EP3757251B1 - Zusammensetzung für die oberflächenbehandlung eines metallsubstrats, und oberflächenbehandlungsverfahren, bei dem eine solche zusammensetzung zum einsatz kommt - Google Patents

Zusammensetzung für die oberflächenbehandlung eines metallsubstrats, und oberflächenbehandlungsverfahren, bei dem eine solche zusammensetzung zum einsatz kommt Download PDF

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EP3757251B1
EP3757251B1 EP20181532.1A EP20181532A EP3757251B1 EP 3757251 B1 EP3757251 B1 EP 3757251B1 EP 20181532 A EP20181532 A EP 20181532A EP 3757251 B1 EP3757251 B1 EP 3757251B1
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Prior art keywords
substrate
composition
compound
corrosion
composition according
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French (fr)
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EP3757251A1 (de
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Marion ELY
Jean-Louis DE LA VERGNE DE CERVAL
Philippe Tingaut
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Socomore
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Socomore
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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
    • 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
    • C25D11/243—Chemical after-treatment using organic dyestuffs
    • 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
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • 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 present invention falls within the field of the surface treatment of metal substrates, in particular aluminum alloy, more particularly treatments of the type aimed at forming a chemical conversion layer on the surface of the substrate, with a view to improving it. corrosion resistance and paint adhesion properties.
  • the present invention relates to an aqueous composition for the surface treatment of a metal substrate, as well as a process for the surface treatment of metal substrates implementing such a composition, and as well as a substrate obtained by such process.
  • metal parts in particular parts made of aluminum or aluminum alloy, or of magnesium or magnesium alloy, must frequently be surface treated in order to improve their corrosion resistance.
  • a technique commonly used for this purpose is that known as chemical conversion, which consists in forming on the surface of the part, by means of a composition based on a corrosion-inhibiting metal cation, a protective coating composed mainly hydroxides, oxyhydroxides and oxyfluorides of the aluminum constituting the part and the corrosion-inhibiting metal cation used.
  • the compositions for the chemical conversion of aluminum surfaces most commonly used at present in the aeronautical industry contain hexavalent chromium as a corrosion-inhibiting metal cation.
  • hexavalent chromium Due to the harmful nature of hexavalent chromium towards the environment and its toxicity for living organisms, it has been sought for some years to replace it in chemical conversion compositions, with less harmful substances.
  • compositions containing corrosion-inhibiting metal cations other than hexavalent chromium, in particular trivalent chromium do not make it possible to form a colored coating on the surface of the treated parts.
  • a coloring compound to these compositions based on a corrosion-inhibiting metal cation other than chromium hexavalent.
  • pyrocatechol violet has been proposed for this purpose, as described in particular in the document WO 2018/144580 for trivalent chromium.
  • compositions containing on the one hand corrosion-inhibiting metal cations other than hexavalent chromium, and more particularly trivalent chromium, and on the other hand the dyes proposed by the prior art, in particular pyrocatechol violet, are used for the chemical conversion of metal surfaces, in particular aluminum surfaces, it is observed that the corrosion resistance properties of the treated parts are insufficient to meet the requirements of the aeronautical field, in particular in terms of performance in the resistance test salt spray. Although not completely explained, this phenomenon seems to be due to a negative effect of the dye on the stability of the conversion layer formed by the chemical conversion composition on the surface of the treated parts.
  • coloring compound which can be used in chemical conversion compositions, in particular aluminum or magnesium, or their respective alloys, in particular in compositions based on trivalent chromium and a fluorinated compound, and which makes it possible to color the surface coating formed on the parts treated with this composition, so that this coating is visually detectable, this without however impacting the corrosion resistance performance of these coatings, compared to those obtained by means of compositions conversion devoid of coloring compound.
  • WO 2013/185131 , WO 2014/151491 and WO 2014/151570 describe aqueous compositions for the surface treatment of substrates, containing a metal fluoride and a coloring compound such as catechol violet or xylenol orange. These compositions are devoid of trivalent chromium.
  • the present invention aims to provide a chemical conversion composition which makes it possible to form on a metal substrate a colored surface layer whose coloring is visually detectable, because it is different from that of the treated substrate, and which has a high degree of resistance to corrosion.
  • the invention also aims for this surface layer to have good uniformity and good adhesion to paints, in particular to the primers commonly used in the aeronautical industry.
  • Xylenol orange or tetrasodium salt of 3,3'-Bis[ N , N -bis(carboxymethyl)aminomethyl]-o-cresolsulfonephthalein, is a dye commonly used for complexometric assays, with the formula:
  • xylenol orange does not have the ability to complex chromium.
  • an aqueous composition for the surface treatment of a metal substrate in particular of the type by chemical conversion.
  • This composition which will be designated in the present description by the expression “chemical conversion composition”, or even “conversion composition”, contains, conventionally in itself for this type of composition, a fluorinated compound and a compound metallic corrosion inhibitor, excluding compounds based on hexavalent chromium. It also contains, as a water-soluble coloring compound, xylenol orange.
  • the corrosion inhibiting metallic compound is a trivalent chromium salt and the pH of the composition is between 3 and 5.
  • this composition makes it possible to form on metal substrates, in particular aluminum or aluminum alloy, magnesium or magnesium alloy, or steel substrates, a colored surface coating which has a high degree of corrosion resistance.
  • This coating also has good uniformity over the entire area of the substrate treated, and good adhesion to the paint systems commonly used in the aeronautical industry.
  • the conversion composition according to the invention can also meet one or more of the characteristics described below, implemented in isolation or in each of their technically effective combinations.
  • the conversion composition according to the invention is preferably substantially free of hexavalent chromium.
  • substantially free is meant the fact that it does not contain hexavalent chromium, except in trace form, that is to say in an amount less than or equal to 0.1% by weight relative to the weight composition total.
  • the composition according to the invention contains no coloring compound other than xylenol orange.
  • the xylenol orange is preferably present in the composition according to the invention in a concentration of between 0.3 and 2 g/l, preferably between 0.5 and 1.5 g/l.
  • concentration range advantageously ensures, on the one hand, that the coating formed on the surface of the metal substrate is sufficiently colored for this coloring to be detectable with the naked eye, and on the other hand that the performance of resistance to corrosion imparted to the treated substrate are maximal. In particular, above 1.5 g/l, these performances prove to be less satisfactory.
  • the conversion composition according to the invention may contain a single fluorinated compound, or a plurality of fluorinated compounds.
  • At least one fluorinated compound is a fluorinated salt, preferably a fluorinated salt of a metal, in particular of a transition metal.
  • This transition metal is preferably chosen from zirconium and titanium.
  • the fluorinated compound is a fluorinated salt of a transition metal and an alkali metal, such as potassium.
  • fluorinated compounds examples include potassium hexafluorozirconate (K 2 ZrF 6 ), dihydrogen hexafluorozirconate (H 2 ZrF 6 ), potassium hexafluorotitanate ( K 2 TiF 6 ) and dihydrogen hexafluorotitanate (H 2 TiF 6 ).
  • the conversion composition according to the invention may otherwise contain, as as a fluorinated compound, sodium hexafluorosilicate (Na 2 SiF 6 ), dihydrogen fluorogermanate (H 2 GeF 6 ) or even dihydrogen fluorophosphonate (H 2 PO 2 F), etc.
  • a fluorinated compound sodium hexafluorosilicate (Na 2 SiF 6 ), dihydrogen fluorogermanate (H 2 GeF 6 ) or even dihydrogen fluorophosphonate (H 2 PO 2 F), etc.
  • a particularly preferred fluorinated compound in the context of the invention since it confers particularly advantageous properties on the coating formed on the surface of the treated metal substrate, is an alkali metal hexafluorozirconate, in particular potassium hexafluorozirconate.
  • the conversion composition according to the invention preferably contains a concentration of between 1 and 15 g/l of fluorinated compound(s), in particular a concentration of between 1 and 15 g/l of potassium hexafluorozirconate.
  • the conversion composition according to the invention may also contain a single corrosion-inhibiting metal compound, or a plurality of such compounds.
  • corrosion-inhibiting metal compound in a conventional manner per se, means a compound containing a corrosion-inhibiting metal ion, in particular a corrosion-inhibiting metal cation.
  • a corrosion-inhibiting metal compound contained in the conversion composition according to the invention is a trivalent chromium salt.
  • This corrosion-inhibiting trivalent chromium salt can be chosen from fluorides, sulphates, chlorides, iodides, nitrates, acetates, carbonates, phosphates, etc., or any one of their mixtures.
  • This salt may contain, in addition to the corrosion-inhibiting trivalent chromium ion, one or more counterions.
  • trivalent chromium fluorides and trivalent chromium sulphates are particularly preferred within the scope of the invention.
  • the trivalent chromium salts used can for example be chosen from the group consisting of chromium trifluoride CrF 3 .xH 2 O, chromium sulphate Cr 2 (SO 4 ) 3 .xH 2 O, potassium chromium sulphate CrK(SO 4 ) 2 .xH 2 O, chromium trichloride CrCl 3 .xH 2 O, chromium nitrate Cr(NO 3 ) 3 .xH 2 O, chromium acetate (CH 3 CO 2 ) 2 Cr,xH 2 O, chromium hydroxide acetate (CH 3 CO 2 ) 7 Cr 3 (OH) 2 ,xH 2 O, etc.
  • the conversion composition according to the invention contains at least potassium chromium sulphate, preferably in the form of CrK(SO 4 ) 2 .xH 2 O hydrate, in particular in the form of CrK(SO 4 ) 2 dodecahydrate, 12H 2 O.
  • the conversion composition according to the invention preferably contains a concentration of between 1 and 10 g/l of corrosion-inhibiting metallic compound(s), in particular a concentration of between 1 and 10 g/l of potassium chromium sulfate dodecahydrate CrK(SO 4 ) 2 .12H 2 O.
  • the pH of the conversion composition is between 3 and 5.
  • the pH may have been adjusted within such a range of values in any manner conventional per se.
  • the conversion composition may contain a pH adjuster, in particular of the basic type, for example sodium hydroxide NaOH, in an adequate quantity to adjust the pH to the desired value.
  • a pH adjuster in particular of the basic type, for example sodium hydroxide NaOH, in an adequate quantity to adjust the pH to the desired value.
  • a particularly preferred conversion composition according to the invention contains at least one zirconium fluoride, a trivalent chromium salt, optionally sodium hydroxide, and xylenol orange.
  • the conversion composition according to the invention contains concentrations of fluorinated compound(s) and of corrosion-inhibiting metallic compound(s) such as the mass ratio of fluorinated compound(s) (s) relative to the corrosion-inhibiting metal compound(s), these compounds being distinct from each other, is between 1 and 2.5, preferably between 1 ,5 and 2.
  • concentrations of fluorinated compound(s) and of corrosion-inhibiting metallic compound(s) such as the mass ratio of fluorinated compound(s) (s) relative to the corrosion-inhibiting metal compound(s), these compounds being distinct from each other, is between 1 and 2.5, preferably between 1 ,5 and 2.
  • the composition contains several fluorinated compounds, it is the total mass of these fluorinated compounds which is taken into account here, likewise for the metallic compounds which inhibit corrosion.
  • Such a characteristic advantageously makes it possible to obtain the best performance in terms of corrosion resistance of the treated parts.
  • the corrosion-inhibiting metallic compound and the fluorinated compound present in the conversion composition according to the invention can consist of two different compounds. In variants of the invention, they consist of one and the same compound, capable of providing the two functions on its own, for example by trivalent chromium fluoride CrF 3 .
  • the viscosity of the conversion composition according to the invention is approximately 1 mPa.s.
  • the conversion composition according to the invention may optionally contain one or more thickening agent(s), preferably soluble(s) in water, making it possible to increase its viscosity.
  • Thickening agents which can be used for this purpose are, for example, cellulose or its derivatives, starch, fumed silica, polyacrylic acid, xanthan gum, etc.
  • the thickening agent(s) are preferably contained in the composition in an adequate amount to give the composition a Brookfield viscosity of between 1000 and 4000 mPa.s, preferably between 2000 and 3000 mPa.s, and preferably between 2100 and 2500 mPa.s, this viscosity being measured with a spindle type LV01 at a temperature of 23° C. and at a speed of 12 rpm.
  • the conversion composition according to the invention may contain microcrystalline cellulose or a cellulose derivative, at a concentration of between 5 and 15 g/l, for example approximately 10 g/l.
  • the conversion composition according to the invention may additionally contain one or more conventional additives per se in the field of chemical conversion compositions, for example surfactants, wetting agents, pH stabilizers, additional corrosion inhibitors , chelating/complexing agents, etc.
  • one or more conventional additives per se in the field of chemical conversion compositions for example surfactants, wetting agents, pH stabilizers, additional corrosion inhibitors , chelating/complexing agents, etc.
  • a process for preparing the conversion solution according to the invention includes the incorporation of the various compounds in the solid state in an aqueous vehicle.
  • the order of incorporation of the compounds into the vehicle is as follows: metal compound(s) corrosion inhibitor(s), then fluorinated compound(s), then coloring compound, then pH adjuster . If necessary, the thickening agent is introduced last.
  • the process for preparing the composition according to the invention is preferably carried out at ambient temperature, that is to say at a temperature of between 20 and 25° C. approximately.
  • the present invention relates to a process for the surface treatment of a metallic substrate, by forming a conversion coating on the surface of this substrate.
  • This method comprises the application of an aqueous composition according to the invention to an area of the surface of the substrate. This zone corresponds, where appropriate, to the entire surface of the substrate.
  • the metallic substrate on which the surface treatment method according to the invention is applied is in particular a substrate made of aluminum or of aluminum alloy, of magnesium or of magnesium alloy, or of steel.
  • the conversion composition is applied to the surface area of the substrate in an amount of between 5 and 100 mg/cm 2 of said surface.
  • the conversion composition contains a thickening agent, and is therefore in the form of a gel
  • it is preferably applied to the surface area of the substrate in an amount of between 10 and 100 mg/cm 2 of said surface, preferably between 30 and 80 mg/cm 2 of said surface, and preferably between 40 and 60 mg/cm 2 of said surface.
  • the conversion composition is devoid of thickening agent, and is therefore in liquid form
  • it is preferably applied to the area of the surface of the substrate in an amount of between 5 and 50 mg/cm 2 of said surface.
  • the choice of values in such ranges advantageously makes it possible to ensure, on the one hand, good visibility of the coloring of the coating formed on the surface of the substrate, and, on the other hand, good corrosion resistance properties of this coating.
  • the application of the conversion composition to the surface of the metallic substrate can be carried out in any conventional manner.
  • the conversion composition is applied to the surface of the substrate according to a so-called retouching mode, by spraying, brushing or wiping.
  • any conventional means of application can be used per se, such as a pen or a pencil, a brush, a pad, a sponge, a wipe, etc.
  • the application of the conversion composition can otherwise be carried out by immersing the substrate, in whole or in part, in said composition.
  • the contact time of the conversion composition with the metal substrate is preferably between 10 seconds and 1 hour, preferably between 30 seconds and 20 minutes, preferably between 2 and 15 minutes, preferably between 3 and 10 minutes and preferably between 3 and 8 minutes.
  • the application is preferably carried out by several series of crossed passes over the surface of the treated zone, a waiting time being preferentially provided between series of passes. successive.
  • the application can be carried out by a single continuous contact of the conversion composition on the surface of the treated area, for a contact time preferably between 30 seconds and 20 minutes, preferably between 2 and 15 minutes, preferably between 3 and 10 minutes and preferably between 3 and 8 minutes.
  • the application of the conversion composition to the surface of the substrate is preferably carried out at a temperature comprised between 5 and 40°C, preferably comprised between 15 and 30°C and preferentially comprised between 20 and 25°C.
  • the method according to the invention may comprise, before the application of the conversion composition to the surface of the substrate, any preliminary step of conventional surface preparation in itself, in particular cleaning, degreasing, pickling, mechanical, acid or basic , etc., so as to remove dirt, grease, oxides, etc. who may be present there.
  • the surface treatment method according to the invention can also be carried out on a substrate which has previously undergone an anodization treatment. It can then be qualified as a sealing process, the composition according to the invention then also being able to be designated by the terms “sealing composition”.
  • the method according to the invention may further comprise a step of drying the surface of the treated substrate.
  • Such a post-treatment method may comprise the application to the surface of the treated substrate of a composition based on a corrosion-inhibiting rare earth salt and an oxidizing compound.
  • a metallic substrate obtained at the end of a surface treatment process according to the invention.
  • This substrate comprises, on at least part of its surface, a coating, more precisely a colored conversion coating containing xylenol orange and chromium oxyfluorides and metal constituting the metal substrate.
  • This coating has a color ranging from pink to purple, depending on the amount of xylenol orange it contains.
  • the xylenol orange may be present therein in any chemical form, in particular in the form complexed with the transition metal which may enter into the constitution of the fluorinated compound contained in the conversion composition according to the invention implemented, for example in complexed form. with some zirconium.
  • the metal substrate according to the invention is preferably formed from aluminum or an aluminum alloy, magnesium or a magnesium alloy, or steel.
  • the conversion coating present on its surface is in particular formed of oxyfluorides, oxyhydroxides and hydroxides of the metal constituting the substrate and of chromium. It can for example be formed from oxides, hydroxides and oxyfluorides of aluminum and of chromium, as well as, where appropriate, of the transition metal entering into the constitution of the fluorinated salt, for example of zirconium.
  • the coating is also preferably present at the surface of the substrate in an amount of between 5 and 100 mg of coating per cm 2 of said coated surface.
  • the coating is present on the surface of the substrate in an amount comprised between 10 and 100 mg/cm 2 of said surface, preferably comprised between 30 and 80 mg/cm 2 of said surface, and preferentially between 40 and 60 mg/cm 2 of said surface.
  • This may in particular correspond to the configurations in which the conversion composition used for the surface treatment contained a thickening agent, and was therefore in the form of a gel.
  • the coating is present on the surface of the substrate in an amount of between 5 and 50 mg/cm 2 of said surface. This may in particular correspond to configurations in which the conversion composition used for the surface treatment was devoid of thickening agent, and was therefore in liquid form.
  • the substrates used are rectangular 2024-T3 aluminum alloy plates with dimensions of 125 mm ⁇ 75 mm and thickness of 1 mm.
  • the substrate is first subjected to a step of pre-treatment, by successive immersion in aqueous alkaline degreasing baths, then sodium attack then acid deoxidation, the substrate being, between each bath and after immersion in the last bath, rinsed by immersion in demineralized water for 3 min, then by spraying with demineralised water.
  • the alkaline degreasing bath is more specifically formed from the product marketed by the applicant under the name Sococlean A3432, at 10% by volume, the immersion being carried out at 55° C. for 15 min.
  • the acid deoxidation bath is more specifically formed from the product marketed by the applicant under the name Socosurf A1858/A1806, 40/10% vol, the immersion being carried out at 50° C. for 5 min.
  • the substrate is then, in all cases, subjected to a surface preparation step, by degreasing using a wipe impregnated with the product marketed by the applicant under the name Diestone DLS; then stripping in a crossed or circular manner using a fine-grained abrasive pad, impregnated with demineralized water, until a surface without breaking the water film is obtained; finally cleaning the sanded area with demineralized water by spraying, and drying by wiping.
  • the conversion composition is then applied to the chosen area of the surface of the substrate by means of crossed passages, by means of a sponge.
  • the composition is first of all applied to the entire area concerned, along a first axis of application, then it is applied along a second axis of application perpendicular to the first. After waiting 2 or 3 minutes, these successive operations are repeated, for a total of 2 or 3 series of applications.
  • the surface thus coated is then left to dry in the open air. These operations are carried out at a temperature between 15 and 30°C.
  • the substrate is first subjected to a surface preparation step, by degreasing with the product marketed by the applicant under the name Sococlean A3432, at 10% by volume, at 55° C. for 15 min, then immersion in demineralised water for 3 min, and rinsing by spraying demineralised water.
  • the substrate is then subjected to deoxidation using the product marketed by the applicant under the denomination Socosurf A1858/A1806, 40/10% vol, at 50° C. for 5 min, then rinsed again by immersion in demineralised water for 3 min and then by spraying with demineralised water.
  • the substrate thus prepared is immersed in the chemical conversion composition, at 40° C. for 10 min, then post-treated by immersion in demineralised water for 3 min and then spraying with demineralised water.
  • This test is carried out according to the protocol described in the ASTM B117 standard.
  • the substrates are exposed to salt spray, and the number of corrosion pits that appear on their surface after various exposure times is counted.
  • the criterion applied here is not to exceed 5 pits on the surface of the substrate after 96 hours of exposure to salt spray.
  • This test is carried out according to the protocol described in standard NF EN ISO 2409 (“cross cut test”). Unless otherwise indicated, the primer used is that marketed under the name MAPAERO P60. Are carried out: a dry evaluation, after 7 days of drying of the primer; and a wet evaluation, for which the substrates are immersed for 14 days in water at room temperature, then the surface is dried just before making the grid. Typical requirements are grade 0 for the dry test and grade 1 for the wet test.
  • This test is carried out according to the protocol described in the ISO 6860 standard, using a conical mandrel having an end with a smaller diameter of 7 mm.
  • the substrate is bent by 180 degrees in 2 to 3 s, at around 23° C. and at a relative humidity of around 50%, then exposed to salt spray for 3000 h.
  • the evolution of pitting corrosion at the bending zone is evaluated.
  • the appearance (uniformity) of the coating formed on the surface of the substrate following the treatment process is assessed visually, as well as the visibility of its coloring (Visib., noted out of 5, the assigned value being all the higher that the coloring is better visible).
  • the coloring compound used is xylenol orange, in accordance with the invention, and the treatment process is carried out in retouching mode.
  • the xylenol orange is tested at different concentrations ([dye]) in the conversion composition: 0.5 g/l, 1 g/l, 2.5 g/l.
  • concentration of KCr(SO 4 ) 2 .12H 2 O is 2.5 g/l.
  • Zr/Cr ratio Variation in the mass ratio of fluorinated compound relative to the corrosion-inhibiting metal compound
  • Salt spray tests are carried out after treatment with compositions in accordance with the invention containing 0.5 g/l of xylenol orange and different concentrations of K 2 ZrF 6 ([K 2 ZrF 6 ]) and KCr(SO 4 ) 2.12H 2 O ([KCr ( SO 4 ) 2.12H 2 O]).
  • compositions in accordance with the invention containing 1 g/l of xylenol orange, 4.5 g/l of K 2 ZrF 6 and 2.5 g/l of KCr(SO 4 ) 2 .12H 2 O, and of pH equal to 3.9 or 5.5, are used to treat substrates in accordance with the invention, directly or after pretreatment. Coated substrates are salt spray tested. The results obtained (in number of bites for each time of exposure to BS salt spray) are indicated in Table 4 below.
  • compositions according to the invention For two of the compositions according to the invention exhibiting the best results, salt spray resistance tests over longer periods and over a larger number of samples are carried out for substrates treated in retouching mode, directly or after pretreatment.
  • These two compositions contain 1 g/l of xylenol orange, 2.5 g/l of KCr(SO 4 ) 2 .12H 2 O and 4 g/l or 4.5 g/l of K 2 ZrF 6 .
  • All of the treated substrates show good visual surface homogeneity, and a violet coloration clearly visible to the naked eye.
  • the substrates treated with the compositions containing 1 g/l or 2 g/l of xylenol orange, 2.5 g/l of KCr(SO 4 ) 2 .12H 2 O and 4 g/l of K 2 ZrF 6 , are subjected to the paint adhesion test by gridding or bending.
  • the thickness of primer deposited on the surface of the substrate is between 25 and 40 ⁇ m.
  • Substrates treated with a composition in accordance with the invention are evaluated in a paint adhesion test using different primers: a hexavalent chromium-free primer, a chromated primer (containing hexavalent chromium) waterborne and a chromated primer (containing hexavalent chromium) solvent.
  • the test carried out is an adhesion test by dry or wet grid. The results obtained are shown in Table 7 below. For each primer tested, the thickness deposited on the surface of the substrate is specified.
  • Substrates are treated by a conversion process in retouching mode, directly or after pretreatment, with compositions containing 7.5 g/l of K 2 ZrF 6 and 4 g/l of KCr(SO 4 ) 2 .12H 2 O , and 0.5 g/l of coloring compound, xylenol orange or pyrocatechol violet.
  • Substrates are treated in retouching mode or in immersion mode, with pretreatment, by chemical conversion processes implementing different dyes at different concentrations in a composition containing 4.5 or 4.8 g/l of K 2 ZrF 6 and 2.5 or 1.9 g/l of KCr(SO 4 ) 2 .12H 2 O.
  • the visual appearance of the coated substrates is evaluated, and the substrates are subjected to the salt spray test on the one hand, and to a paint adhesion test (wet adhesion grid) on the other hand.
  • pyrocatechol violet at 0.01% w/w gives good results. to the salt spray test, but does not stain the plate. At 0.05% w/w, it colors the plate well but gives very poor results in salt spray.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Paints Or Removers (AREA)

Claims (12)

  1. Wässrige Zusammensetzung zur Oberflächenbehandlung eines Metallsubstrats, wobei die Zusammensetzung eine fluorierte Verbindung, eine korrosionshemmende Metallverbindung, ausgenommen Verbindungen auf der Basis von sechswertigem Chrom, und eine wasserlösliche Farbverbindung enthält, dadurch gekennzeichnet, dass die Farbverbindung Xylenolorange ist, die korrosionshemmende Metallverbindung ein dreiwertiges Chromsalz ist und der pH-Wert der Zusammensetzung zwischen 3 und 5 liegt.
  2. Zusammensetzung nach Anspruch 1, wobei die fluorierte Verbindung ein fluoriertes Salz eines Übergangsmetalls ist.
  3. Zusammensetzung nach Anspruch 2, wobei das Übergangsmetall aus Zirkonium und Titan ausgewählt wird.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei das dreiwertige Chromsalz aus Fluoriden und Sulfaten des dreiwertigen Chroms ausgewählt wird.
  5. Zusammensetzung nach Anspruch 4, wobei das dreiwertige Chromsalz Kaliumchromsulfat ist.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, ein Verdickungsmittel enthaltend.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, 0,5 bis 1,5 g/l Xylenolorange enthaltend.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, wobei das Massenverhältnis der fluorierten Verbindung im Vergleich zur korrosionshemmenden Metallverbindung zwischen 1 und 2,5 beträgt.
  9. Zusammensetzung nach Anspruch 8, wobei das Massenverhältnis der fluorierten Verbindung im Vergleich zur korrosionshemmenden Metallverbindung zwischen 1,5 und 2 beträgt.
  10. Verfahren zur Oberflächenbehandlung eines Metallsubstrats, dadurch gekennzeichnet, dass es das Auftragen einer Zusammensetzung nach einem der Ansprüche 1 bis 9 auf einen Bereich der Oberfläche des Substrats umfasst.
  11. Verfahren nach Anspruch 10, wobei die Zusammensetzung auf den Bereich der Oberfläche des Substrats mit einer Menge zwischen 5 und 100 mg/cm2 der Oberfläche aufgetragen wird.
  12. Metallsubstrat, erhalten durch ein Verfahren nach einem der Ansprüche 10 bis 11, auf mindestens einem Teil seiner Oberfläche eine farbige Beschichtung aufweisend, die Xylenolorange und Chromoxyfluoride und Metall enthält, das das Metallsubstrat bildet.
EP20181532.1A 2019-06-27 2020-06-23 Zusammensetzung für die oberflächenbehandlung eines metallsubstrats, und oberflächenbehandlungsverfahren, bei dem eine solche zusammensetzung zum einsatz kommt Active EP3757251B1 (de)

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DE102022105844A1 (de) * 2022-03-14 2023-09-14 Carl Freudenberg Kg Passivierungsschicht für metallhaltige Substrate
CN115142055B (zh) * 2022-07-09 2024-02-23 重庆理工大学 一种疏水化学转化成膜液及铝合金表面处理方法

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EP2859132B1 (de) * 2012-06-08 2021-08-04 PRC-Desoto International, Inc. Indikatorbeschichtungen für metalloberflächen
CN108914108A (zh) * 2013-03-16 2018-11-30 Prc-迪索托国际公司 作为腐蚀抑制剂的金属络合物
EP4039851A1 (de) * 2013-03-16 2022-08-10 PRC-Desoto International, Inc. Azolverbindungen als korrosionsinhibitoren
CN103773234B (zh) * 2014-01-10 2016-04-06 湖南金裕化工有限公司 硅烷表面处理剂及其制备方法
CN106702360A (zh) * 2016-04-16 2017-05-24 佛山瑞箭体育器材有限公司 环保表面处理剂及其制备方法
WO2017214992A1 (zh) * 2016-06-17 2017-12-21 深圳市恒兆智科技有限公司 陶化剂、金属件及其陶化处理方法
JP6837332B2 (ja) * 2016-12-28 2021-03-03 日本パーカライジング株式会社 化成処理剤、化成皮膜の製造方法、化成皮膜付き金属材料、及び塗装金属材料
EP4092087B1 (de) 2017-02-01 2025-08-13 Chemeon Surface Technology, LLC Gefärbte trivalente chromumwandlungsbeschichtungen und verfahren zu ihrer verwendung

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FR3097880B1 (fr) 2021-12-31

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