EP3301205B1 - Saure wässrige zusammensetzung zur herstellung einer korrosionsbeständigen beschichtung auf einem metallsubstrat, verfahren zur behandlung des metallischen substrats mit der zusammensetzung - Google Patents

Saure wässrige zusammensetzung zur herstellung einer korrosionsbeständigen beschichtung auf einem metallsubstrat, verfahren zur behandlung des metallischen substrats mit der zusammensetzung Download PDF

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EP3301205B1
EP3301205B1 EP17188823.3A EP17188823A EP3301205B1 EP 3301205 B1 EP3301205 B1 EP 3301205B1 EP 17188823 A EP17188823 A EP 17188823A EP 3301205 B1 EP3301205 B1 EP 3301205B1
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range
aluminium
composition
concentration
acid
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French (fr)
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EP3301205A1 (de
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Richard Johannes Van Der Net
Robin Arthur LANGELAAR
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Ad Productions BV
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Ad Productions BV
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    • 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
    • C23C22/05—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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to an acidic aqueous composition for preparing a corrosion resistant coating on a metal substrate, a method of providing a corrosion resistant coating on a metal substrate, as well as a post-treatment composition, in particular for use in said method.
  • an aqueous solution for forming a protective coating on a metal surface includes Cr 2 (GF 6 ), in which G is a Group IV-B element (Zr, Ti or Hf), in particular Cr 2 (ZrF 6 ) 3 at least one polymer having a plurality of carboxylic acid groups such as polyacrylic acid and copolymers of methyl vinyl ether and maleic acid, and at least one polymer having a plurality of hydroxyl groups for example polyvinyl alcohols and homopolymers or copolymers of hydroxyethyl methacrylate, and/or at least one polymer having a plurality of both carboxylic acid and hydroxyl acid groups exemplified by free-radical copolymers of hydroxyl-ethyl methacrylate and methacrylic acid, wherein the composition contains less than 500 ppm of alkali metal ions and less than 200 ppm of halide ions relative to chromium.
  • G is a Group IV-B element (Zr,
  • the Zr : Cr molar ratio is typically determined by the stoichiometry of the compound, but due to the optional presence of other components the weight ratio Zr : Cr is typically in the range of 2.4 : 1 - 3.0 : 1, most typically 2.6:1 -2.8:1.
  • Any metal may be treated, with apparently good results being obtained on zinc, zinc alloy, aluminium and aluminium alloy surfaces.
  • organo-functional silanes such as aminoproyl triethoxysilane may improve adhesion of subsequently applied coatings such as paints) to the treated surfaces, while maintaining good corrosion results.
  • the pH of a treatment solution comprising the above polymers is in a range from 2.5 - 4.0, more typically 2.8-3.2.
  • US 6375726 B1 has disclosed an acidic aqueous solution for the protection and surface treatment of aluminium, aluminium alloys and coated aluminium substrates against corrosion.
  • the solution comprises at least one trivalent chromium salt such as trivalent chromium sulphate, at least one alkali metal hexafluorozirconate in combination with at least one water soluble or dispersible thickening agent and a water soluble surfactant.
  • the corrosion resistant aluminium substrates of this invention have improved adhesion for overlaying coatings e.g. paints and a lower electrical resistance contact.
  • WO 2006/088519 A2 discloses an acidic aqueous solution for treating metal substrates, such as aluminium alloy or iron alloy or a metal substrate having a pre-existing metal coating for example anodized aluminium to improve the adhesion bonding and corrosion protection, which comprises water soluble trivalent chromium compounds, fluorozirconates, fluorometallic compounds, zinc compounds, thickeners, surfactants, and at least about 0.001 mole per litre of the acidic solution of at least one polyhydroxy and/or carboxylic compound as the stabilizing agent for the aqueous solution.
  • the carboxylic compounds contain one or more carboxylic functional groups having the formula R-COO- wherein R is hydrogen or a lower molecular weight organic radical or functional group, and can be used in the form of their acids or salts.
  • the stabilizers are said to result in improved shelf-life and working stability of the solutions. According to this document after treating with the acid aqueous solution, application of a strong oxidizing solution can yield a film having additional corrosion resistance, which is presumed to be due to the formation of hexavalent chromium in the film derived from the trivalent chromium.
  • an acidic, aqueous composition that contains a trivalent chromium compound, an organo-functional silane, and a compound of a group IV-B element, is known from US 2009/0280253 A1 .
  • the composition is said to protect metal surfaces, preferably aluminium and aluminium alloys, against corrosion and improves their paint adhesion.
  • the trivalent chromium compound may comprise chromium fluoride and optionally others, such as chromium nitrate.
  • the organo-functional silane is preferably an aminopropyltriethoxy silane, and the compound of a group IV-B element is preferably fluorozirconic acid.
  • the composition can either be dried-in-place or rinsed before a further coating layer is applied.
  • the composition may also include at least one polymer having a plurality of both carboxylic functional groups, alone or with hydroxyl groups.
  • the document also discloses a process using the aqueous composition either with or without the organo-functional silane along with a sealing step following the application of the aqueous composition; wherein the sealing step involves applying a sealing composition, including an organo-functional silane, to the metal surface.
  • a process for surface treatment of a part made of aluminium, magnesium, or one of the alloys thereof, is known in order to protect the part from corrosion.
  • the method comprises consecutively immersing the part in a first aqueous bath containing a corrosion-inhibiting metal salt such as trivalent chromium salt and an oxidizing compound such as K 2 ZrF 6 , and a second aqueous bath containing an oxidizing compound like hydrogen peroxide and a corrosion-inhibiting rare-earth salt.
  • the method can be carried out for the chemical conversion of aluminium or the alloys thereof, and of magnesium or the alloys thereof, on parts that have not been previously treated, or after anodizing the part to seal the anodic layer.
  • US 6648986 B1 teaches an acidic aqueous solution that contains a water soluble trivalent chromium compound, a water soluble fluoride compound, an alkaline pH adjustment reagent and provided with a solution stability additive for reducing precipitation of trivalent chromium over time.
  • the solution stability additive comprises a complexing agent that is selected from the group consisting of organic acids (single coordination acids and bidentate chelating compounds) and amino acids.
  • concentration of the solution stability additive varies based on the complexing capability of the additive.
  • US 2010/0132843 A1 discloses a low sludge trivalent chromium based conversion coating bath that forms corrosion resistant coatings on aluminium and aluminium alloys by immersion in aqueous solutions containing trivalent chromium ions and fluorometallate ions followed by optional rinsing. Trivalent chromium coated aluminium also serves as an effective base for paint primers.
  • US 2006/240191 A1 discloses a process for treating metal substrates to improve the corrosion protection and adhesion bonding strength which comprises treating the metal substrates with an acidic aqueous solution having a pH ranging from 1.0 to 5.5, wherein the acidic solution comprises a trivalent chromium compound, a fluorozirconate compound and at least one stabilizing agent compound selected from the group consisting of polyhydroxy compounds, carboxylic compounds and mixtures thereof.
  • Another object is to provide such a stable treatment solution that offers an enhanced layer formation.
  • a further object is to provide a method of applying a treatment composition to such a metal substrate in order to achieve corrosion resistance and/or adhesion.
  • the invention provides an acidic aqueous composition for preparing a corrosion resistant layer on substrates of aluminium, aluminium alloys, anodized aluminium, zinc or zinc alloy coated steel, aluminized steel, wherein the composition comprises: trivalent chromium (Cr 3+ ): 0.04 - 6 g/l zirconium (Zr 4+ ): 0.08 - 8 g/l total fluoride (F - ): 0.1 - 9 g/l stabilizing agent comprising a hydroxyl carboxylic acid or corresponding bases thereof (calculated as the acid): 0.2 - 9 g/l wherein
  • the aqueous composition according to the invention when used as a bath is stable in time and does not form deposits and/or sludge in the bath.
  • the surface which is essentially free of Cr 6+ , shows good corrosion resistance and if present, durable bonding to a subsequently applied paint system or adhesive bonding system.
  • the acidic aqueous composition according to the invention comprises as main active components trivalent chromium, tetravalent zirconium and fluoride in specific concentrations and ratios, as well as one or more hydroxyl carboxylic acids as stabilizing agent.
  • Trivalent chromium is present in an amount of 0.04-6 g/l, preferably 0.2-1.0 g/l for dipping and spraying applications. For touch-up, maintenance and repair applications using e.g. brushing and wiping a broader range of 0.5-5.0 g/L is advantageous. If the amount of chromium (III) is lower, then within industrially acceptable processing times, the rate of layer formation is low resulting in a layer having an insufficient thickness and thus inadequate protection and/or bonding.
  • the trivalent chromium can be derived from organic chromium salts, in particular citrate, glycolate, tartrate, and combinations thereof.
  • Another attractive route for obtaining trivalent chromium is by reducing chromic acid (H 2 CrO 4 ) with chemical agents that can be oxidized by chromic acid like methanol or hydrogen peroxide leaving no residual products in the starting solution after heating.
  • Another attractive source for trivalent chromium and fluoride is using OF 3 .4H 2 O as a starting material. This compound is hardly soluble in water, but accompanied by acidic components like HF, acidic hydroxyl carboxylic stabilizing agents and water soluble acidic polymers or combinations thereof, it is.
  • HF is preferably used as it does not introduce extraneous anions other than those required.
  • Tetravalent zirconium is present in an amount of 0.08-8 g/l, preferably in the range of 0.2-2.0 g/l.
  • Suitable starting materials comprise hexafluozirconic acid and its ammonium salt, zirconium salts of lactate, carbonate, glycolate and citrate, ammonium zirconium carbonate and zirconium triethanol amine, and combinations thereof.
  • the high zirconium content is believed to enhance co-precipitation of Cr and Zr as Cr(OH) 3 and Zr(OH) 4 and thereby layer formation.
  • F- ions are present in the range of 0.1-9 g/l, preferably 0.2-2.0 g/l.
  • the fluoride can be obtained from HF, alkali metal fluoride like sodium fluoride, ammonium bi fluoride (ABF), chromium fluoride, hexafluo zirconic acid and its ammonium salt, as well as combinations thereof. If hexafluo zirconic acid is used as a starting material, at least one other zirconium component is present, otherwise the ratio of Zr : F is not within the required range. High fluoride contents compared to Cr and Zr results in excessive etching hindering layer formation. Without being bound to any theory it is believed that fluoride contents in the solution according to the invention will prevent over-etching during layer formation and might prevent accumulation of fluorides in the layer that could weaken the conversion layer during exposure in corrosive environment.
  • Low fluoride contents have the opposite effect and may reduce stability of the composition.
  • the molar ratio Zr 4+ : Cr 3+ is in the range of 0.8 : 1 to 2.0 : 1; preferably 0.9:1 - 1.3 : 1, such as 1.04: 1.0; and the molar ratio Zr 4+ : F - is in the range of 1: 5.5 to 1.0 : 2.0.
  • the acidic aqueous comprises a stabilizing agent being a hydroxy carboxylic acid or a corresponding base thereof in a concentration of 0.2-9 g/l, preferably in the range of 0.2- 5 g/l, more preferably 0.3 - 3 g/l (calculated as the acid).
  • the stabilizing agent can be used as the acid or a water soluble salt thereof.
  • Suitable hydroxyl carboxylic acids are lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid and combinations thereof.
  • the stabilizing agent may be introduced in the composition by the chromium or zirconium compound as well as shown above in the form of the zirconium and/or chromium (III) salt of the conjugated base of the hydroxy carboxylic acid, or as a similar part of the pH adjusting agents as discussed below.
  • the stabilizing agent acts to stabilize the solution as a dipping bath having the composition according to the invention in time, which bath would otherwise at the given concentrations and ratios of its components deteriorate rapidly. It is assumed that the acid becomes part of the resulting layer comprising the hydroxides and oxides of chromium and zirconium. Higher contents of hydroxyl carboxylic acids results in coating layers that are sensitive to dissolving.
  • the composition according to the invention has a pH in the range of 3.0-5.0, preferably 3.4-4.4. If the pH is too low then the formation of the protective layer on the substrate is limited by the simultaneous attack of the formed layer by the acidic components. Thus the composition as a whole offers a balance between components and the amount thereof, their functional properties and processing possibilities.
  • the composition may contain pH adjusting agents, typically bases, such as one or more alkali metal hydroxides like sodium hydroxide, potassium hydroxide and ammonia.
  • the pH adjusting agent may be a source of the base of the hydroxyl carboxylic acid stabilizing agent.
  • examples include lactate, citrates of ammonium and/or sodium and the like.
  • the pH adjusting agent is present in amount of 0-1.0 g/l.
  • the alkali metal cations do not - or to a negligible extent - affect the formation of the protective layer.
  • the pH rises to values above 5 the composition can easily become instable. At pH less than 3.0 it is hard to form substantial coating weight in view of corrosion resistance.
  • the composition may also comprise one or more water soluble surfactants for improving the wetting properties, advantageously in a concentration of 0-1.0 g/l, preferably 0.001-0.5 g/l.
  • surfactants that can be used in the composition according to the invention include acid stable low foaming anionic and non-ionic surfactants like alkaryl sulfonates and poly ethylene glycol fatty amines. The surfactant provides uniform wetting of the substrate. If the amount of surfactant is too high, it can cause excessive foaming in the process.
  • compositions according to the invention comprise water soluble polymers and organo-functional silanes and/or their hydrolysed oligomers.
  • the water soluble polymers include homopolymers and copolymers that preferably are based on the following monomers: acrylic acid, methacrylic acid, vinylalcohol, vinylether, maleic acid, monohydroxy acrylic ester, vinylphosphonic acid, vinylsulphonic acid, methyl vinylether, monohydroxy methacrylic ester and combinations thereof, up to 4.0 g/l, preferably 0.01-4.0 g/l, more preferably 0.1-1 g/l. These polymers improve wetting behaviour of the treatment composition, as well as adhesion of subsequently applied organic coatings. Too high concentrations will reduce wet adhesion of an organic coating.
  • the concentration of the silanes or oligomers, if present, ranges up to 4.0 g/l.
  • the reactive functional group is at least one selected from a mercapto group, an amino group, a vinyl group, an epoxy group and a methacryloxy group, advantageously in an amount of 1 to 40 mg/l based on Si.
  • the invention relates to a method of treating a substrate of aluminium, aluminium alloy, anodized aluminium, aluminized steel, zinc or zinc alloy coated steel for corrosion protection, adhesion of an organic coating or adhesive bonding system, which method comprises a step of applying the acidic aqueous solution according to the invention as explained above onto a substrate of aluminium, aluminium alloy, anodized aluminium, aluminized steel, zinc or zinc alloy coated steel.
  • the metal surface to be treated with the composition according to the invention is pre-treated using known mechanical and/or chemical pre-treatment processes or combination thereof for obtaining a wettable surface, which typically requires the surface to be roughened and to be substantially free of rust, fat, oil and the like.
  • Mechanical pre-treatment processes comprise grit blasting, shot peening, scuffing, scotch brite® and abrading.
  • Chemical pre-treatment includes e.g. (acidic/alkaline/solvent) degreasing, de-oxidation, desmutting, pickling.
  • each chemical pre-treatment is followed by a rinsing step using tap water or demineralised water. Combinations of mechanical pre-treatment and chemical pre-treatment in any order is also possible.
  • the surface may be anodized.
  • treatment according to the invention of bare aluminium will form a conversion layer. Treating anodized aluminium according to the invention will result in a sealing layer.
  • the way of applying the composition according to the invention to the metal surface is not limited. However, homogeneity and uniformity of the applied wet film on the substrate before drying will be advantageous. Suitable application methods include touch-up methods, spraying, dipping, wiping, brushing, roll coating and the like. Excess of treatment fluid on parts with intricate geometries can be removed with water rinsing, compressed air or wiping. After applying the acidic aqueous composition one or more rinsing steps with demi water are performed, preferably the last rinsing step with demi water having an electrical conductivity in the range of 5-200 microS, and a drying step of drying the thus rinsed substrate, in particular at a temperature in the range of 10-50 °C.
  • the method according to the invention is performed with the composition having a temperature in the range of 10-80°C, preferably 15-50 °C.
  • the processing time ranges from 1-30 minutes, preferably from 3-15 minutes. Processing times of less than 3 minutes are practically not feasible on industrial scale in view of reproducible coating results. Processing times of more than 30 minutes may interfere with other operations on a continuous production line.
  • the coating weight as measured by XRF after drying, is typically in the range of 5-200 mg Cr/m 2 , such as 15-100 mg Cr/m 2 .
  • coating weight can be controlled by adjusting concentration, pH, bath temperature and immersion time. Too high coating weights will give corrosion resistance, but may reduce adhesion properties and increase the surface electrical resistivity. Low electrical resistivity of the metal surface is important for certain applications as it prevents build-up of static electricity and will not influence welding properties.
  • the method according to the invention is very suitable for maintenance and repair of damaged aluminium surfaces, like aerostructural parts, in particular where electrical resistivity of the resulting protective layer should be low, e.g. as detailed in MIL-DTL-5541F Class 3 coatings.
  • This further treatment step comprises post-treating the substrate that has been treated with the acidic aqueous composition, with a second acidic aqueous composition comprising an oxidizing agent and an acidifying component, which second composition has a pH in the range of 1-5, preferably 1-3. It has been shown that the risk of formation of Cr 6+ in the formed protective layer is reduced by using the acidic second solution. Cr 6+ was less than the detection limit ( ⁇ 0.03 ⁇ g/cm 2 ) in the used second solution and in the thus obtained protective layer.
  • the oxidizing component is a water soluble peroxide, preferably hydrogen peroxide.
  • Hydrogen peroxide functions as a reductor with respect to Cr 6+ in an acidic environment.
  • trivalent chromium will not be converted into hexavalent chromium.
  • concentration of the oxidizing component ranges typically from 10-100 g/l, preferably from 25-100 g/l.
  • the acidifying component is present in a concentration of 0.2-20 g/l, preferably 0.5-5.0 g/l.
  • the acidifying component is advantageously a non-halogenated inorganic acid such as nitric acid, or a metal salt thereof excluding rare earth metals, preferably a salt of aluminium, zirconium and/or trivalent chromium, preferably the nitrate salt thereof.
  • These acidic components should not dissolve the applied coating by the first composition nor etch aluminium.
  • Nitric acid is a strong acid but has shown not to attack the coating from the first solution. Other strong acids like hydrogen chloride and sulphuric acid are too aggressive towards the first deposited layer.
  • the second composition should be acidic enough to avoid formation of hexavalent chromium.
  • the temperature of the second composition is preferably in the range of 10-50 °C, more preferably at ambient temperature, like 20-30 °C. Such a low temperature is advantageous in order to avoid fast decomposition of peroxides.
  • Treating time is typically 1-30 minutes, preferably 3-15 minutes.
  • Suitable application methods for the second composition include spraying, dipping, wiping, brushing, roll coating and the like.
  • the invention is illustrated by the following Examples and Tests.
  • Composition 1 and 2 as indicated in Table 1 were prepared from commercially available compounds, as well as a Comparative Example without any hydroxy carboxylic acid. It appears that the composition of the Comparative Example is not stable. Table 1. Examples starting Compositions according to the invention and Comparative Example and their stability Composition 1 (wt.%) Composition 2 (wt.%) Comparative Example (wt.%) Zirconium triethanolamine (13.8 wt.% Zr) 4 Hexafluoro zirconium acid (19.8 wt.% Zr) 1.41 Ammonium zirconium carbonate (14.8 wt.%Zr) 4.5 4.5 Chromium trifluoride *4 H 2 O (28,7 wt.% Cr) 1.51 1,03 1.03 Hydrogen fluoride (20%) 0.9 0.9 Malic acid (99%) 0.9 0.7 Remainder water Zr : Cr mol ratio 1.1 : 1 1.3 : 1 1.3:1 Zr : F mol ratio 1 : 4.8 1 : 3.6 1:3.6 St
  • Table 4 shows the various (optional) method steps and the conditions thereof, which are carried out according to the invention.
  • Table 4. General process conditions, preferred conditions and actual test values.
  • Product Concentration [wt.%] Treatment time [min] Temp. [°C] pH Alkaline degreasing (Cleaner ABF) 3.0 3-7 (5) 50-55 (53) 9-10 (9.5) Tap water rinsing Acidic deoxidation/ desmutting (Adeox 11) 3.5 3-7 (5) 15-25 (20) 1-3 (1) Tap water rinsing Demi water rinsing First treatment solution (C2) 5-20 2-20 [5--15] (10) 10--80 [30 - 45] (40) 3-5 [3.4- 4.4] (3.9) Demi water rinsing Forced hot air drying (optionally) 10-- 80 [40 --60] Second treatment solution (P1) 0 -60 [3--7] (5) 5--60 [15-- 30] (20) 1-5 [1-3] (2.5) Demi water rin
  • Alodine 1200S treated samples the aluminium substrate panels were subjected to the steps as summarized in below Table 5. Table 5.
  • Pre-treatment and treatment steps for Alodine 1200 treated samples Product Immersion time [min] Temperature [°C] Alkaline Predegreasing Turco 6849 10 60 Alkaline degreasing Turco 4215 10 65 Tap water rinsing Acidic deoxidation/desmutting Socosurf 1858 5 45 Tap water rinsing Demi water rinsing Conversion Coating Alodine 1200S 2 RT Demi water rinsing
  • Table 7 shows data of the resulting layer weight of a conversion coating applied to AA2024 steel using 8 wt% solution of composition 2 (C2) under varying process time, using varying immersion (dipping) times, pH and T conditions.
  • Tthe aluminium was pre-treated as listed in Table 4.
  • AA2024-T3 panels were treated with first treatment solution C1 under the same conditions as listed in Table 4 for C2 and various second treatment solutions.
  • Table 8 shows the corrosion test results of 2024 aluminium alloy, as well as the Cr 6+ content present in conversion coating determined by boiling water extraction.
  • Table 9 Coating weight [mg Cr/m 2 ] contact resistance MIL-DTL-81706 B Class 3 conversion coating ⁇ 5 m ⁇ /in2) [m ⁇ /in2] corrosion resistance MIL-DTL-5541F ASTM-B117 >168 hrs [hrs] AA2024-T3 23 0.4 >168 AA2024-T81 15 0.5 >168 AA6061-T6 30 1.6 >3000 AA7075-T73 30 1.5 >168 AA5083-H111 41 2.3 >168
  • the method and compositions according to the invention are also suitable for maintenance and repair purposes, such as maintenance of aeroplanes, using the so-called touch-up or brush (wipe) methods, wherein the respective Al parts are degreased and any oxide skin is removed mechanically. Thereafter the first and second treatment solutions according to the invention are applied using a double (vertical and horizontal) wipe technique with dust free cloth.
  • Table 11 presents further corrosion results of various metal substrates when treated according to the invention with C2 and optionally P1.
  • Table 11. Overview corrosion test results various aluminium alloys treated with C2, optionally followed by post-rinse P1 at room temperature during 5 minutes.

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Claims (15)

  1. Saure wässrige Zusammensetzung zur Herstellung einer korrosionsbeständigen Schicht auf Substraten aus Aluminium, Aluminiumlegierungen, eloxiertem Aluminium, mit Zink oder Zinklegierung beschichtetem Stahl oder aluminiertem Stahl, wobei die Zusammensetzung umfasst: dreiwertiges Chrom (Cr3+): 0,04 - 6 g/l Zirkonium (Zr4+): 0,08 - 8 g/l Gesamtfluorid (F-): 0,1 - 9 g/l Stabilisierungsmittel, umfassend eine Hydroxylcarbonsäure oder entsprechende Base(n) davon (berechnet als die Säure): 0,2-9 g/l
    wobei
    das Molverhältnis Zr4+ : Cr3+ im Bereich von 0,8 : 1 bis 2,0 : 1 liegt;
    das Molverhältnis Zr4+ : F- im Bereich von 1 : 5,5 bis 1,0 : 2,0 liegt; und
    der pH-Wert im Bereich von 3,0 - 5,0 liegt.
  2. Die Zusammensetzung nach Anspruch 1, wobei die Konzentration an dreiwertigem Chrom (Cr3+) im Bereich von 0,2 - 1,0 g/L oder im Bereich von 0,5 - 5,0 g/L liegt.
  3. Die Zusammensetzung nach Anspruch 1 oder 2, wobei die Konzentration von Zirkonium (Zr4+) im Bereich von 0,2 - 2,0 g/L liegt.
  4. Die Zusammensetzung nach einem der vorstehenden Ansprüche, wobei die Konzentration an Fluoridionen (F-) im Bereich von 0,2 - 2,0 g/L liegt.
  5. Die Zusammensetzung nach einem der vorstehenden Ansprüche, wobei die Konzentration des Stabilisierungsmittels, das eine Hydroxylcarbonsäure oder entsprechende Base(n) davon umfasst, im Bereich von 0,2 - 5 g/L, bevorzugt 0,3 - 3 g/L (berechnet als Säure) liegt.
  6. Die Zusammensetzung nach einem der vorstehenden Ansprüche, wobei der pH-Wert im Bereich von 3,4 - 4,4 liegt.
  7. Die Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend ein oder mehrere wasserlösliche Tenside in einer Konzentration von 0 - 1,0 g/L, bevorzugt 0,001 - 0,5 g/L, pH-Einstellmittel in einer Konzentration von 0 - 1,0 g/L, wasserlösliche Polymere, organofunktionelle Silane oder Oligomere in einer Konzentration von bis zu 4,0 g/L.
  8. Verfahren zum Behandeln eines Substrats aus Aluminium, Aluminiumlegierung, eloxiertem Aluminium, aluminiertem Stahl, mit Zink oder Zinklegierung beschichtetem Stahl zum Korrosionsschutz, zur Haftung eines Beschichtungs- oder Klebebindungssystems, wobei das Verfahren einen Schritt des Auftragens der sauren wässrigen Lösung nach einem der vorhergehenden Ansprüche 1 - 7 auf ein Substrat aus Aluminium, Aluminiumlegierung, eloxiertem Aluminium, aluminiertem Stahl, mit Zink oder Zinklegierung beschichtetem Stahl umfasst.
  9. Das Verfahren nach Anspruch 8, wobei die Zusammensetzung eine Temperatur im Bereich von 10 - 80 °C, bevorzugt 15-50 °C, aufweist.
  10. Das Verfahren nach Anspruch 8 oder 9, wobei die Behandlungszeit 1 - 30 Minuten, bevorzugt 3 - 15 Minuten beträgt.
  11. Das Verfahren nach einem der vorhergehenden Ansprüche 8 - 10, weiter umfassend einen oder mehrere Schritte des Spülens des behandelten Substrats mit entmineralisiertem Wasser, wobei bevorzugt der letzte Spülschritt unter Verwendung von entmineralisiertem Wasser mit einer Leitfähigkeit im Bereich von 5 - 200 mikroS durchgeführt wird, und mehr bevorzugt einen Schritt des Trocknens des gespülten Substrats, insbesondere bei einer Temperatur von 10 - 50 °C.
  12. Das Verfahren nach einem der vorhergehenden Ansprüche 8 - 11, wobei das Beschichtungs- gewicht im Bereich von 5 - 200 mg Chrom/m2 liegt, gemessen durch RFA nach dem Trocknen.
  13. Das Verfahren nach einem der vorhergehenden Ansprüche 8 - 12, weiter umfassend einen Schritt der Nachbehandlung des Substrats, das mit der sauren wässrigen Zusammensetzung nach einem der Ansprüche 1 - 7 behandelt wurde, mit einer zweiten sauren wässrigen Zusammensetzung, die ein Oxidationsmittel und eine säuernde Komponente umfasst und einen pH-Wert im Bereich von 1 - 5, bevorzugt 1 - 3 aufweist.
  14. Das Verfahren nach Anspruch 13, wobei die Konzentration des Oxidationsmittels im Bereich von 5 - 100 g/L, bevorzugt 8-50 g/L liegt, und/oder wobei das Oxidationsmittel ein wasserlösliches Peroxid, bevorzugt Wasserstoffperoxid, ist.
  15. Das Verfahren nach einem der vorhergehenden Ansprüche 13 - 14, wobei die Konzentration der säuernden Komponente im Bereich von 0,2 - 20,0 g/L liegt, bevorzugt von 0,5 - 5,0 g/L, und/oder wobei die saure Komponente ein Salz von Aluminium, Zirkonium oder dreiwertigem Chrom ist, bevorzugt ein Nitratsalz davon.
EP17188823.3A 2016-09-02 2017-08-31 Saure wässrige zusammensetzung zur herstellung einer korrosionsbeständigen beschichtung auf einem metallsubstrat, verfahren zur behandlung des metallischen substrats mit der zusammensetzung Active EP3301205B1 (de)

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WO2024003504A1 (fr) * 2022-06-30 2024-01-04 Safran Landing Systems Piece en alliage d'aluminium et procede de fabrication associe
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