride content in the pickling solution is at least 0.02 g / kg, particularly preferably at least 0.05 g / kg, very particularly preferably at least 0.1 g / kg calculated as F.
  • 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 as described above.
  • the proportion of free fluoride in the pickling solution is to be kept low for a moderate pickling rate of the aluminum material.
  • the proportion of free fluoride is therefore less than 10 mg / kg, more preferably less than 5 mg / kg each potentiostatically determined directly in the pickling solution at 20 ° C by means of calibrated fluoride-sensitive electrode.
  • Suitable sources of fluoride ions are, for example, ammonium bifluoride, sodium fluoride and / or complex fluorides, in particular hexafluorotitanic acid and its salts.
  • complex fluorides of the element Zr should not be included in the pickling solution since these are also likely to cause the surfaces of the aluminum-made component to adhere and therefore compete with the conditioning of the aluminum surfaces achieved by the water-soluble compounds of the element Ti.
  • the pickling solution therefore contains a total of less than 0.02 g / kg, more preferably less than 0.01 g / kg, most preferably less than 0.004 g / kg of water-soluble compounds of the element Zr calculated as Zr ,
  • the pickling solution preferably has a pH below 2.0 in a process according to the invention. This ensures on a regular basis that a sufficient stain can take place in the pretreatment stage.
  • the pickling solution has a free acid content of at least 6 points, so that a pickling removal which is largely independent of the type of aluminum material to be treated and sufficiently adequate for the subsequent conversion treatment is ensured, for example in the series treatment of different aluminum materials manufactured individual components or in the series treatment of individual components produced from a mix of different aluminum materials.
  • the free acid content in points should preferably not be greater than 10 in order to effect sufficient conditioning of the aluminum surfaces on the basis of the water-soluble compounds of Ti element contained in the pickling solution.
  • 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 presence of a certain buffer capacity or a certain acidity has proven to be a stable process control in a 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 12 points, but preferably not more than 18 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.
  • An aqueous pickling solution is sulfuric if it contains sulfuric acid to adjust the pH and the proportion of other acids with a pKS 1 value of less than 2.5 for the first deprotonation step is less than 1 g / kg, more preferably less than 0 5 g / kg, more preferably less than 0.1 g / kg.
  • the pickling solution in the process according to the invention for preventing the precipitation of sparingly soluble salts and the film formation on the surfaces of the aluminum-made component is phosphate-free.
  • An aqueous pickling solution is phosphate-free if it contains less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0.05 g / kg of phosphates dissolved in water, calculated as PO 4 .
  • 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.
  • 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 component in the process of the invention, it is advantageous for sufficient staining and conditioning of the aluminum surfaces, and therefore also preferred, for the component to be contacted with the pickling solution for a duration sufficient to contain at least 2 mg of aluminum per square meter of surface area contacted to pickle the component and particularly preferably also sufficient to produce a coating layer of at least 4 mg of titanium per square meter on the contacted surface of the component.
  • the pickling solution is also preferably adjusted for the observance of pretreatment-typical treatment times such that for a alloy according to EN AW-6014 (AIMg0.6Si0.6V) at 40 ° C in an unstirred pickling solution of the method according to the invention, a pickling rate of at least 15 mgm -2 s -1 based on the element aluminum results.
  • EN AW-6014 AIMg0.6Si0.6V
  • a conversion layer based on the elements Zr and / or Ti is applied in the method according to the invention.
  • a layer of at least 50 .mu.mol / m 2 preferably at least 100 .mu.mol / m 2 , more preferably at least 200 .mu.mol / m 2 , but preferably determined by not more than 500 .mu.mol / m 2 by X-ray fluorescence analysis (RFA) based on the sum of the elements Zr and Ti, and the components made of aluminum are therefore brought into contact with the conversion treatment solution for such a duration that a corresponding layer support is realized.
  • RFA X-ray fluorescence analysis
  • At least 0.1 mmol / kg more preferably at least 0.5 mmol / kg of water-soluble compounds of the elements Zr and / or Ti calculated as a corresponding amount of the elements Zr and / or Ti however, for economic reasons, preferably not more than 5 mmol / kg, more preferably not more than 3 mmol / kg.
  • Suitable representatives of water-soluble compounds are ammonium zirconium carbonate ((NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 ), titanyl sulfate (TiO (SO 4 )), zirconium sulfate (Zr (SO 4 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 Zirconium nitrate (Zr (NO 3 ) 4 ), zirconyl nitrate (ZrO (NO 3 ) 2 ), titanyl nitrate (TiO (NO 3 ) 2 ), ammonium zirconium lactate (NH 4 Zr (C 3 H 5 O 3 ) 5 ), zirconium perchlorate ( Zr (ClO 4 ) 4 ), titanium perchlorate (Ti (ClO 4 ) 4 ), and / or hexafluorotitanic acid (H 2 TiF 6 ) or hexafluorozirconic acid (H 2
  • the molar ratio of the total content of water-soluble compounds of the elements Zr and Ti relative to the respective elements to the total fluoride content in the conversion treatment solution is at least zero , 1, more preferably at least 0.4. It has surprisingly been found that the use
  • the pH of the conversion treatment solution in the pretreatment stage is at least 1.8, more preferably at least 2.0.
  • the conversion treatment solution therefore contains a total of less than 0.1 g / kg of water-soluble compounds of the element chromium calculated as Cr.
  • the addition of phosphate ions to the conversion treatment solution is not advantageous, so that selbige in the process according to the invention is analogous to the pickling solution phosphate-free and therefore less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0 , 05 g / kg of phosphates dissolved in water, calculated as PO 4 .
  • Components made of aluminum which are treated in accordance with the present invention corrosion protection, are those whose metallic component consists of aluminum and / or aluminum alloys, in particular aluminum casting alloys, or is composed.
  • An alloy is an aluminum alloy in that it consists of at least 50 at.% Of the element Al.
  • Suitable components made of aluminum in the method according to the invention are for example selected from semi-finished products such as sheet metal, strip, coil or wire or from complex three-dimensional production objects such as rims for the automotive sector.
  • the components may be formed from strip material or sheets and / or joined together or made by casting.
  • the treatment of components made of cast aluminum alloys for example AA 6014, in particular rims for the automotive sector is preferred.
  • a pretreatment step in the sense of the present invention is a process step which is separate from the application of the paint finish and which comprises the process steps of pickling and conversion treatment which are separated from one another with the aid of liquid compositions in the form of the pickling liquor and each independently stored in system tanks Conversion treatment solution.
  • the components made of aluminum are pretreated in series in the pretreatment stage of the process according to the invention.
  • pretreatment in series involves contacting a plurality of components made of aluminum with the pickling and conversion treatment solution respectively stored in a system tank, without a complete exchange with a new batch of the following in each of the pretreatment of a single component made of aluminum System tanks of pre-treatment stage stockpiled pickling and conversion treatment solutions takes place.
  • the transition of the component from the stain into the conversion treatment takes place "directly".
  • a "rinsing step" in the sense of the present invention denotes a process which is intended solely to remove as far as possible active components from an immediately preceding wet-chemical treatment step, which are dissolved in a wet film adhering to the component, by means of a rinsing solution from the surface of the component. without replacing the active components to be removed by others. Active components are dissolved in water compounds that consume already by the mere contacting of the metallic surfaces of the component with the rinsing liquid.
  • the rinsing fluid can be city water.
  • the components to be treated in the process according to the invention originate from an upstream production process whose surfaces should therefore first be freed from impurities, such as mold release aids, in order to ensure good pickling.
  • the component is therefore supplied in the pretreatment stage before being brought into contact with the pickling solution to an alkaline degreasing, more preferably by contacting with an alkaline aqueous composition having a pH above 9, however, preferably below 12, and having a free alkalinity of at least 3 points, but preferably less than 6 points, and optionally containing surface active compounds, preferably selected from nonionic surfactants.
  • a rinsing step but preferably no drying step takes place.
  • the application of the cleaning, pickling and conversion treatment solution stored in the respective system tanks of the pre-treatment stage can be carried out by all methods known in the art, with immersion and spraying methods for bringing the aluminum made into contact
  • the spray method is particularly preferred as the type of application.
  • 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 aluminum-made component, wherein the cover layer resulting from the coating in the dried or cured state has 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, in particular those containing less than 10% by weight of organic solvent constituents, which have a boiling point below 150 ° C. at 1 bar, is particularly advantageous.
  • 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 the pretreatment and before the painting of a sink, which serves to remove an adhering to the surface wet film of the conversion solution before the paint is applied. Furthermore, it is usual and may therefore be preferred that the component is dried before the application of the paint. This is the case in particular when a powder coating is to be applied, for which a particularly good paint adhesion base is provided in the method according to the invention and therefore there is a preference.
  • the sludge-inhibiting effect of the polybasic ⁇ -hydroxycarboxylic acids is illustrated in Table 2, which assesses the sludge formation in a pickling solution according to the above process step II, but added a total of 1 g / kg of aluminum ions in the form of aluminum sulfate. From this table shows that an inhibition of sludge formation, ie the precipitation of aluminum and titanium salts, succeed in the presence of citric acid or tartaric acid.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (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)

Claims (15)

  1. Procédé de traitement anticorrosion de composants en aluminium, comprenant une étape de prétraitement et un laquage ultérieur, dans lequel le composant dans l'étape de prétraitement est d'abord traité avec un acide sulfurique aqueux et une solution de décapage sans phosphate qui présente un pH de 1 à 2,5, une acidité libre en points d'au moins 5 et au moins un composé soluble dans l'eau de l'élément Ti ;
    une source d'ions fluorure et au moins un acide polybasique α-hydroxycarboxylique, puis mise en contact avec une solution de traitement de conversion aqueuse ayant un pH de 1 à 3,5 et au moins un composé soluble dans l'eau des éléments Zr et/ou Ti.
  2. Procédé selon la revendication 1, caractérisé en ce quela proportion d'acides α-hydroxycarboxyliques dans la solution de décapage est d'au moins 0,1 g/kg, de préférence d'au moins 0,5 g/kg, plus préférablement d'au moins 1 g/kg, mais de préférence pas plus de 4 g/kg, plus préférablement pas plus de 2 g/kg.
  3. Procédé selon l'une quelconque des revendications précédentes ou les deux, caractérisé en ce que les acides α-hydroxycarboxyliques dans la solution de décapage sont choisis parmi l'acide citrique et/ou l'acide tartrique ou de préférence l'acide citrique.
  4. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que la proportion de composés solubles dans l'eau de l'élément Ti dans la solution de décapage est d'au moins 0,04 g/kg, de préférence d'au moins 0,1 g/kg, mais de préférence de 0,6 g/kg, plus préférablement pas plus de 0,3 g/kg, chacun par rapport au élément Ti.
  5. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que la solution de décapage a un pH inférieur à 2.
  6. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que la solution de décapage a une acidité libre en points d'au moins 6, mais de préférence d'au plus 10.
  7. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que la solution de décapage a une acidité totale en points d'au moins 12, mais de préférence d'au plus 18.
  8. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que la proportion de composés solubles dans l'eau des éléments Zr et/ou Ti dans la solution de traitement de conversion est d'au moins 0,1 mmol/kg, de préférence d'au moins 0,5 mmol/kg, mais de préférence de 5 mmol/kg, plus préférablement de 3 mmol/kg, chacun calculé comme quantité correspondante des éléments Zr et/ou Ti.
  9. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que les composés solubles dans l'eau des éléments Zr et/ou Ti sont choisis parmi les composés solubles dans l'eau de l'élément Zr, qui à leur tour sont choisis de préférence parmi l'acide hexafluorozirconique et ses sels.
  10. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que le composant est mis en contact avec la solution de décapage pendant une durée suffisante pour décaper au moins 2 mg d'aluminium par mètre carré de la surface en contact du composant, et de préférence également au moins une couche de recouvrement d'au moins 4 mg de titane par mètre carré de la surface en contact du composant.
  11. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que le composant est soumis à un dégraissage alcalin avec la solution de décapage avant de la mettre en contact, de préférence en le mettant en contact avec une composition aqueuse alcaline ayant un pH supérieur à 9, mais de préférence inférieur à 12, et une alcalinité libre d'au moins 3 points, mais de préférence moins de 6 points, et contenant éventuellement des composés tensioactifs, choisis de préférence parmi les tensioactifs non ioniques.
  12. Procédé selon la revendication 11, caractérisé en ce qu' après le dégraissage alcalin et avant la mise en contact avec la solution de décapage, une étape de rinçage, mais de préférence pas d'étape de séchage, est effectuée.
  13. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce qu' après la mise en contact avec la solution de décapage avant la mise en contact avec la solution de traitement de conversion, une étape de rinçage, mais de préférence pas de séchage, est effectuée.
  14. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce qu' après la mise en contact avec la solution de traitement de conversion et avant du laquage une étape de rinçage et de préférence avant le laquage, de préférence également une étape de séchage est effectuée.
  15. Procédé selon l'une quelconque ou plusieurs des revendications précédentes, caractérisé en ce que le composant est revêtu dans le laquage ultérieur d'un revêtement en poudre.
EP17191578.8A 2017-09-18 2017-09-18 Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion Active EP3456864B1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
ES17191578T ES2767852T3 (es) 2017-09-18 2017-09-18 Tratamiento previo de aluminio en dos etapas, en particular de aleaciones de aluminio, que comprende el decapado y tratamiento de conversión
PL17191578T PL3456864T3 (pl) 2017-09-18 2017-09-18 Dwuetapowa obróbka wstępna aluminium, zwłaszcza stopów odlewniczych aluminium, obejmująca wytrawianie i obróbkę konwersyjną
EP17191578.8A EP3456864B1 (fr) 2017-09-18 2017-09-18 Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion
HUE17191578A HUE048447T2 (hu) 2017-09-18 2017-09-18 Pácolási és konverziós kezelést alkalmazó kétlépéses alumínium, különösen alumíniumötvözet elõkezelés
MX2020001673A MX2020001673A (es) 2017-09-18 2018-06-26 Pretratamiento de aluminio en dos etapas, en particular aleaciones de fundicion de aluminio, que comprende tratamiento de decapados y conversion.
CN201880060188.5A CN111094624B (zh) 2017-09-18 2018-06-26 包括酸洗和转化处理的铝(特别是铸造铝合金)的两级预处理
KR1020207007534A KR102538202B1 (ko) 2017-09-18 2018-06-26 산세 및 전환 처리를 포함하는, 알루미늄, 특히 알루미늄 캐스팅 합금의 2-단계 전처리
PCT/EP2018/067027 WO2019052701A1 (fr) 2017-09-18 2018-06-26 Prétraitement d'aluminium, en particulier d'alliages d'aluminium pour fonderie, en deux étapes, comprenant un décapage et un traitement de conversion
US16/817,044 US11499237B2 (en) 2017-09-18 2020-03-12 Two-stage pretreatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17191578.8A EP3456864B1 (fr) 2017-09-18 2017-09-18 Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion

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EP3456864A1 EP3456864A1 (fr) 2019-03-20
EP3456864B1 true EP3456864B1 (fr) 2019-11-13

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US (1) US11499237B2 (fr)
EP (1) EP3456864B1 (fr)
KR (1) KR102538202B1 (fr)
CN (1) CN111094624B (fr)
ES (1) ES2767852T3 (fr)
HU (1) HUE048447T2 (fr)
MX (1) MX2020001673A (fr)
PL (1) PL3456864T3 (fr)
WO (1) WO2019052701A1 (fr)

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CN114622196B (zh) * 2021-11-11 2022-11-29 四川亨通兴达科技有限公司 基于无磷金属表面处理用环保纳米陶化剂及制备方法

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JPS5173938A (en) * 1974-12-25 1976-06-26 Nippon Packaging Kk Aruminiumuoyobi sonogokinnohyomenshoriho
DE4317217A1 (de) 1993-05-24 1994-12-01 Henkel Kgaa Chromfreie Konversionsbehandlung von Aluminium
DE19921842A1 (de) 1999-05-11 2000-11-16 Metallgesellschaft Ag Vorbehandlung von Aluminiumoberflächen durch chromfreie Lösungen
US6821633B2 (en) 2002-05-17 2004-11-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Non-chromate conversion coating compositions, process for conversion coating metals, and articles so coated
GB0500071D0 (en) * 2005-01-05 2005-02-09 Houghton Australia Pty Ltd Cleaning formulation
CN101463475A (zh) * 2007-12-19 2009-06-24 鸿富锦精密工业（深圳）有限公司 镁合金磷化方法及其化成溶液
DE102012215679A1 (de) * 2012-09-04 2014-05-15 Henkel Ag & Co. Kgaa Verfahren zur korrosionsschützenden Oberflächenbehandlung von metallischen Bauteilen in Serie
WO2015052546A1 (fr) * 2013-10-09 2015-04-16 ArcelorMittal Investigación y Desarrollo, S.L. Tôle à revêtement znaimg à flexibilité améliorée et procédé de réalisation correspondant
DE102014206407A1 (de) * 2014-04-03 2015-10-08 Henkel Ag & Co. Kgaa Zweistufen-Vorbehandlung von Aluminium umfassend Beize und Passivierung

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Publication number Publication date
EP3456864A1 (fr) 2019-03-20
HUE048447T2 (hu) 2020-08-28
US20200208273A1 (en) 2020-07-02
MX2020001673A (es) 2020-07-13
US11499237B2 (en) 2022-11-15
WO2019052701A1 (fr) 2019-03-21
CN111094624B (zh) 2023-01-24
PL3456864T3 (pl) 2020-05-18
KR20200054974A (ko) 2020-05-20
KR102538202B1 (ko) 2023-05-30
CN111094624A (zh) 2020-05-01
ES2767852T3 (es) 2020-06-18

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