EP3728693B1 - Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques - Google Patents

Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques Download PDF

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EP3728693B1
EP3728693B1 EP18812172.7A EP18812172A EP3728693B1 EP 3728693 B1 EP3728693 B1 EP 3728693B1 EP 18812172 A EP18812172 A EP 18812172A EP 3728693 B1 EP3728693 B1 EP 3728693B1
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less
particularly preferably
composition
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total
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German (de)
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EP3728693A1 (fr
Inventor
Jerzy-Tadeusz Wawrzyniak
Dalija EHMANN
Nils BONGARTZ
Matilde SENATORE
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • the present invention relates to a multi-stage process for the anti-corrosion pretreatment of components, which is at least partially made of a metallic material composed predominantly of one or more of the elements iron, zinc and/or aluminum, in which the components are first treated with an acidic aqueous Composition (A) containing water-soluble compounds of the elements Zr and/or Ti and then brought into contact with an acidic aqueous composition (B) containing phosphate ions and an accelerator.
  • A acidic aqueous Composition
  • B acidic aqueous composition
  • the method is particularly suitable for pre-treatment before electrocoating.
  • the anti-corrosion pretreatment of metallic surfaces before subsequent painting is carried out in the prior art, depending on the desired profile of requirements and the type of paint to be applied, with different wet-chemical treatment methods, which are often based on the conversion of the metal surfaces with a homogeneous passivating coating with an inorganic material, where the inorganic material is deposited in crystalline or amorphous form by pickling the metallic substrate as a poorly soluble compound of a metal and/or semi-metal element.
  • the metal and/or semi-metal element of the inorganic material separated after the conversion of the metal surface originates either predominantly from the metal of the treated substrate, as in the case of non-layer-forming phosphating, for example iron phosphating, or from active components of these metal and/or metal elements contained in the pickling solution or semi-metal elements, such as in layer-forming phosphating, for example zinc phosphating.
  • non-layer-forming phosphating for example iron phosphating
  • active components of these metal and/or metal elements contained in the pickling solution or semi-metal elements such as in layer-forming phosphating, for example zinc phosphating.
  • layer-forming phosphating for example zinc phosphating.
  • the layer-forming phosphating provides at least partially crystalline phosphate coatings, the layer coverage of which is regularly above 1.5 g/m 2 .
  • Phosphating in particular is very well established in terms of process technology and is still an important anti-corrosive pre-treatment method before electrocoating components made of metallic materials made of the elements iron, zinc and/or aluminum, despite the complex reprocessing of the phosphating bath and the rinsing water and the phosphate sludge that forms during processing are made.
  • non-layer-forming phosphating which is particularly well mastered for ferrous materials and provides homogeneous, thin, amorphous coatings.
  • the non-layer-forming phosphating is significantly less is material-intensive and can be operated with less effort in the treatment of the phosphating bath and the rinsing water because of the lower phosphate load.
  • the DE 44 17 965 A1 describes such a phosphating solution for the non-layer-forming phosphating of surfaces made of steel, zinc and/or aluminum, with layers of phosphating in the range of 0.5-1 g/m 2 being to be achieved in particular on the iron surfaces, while on surfaces of the materials which are mainly composed of zinc and aluminum, a moderate pickling takes place, which increases the roughness and is beneficial for the subsequent paint layer build-up on these materials.
  • the phosphating bath must contain dissolved phosphate, nitrobenzene sulfonic acid as an accelerator and monocarboxylic acids specified there.
  • the phosphating baths can also contain other auxiliaries, for example free and/or complex-bound fluoride.
  • the first task is to reduce the phosphate sludge produced in the non-layer-forming phosphating and in processes with subsequent electrocoating to reduce the required layer thickness while maintaining the same corrosion resistance.
  • Another important aspect is to improve the passivation achieved with the non-layer-forming phosphating for subsequent electrocoating in such a way that, in the case of more complex components, the coating coverage in areas of the component that are largely shielded from the electrical field of the electrocoating is increased.
  • the DE 10 2009 047523 A1 The task is also to establish a process for anti-corrosion pretreatment that is suitable for the subsequent application of organic paint systems, does not include any electrolytic process steps and in which the deposition of small amounts of active components is sufficient for effective corrosion protection without significant amounts of deposit these active components in the treatment bath due to precipitation reactions due to the process.
  • the object is achieved there by a multi-stage process in which the surfaces of zinc, after cleaning and degreasing, undergo a passivating treatment using compositions containing water-soluble compounds of the elements zirconium, titanium and/or hafnium and copper ions and then electroless with a composition containing at least 100 ppm of nickel ions are treated.
  • a "metallic material” is predominantly composed of one or more of the elements iron, zinc and/or aluminum if the sum of these elements in the material is greater than 50 at.%, preferably greater than 80 at.%.
  • Such materials are steel, iron, zinc, aluminum, for example as a die-cast alloy, but also substrates plated with metallic coatings in a layer thickness of at least 1 ⁇ m, the metallic coating then being a material in the context of the present invention.
  • Such coatings are, for example, in electrolytically or hot-dip galvanized steel, or plating in the form of zinc (Z), aluminum-silicon (AS), zinc-magnesium (ZM), zinc-aluminum (ZA), aluminum-zinc (AZ) or Zinc-iron (ZF) realized.
  • the invention is characterized in that the materials mentioned are provided with a passivation that protects against corrosion, which offers excellent corrosion protection and paint adhesion, especially on those materials that consist predominantly of the element iron (so-called "ferrous materials"), for example on steel .
  • Steel includes metallic materials whose mass fraction of iron is greater than that of any other element and whose carbon content is less than 2.06% by weight without taking carbides into account.
  • the method according to the invention therefore includes the anti-corrosion pretreatment of metallic surfaces of a component which consists at least partially of a metallic material which is predominantly composed of the element iron.
  • a further preferred embodiment of the method according to the invention is characterized in that metallic surfaces of such components are pretreated, which consist of more than one metallic material, the predominant is composed of one or more of the elements iron, zinc and/or aluminum (so-called "composite construction"), in particular those components that consist at least partially of an iron material and in composite construction with a material that consists predominantly of one or both of the Elements composed of zinc and/or aluminum are produced.
  • the components treated according to the present invention can be any three-dimensional structure of any shape and design that originates from a manufacturing process, in particular semi-finished products such as strips, sheet metal, rods, pipes, etc. and composite structures assembled from the aforementioned semi-finished products, the semi-finished products preferably being assembled by gluing, Welding and / or flanging are connected to the composite structure.
  • semi-finished products such as strips, sheet metal, rods, pipes, etc.
  • composite structures assembled from the aforementioned semi-finished products the semi-finished products preferably being assembled by gluing, Welding and / or flanging are connected to the composite structure.
  • the total proportion of water-soluble compounds of the elements Zr and/or Ti in the acidic aqueous composition (A) of the process according to the invention is at least 0.05 mmol/kg, particularly preferably at least 0.1 mmol/kg, very particularly preferably at least 0.2 mmol/kg, with a total of preferably not more than 1.5 mmol/kg, particularly preferably not more, for economic reasons and to avoid overpickling of the conversion layer than 1.0 mmol/kg of water-soluble compounds of the elements Zr and/or Ti are contained in an acidic aqueous composition (A) of the process according to the invention.
  • water-soluble includes compounds which at 20° C. have a solubility in deionized water ( ⁇ 1 ⁇ Scm ⁇ 1 ) of at least 1 g/kg.
  • Suitable representatives of the water-soluble compounds of the elements Zr and/or Ti which can be contained in the acidic aqueous composition (A), are compounds which dissociate into anions of fluorocomplexes in aqueous solution.
  • Examples of such preferred compounds are H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds.
  • Fluorine-free compounds of the elements Zr or Ti, in particular the element Zr can also be used according to the invention as water-soluble compounds, for example (NH 4 ) 2 Zr(OH) 2 (CO 3 ) 2 or TiO(SO 4 ).
  • the acidic aqueous composition contains fluorometalates of the elements Zr and/or Ti and their fluoroacids, particularly preferably hexafluorozirconates and/or hexafluorotitanates and their free acids.
  • the respective water-soluble compounds of the element Zr are to be used with preference over the compounds of the element Ti.
  • the one acidic composition (A) in process step (I) of the process according to the invention contains a source for fluoride ions.
  • Any inorganic compound capable of releasing fluoride ions dissolved or dispersed in water is suitable as a source of fluoride ions.
  • One preferred sources of fluoride ions are complex or simple fluorides. The skilled worker understands simple fluorides to mean hydrofluoric acid and salts thereof such as alkali metal fluorides, ammonium fluoride or ammonium bifluoride, while complex fluorides according to the invention represent coordination compounds in which fluorides are present as coordinated ligands of one or more central atoms. Accordingly, preferred representatives of the complex fluorides are the aforementioned fluorine-containing complex compounds of the elements Zr and/or Ti.
  • the proportion of compounds that represent a source of fluoride ions is preferably at least so large in an acidic aqueous composition of the method according to the invention that an amount of free fluoride of at least 1 mg/kg, particularly preferably at least 10 mg/kg, but preferably not more than 100 mg/kg in the acidic aqueous composition (A).
  • the free fluoride content is determined directly in the acidic aqueous composition (A) at 20° C. using a calibrated fluoride-sensitive electrode. If the free fluoride content is referred to below, it must always be determined directly in the relevant composition in an analogous manner.
  • the molar ratio of the total fluoride content to the total amount of the elements Zr and/or Ti is greater than 4, 5, preferably greater than 5.0, more preferably greater than 5.5.
  • the total fluoride content is determined with a fluoride-sensitive electrode in a TISAB-buffered aliquot of an acidic aqueous composition (A) of the method according to the invention at 20 ° C (TISAB: "Total Ionic Strength Adjustment Buffer"), the volume-based mixing ratio of buffer to the aliquot of the acidic aqueous composition (A) is 1:1.
  • the TISAB buffer is prepared by dissolving 58 g NaCl, 1 g sodium citrate and 50 ml glacial acetic acid in 500 ml deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and adjusting the pH to 5.3 using 5 N NaOH and making up to a total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ). If the total fluoride content is referred to below, it must always be determined in an analogous manner for the composition in question.
  • a first conversion of the metal surface of the component to be pretreated according to the invention with an anti-corrosion coating based on the elements Zr and/or Ti takes place in the acidic aqueous composition (A).
  • Optimum process results require a balance between pickling and deposition rates that leads to coatings that are ideally suited for the subsequent non-layer-forming phosphating.
  • the pH of the acidic aqueous composition (A) in process step (I) is preferably less than 5.8, more preferably less than 5.2, but preferably not less than 3.9, more preferably not less than 4.2, since even low pickling rates are sufficient to bring about sufficient conversion of the metal surfaces.
  • the acidic aqueous composition (A) has a free acid content of at least 1 point, but particularly preferably of less than 5 points.
  • the free acid is determined by diluting 2 ml of the acidic aqueous composition (A) to 50 ml with deionized water ( ⁇ 1 ⁇ Scm -1 ), titrating with 0.1 N sodium hydroxide solution to a pH of 4.0 .
  • the consumption of acid solution in ml gives the score of the free acid. If the free acid content in points is referred to below, this must always be determined in an analogous manner for the composition in question.
  • the acidic aqueous composition (A) for accelerating the conversion of the metal surfaces which are brought into contact with the acidic composition (A) in process step (I) additionally contains at least one water-soluble compound which is a source of Represents copper ions, preferably in the form of a water-soluble salt, for example copper sulphate, copper nitrate and copper acetate.
  • copper ions preferably in the form of a water-soluble salt, for example copper sulphate, copper nitrate and copper acetate.
  • the content of copper ions from water-soluble compounds in the acidic aqueous composition (A) is preferably at least 0.001 g/kg, particularly preferably at least 0.005 g/kg.
  • the content of copper ions is preferably not above 0.1 g/kg, particularly preferably not above 0.05 g/kg, since otherwise the deposition of elemental copper begins to dominate over the formation of the conversion layer.
  • the acidic aqueous composition (A) in the method according to the invention additionally contains at least one water-soluble compound which has a standard reduction potential at pH 0 above +0.2 V (SHE).
  • Water-soluble compounds which have such a standard reduction potential are preferably selected from inorganic nitrogen compounds, particularly preferably from nitric acid and/or nitrous acid and salts thereof.
  • the proportion of water-soluble compounds for accelerating the formation of the conversion layer is preferably at least 1 mmol/kg, preferably at least 10 mmol/kg, but for reasons of economy preferably less than 200 mmol/kg based on the acidic aqueous composition (A).
  • the acidic aqueous composition (A) in process step (I) may contain at least one aliphatic saturated polyhydroxy compound having at least 4 but not more than 8 carbon atoms.
  • the acidic aqueous composition (A) is able to free the surfaces of the component from organic contaminants without adversely affecting the formation of the conversion layer. This makes processes according to the invention accessible which develop a cleaning effect in process step (I) and therefore may not have to resort to a preceding cleaning stage.
  • the aliphatic polyhydroxy compound to be used in this context is an aliphatic compound having more than two hydroxyl groups, preferably more than three hydroxyl groups, with at least two hydroxyl groups preferably being linked to one another by no more than two carbon atoms ("vicinal hydroxyl -Groups").
  • Particularly preferred polyhydroxy compounds are alditols, which in turn preferably have no more than 6 carbon atoms and are particularly preferably selected from erythritol, threitol, xylitol, arabitol, ribitol, mannitol or sorbitol, and are particularly preferably sorbitol.
  • a preferred acidic aqueous composition (A) containing the polyhydroxy compound preferably additionally contains at least one aliphatic diol which has at least 4 carbon atoms but not more than 10 carbon atoms.
  • the aforementioned aliphatic diols are preferably selected from diols whose hydroxyl groups are linked to one another via no more than 3 carbon atoms, and particularly preferably from acyclic alkanediols which have no more than 8 carbon atoms, but preferably at least 5 carbon atoms, and particularly preferably 2-methylpentane -2,4-diol.
  • the acidic aqueous composition (A) in process step (I) contains at least 0.01% by weight of the aliphatic saturated polyhydroxy compound and optionally at least 0.003% by weight of the aliphatic diol.
  • Excellent cleaning performance is achieved when the mass-related ratio of the aforementioned polyhydroxy compounds to the aforementioned aliphatic diols is at least 0.4. Such a relative minimum amount of polyhydroxy compounds is therefore preferred in acidic aqueous compositions (A) in the process of the invention.
  • the aforementioned ratio is particularly preferably at least 1.0, particularly preferably at least 2.0. If the relative proportions of the aforementioned polyhydroxy compounds are too high, the good cleaning performance cannot be maintained with an otherwise constant total amount of active components, and the simultaneous conversion of the metal surface also loses homogeneity.
  • the mass-related ratio of the aforementioned polyhydroxy compounds to the aforementioned diols in the preferred acidic aqueous composition (A) is not greater than 20.0, particularly preferably not greater than 10.0, very particularly preferably not is greater than 6.0.
  • an acidic aqueous composition (A) which additionally contains the aforementioned mixture of aliphatic diols and aliphatic saturated polyhydroxy compounds
  • a preceding cleaning step can be dispensed with entirely.
  • there is therefore no wet-chemical cleaning immediately before the component is brought into contact with the preferred acidic aqueous composition (A) containing the aforementioned mixture of aliphatic diols and aliphatic saturated polyhydroxy compounds in method step (II). of the component especially not if the bringing into contact takes place by spraying or spraying on.
  • wet-chemical cleaning is cleaning by bringing it into contact with a water-based composition which contains at least 0.1% by weight of surfactants and/or wetting agents in total, with surfactants and/or wetting agents comprising all organic compounds which Decreasing the surface tension of water at 20 °C and a proportion of 0.1% by weight determined using the Wilhelmy plate method.
  • An important advantage of a method according to the invention which also contains a mixture of aliphatic diols and aliphatic saturated polyhydroxy compounds based on the bringing into contact with an acidic aqueous composition (A), is that cleaning the metallic surfaces of the component from Auxiliaries based on organic compounds such as anti-corrosion oils, cutting oils and cooling lubricants from upstream production stages can be achieved even at relatively low working temperatures.
  • the acidic aqueous composition (A) is therefore brought into contact at a temperature of the composition of less than 40° C., particularly preferably less than 35° C., particularly preferably less than 30° C, but preferably at least 20°C.
  • the acidic aqueous composition (A) is brought into contact in the process according to the invention by spraying or injecting, particularly preferably by spraying, particularly preferably at an injection pressure of at least 1 bar, in order to achieve optimal cleaning and to achieve rapid conversion of the metal surfaces.
  • the acidic aqueous composition (B) contains a total of less than 1 g/kg, particularly preferably less than 0.2 g/kg, of organic polymers.
  • Organic polymers in this sense have a molecular weight of at least 1000 g/mol determined on the basis of molecular weight distribution curves measured using gel permeation chromatography (GPC) with an RI detector after calibration using polystyrene standards after elution with tetrahydrofuran at an eluate temperature in the detector of 40 °C.
  • GPC gel permeation chromatography
  • the acidic aqueous composition (A) in process step (I) is “phosphate-free” and/or “chromium-free”.
  • a composition is "phosphate-free” if the proportion of phosphates dissolved in water is less than 100 mg/kg, preferably less than 20 mg/kg, calculated as the amount of phosphorus.
  • a composition is "chromium(VI)-free” if the proportion of compounds of the element chromium dissolved in water in the +VI oxidation state is less than 100 mg/kg, preferably less than 20 ppm.
  • the component has been brought into contact with the acidic aqueous composition (A) in process step (I) - with or without an intermediate rinsing and/or drying step, preferably with a rinsing step, but particularly preferably without a drying step - takes place in the process according to the invention contacting with the acidic aqueous composition (B) in the non-layer phosphating process step (II).
  • the two wet-chemical process steps (I) and (II) can also follow one another directly in a particularly optimized process sequence and therefore in a particularly preferred method according to the invention, without an intermediate rinsing step or an intermediate drying step taking place.
  • a "rinsing step" in the sense of the present invention denotes a process which is solely intended to remove active components from an immediately preceding wet-chemical treatment step, which are present dissolved in a wet film adhering to the component, from the surface of the component as far as possible by means of a rinsing solution, without the active components to be removed being replaced by others.
  • Active components in this context are constituents contained in a liquid phase, which cause an analytically verifiable coating of the metal surfaces of the component with elementary constituents of the active components.
  • a “drying step” within the meaning of the present invention refers to a process in which the surfaces of the metallic component that have a wet film are to be dried with the aid of technical measures, for example supplying thermal energy or transferring an air stream.
  • the modification of the metallic surfaces of the component produced in process step (II) by bringing them into contact with the composition (B) causes a coating with phosphates.
  • a layer weight of at least 0.1 g/m 2 , particularly preferably at least 0.2 g/m 2 is preferably achieved on at least one of the metallic surfaces, in particular on a surface of a ferrous material.
  • the preferred non-layer-forming phosphating is switched off in the process according to the invention, activation of the metal surfaces is not necessary.
  • process steps (I) and (II) follow one another directly - with or without an intermediate rinsing step.
  • the layer weight of phosphates is determined according to the invention after removing the phosphate coating with aqueous 5% by weight CrOs pickling solution at 25° C. for 5 minutes and determining the phosphorus content in the same pickling solution using plasma-coupled optical emission spectroscopy (ICP-OES).
  • ICP-OES plasma-coupled optical emission spectroscopy
  • the treatment temperature, the treatment time or the concentration of the phosphate ions or the accelerator can be increased.
  • compositions (B) which are essentially free of dissolved compounds of the element Ni, preferably essentially free of dissolved compounds of the elements Ni, Co and Cu and particularly preferably essentially free of dissolved compounds of the elements Ni, Co, Cu and Mn.
  • compositions (B) are essentially free of these heavy metals if their total content is less than 100 ppm, preferably less than 10 ppm, based on the composition.
  • water-soluble organic or inorganic compounds whose standard reduction potential is greater than +0.2 V (SHE) can preferably be used as the accelerator contained in the composition (B).
  • Suitable accelerators are preferably selected from organic or inorganic compounds containing at least one non-metal atom selected from nitrogen, phosphorus, oxygen, sulfur, chlorine and/or bromine in an oxidation state that does not correspond to the lowest possible level of the element in question, or at least one oxoanion of an element of Subgroup VIB or VIIB of the periodic table.
  • the oxidation state of an atom that is part of a compound is defined for the purposes of the present invention as that hypothetical charge on the atom that it would have if only those bonding electrons were fully attributed to the atom that are shared with atoms that have a lower electronegativity , while bond electrons shared with atoms of equal electronegativity would be attributed to the atom assuming homolytic bond separation, using the general IUPAC rules for determining the oxidation state ("Oxidation State", IUPAC, Compendium of Chemical Terminology, Gold Book, version 2.3.3, page 1049).
  • Preferred accelerators based on non-metal atoms selected from nitrogen, phosphorus, oxygen, sulfur, chlorine and/or bromine in an oxidation state that does not correspond to the lowest possible level of the respective element are nitrates, chlorates, bromates, aromatic nitro compounds such as nitrobenzenesulfonic acid, in particular m -Nitrobenzenesulfonic acid, nitroarginine, 5-nitro-2-furfurylidenedicarboxylic acid, N-methylmorpholine-N-oxide, hydroxylamine, nitroguanidine, hydrogen peroxide.
  • Preferred accelerators based on the oxoanions of an element from subgroup VIB or VIIB of the periodic table are selected from molybdates, tungstates and/or manganates, particularly preferably from molybdates and/or tungstates.
  • compositions (B) that preferably have a total of at least 0.1 mmol/kg, particularly preferably a total of at least 0.2 mmol/kg, very particularly preferably a total of at least 0.4 mmol/kg of accelerators, but preferably a total of no more than 5 mmol/kg, particularly preferably a total of no more than 2 mmol/kg, very particularly preferably a total of no more than 1 mmol /kg of accelerators.
  • the proportion of phosphates in the composition should bring about adequate coverage at least of the surfaces of the materials, which are predominantly composed of iron.
  • the composition (B) contains at least 0.5 g/kg, particularly preferably at least 1 g/kg, of phosphate ions.
  • the composition (B) contains no more than 10 g/kg, particularly preferably no more than 4 g/kg, of phosphate ions contains.
  • composition (B) additionally contains complexing agents, preferably selected from ⁇ -hydroxycarboxylic acids, preferably having at least 4 but not more than 8 carbon atoms, particularly preferably selected from citric acid, tartaric acid and/or gluconic acid and contains their water-soluble salts.
  • complexing agents preferably selected from ⁇ -hydroxycarboxylic acids, preferably having at least 4 but not more than 8 carbon atoms, particularly preferably selected from citric acid, tartaric acid and/or gluconic acid and contains their water-soluble salts.
  • the composition (B) therefore contains at least 10 mg/kg, but preferably not more than 100 mg/kg, very particularly preferably not more than 50 mg/kg, of iron ions. This applies in particular to the treatment of metallic components that are at least partially made of a ferrous material.
  • the mordanting effect of the composition (B) is in the method according to the invention, however, with the preceding conversion treatment based on the elements Zr and/or Ti, so that the pH of the composition is preferably not less than 4.0, more preferably not less than 4.4, and most preferably not less than 4.8 to minimize corrosion of the conversion coating.
  • the total acidity of the composition (B) is also an important control parameter. This should preferably be at least 1 point, particularly preferably at least 3 points, to provide a certain buffer capacity, but preferably not to avoid overpickling of the conversion-treated metallic surfaces of the component greater than 16 points, particularly preferably not greater than 9 points.
  • the total acidity in points is determined within the scope 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 8.5. The consumption of milliliters of caustic soda indicates the number of points.
  • the proportion of water-soluble compounds that release fluoride ions is low.
  • small amounts of such compounds, in particular complex-bound fluorides are tolerated, so that in a preferred embodiment of the process according to the invention, a rinsing step immediately after process step (I) and immediately before process step (II) can be dispensed with.
  • the proportion of free fluoride in the aqueous composition is less than 10 mg/kg, particularly preferably less than 5 mg/kg, very particularly preferably less than 1 mg/kg.
  • the total fluoride content in the composition (B) is also less than 100 mg/kg, preferably less than 50 mg/kg, particularly preferably less than 10 mg/kg.
  • the composition (B) should preferably contain less than 1 g/kg, more preferably less than 0.5 g/kg, most preferably less than 0.2 g/kg of zinc contain ions.
  • the presence of organic polymeric components in the composition (B) can be tolerated to a certain extent, for example for complexing metal ions.
  • the presence of polymeric components usually makes bath care considerably more difficult and can prevent the formation of an amorphous phosphate layer or at least shift it to the disadvantage of a coating consisting essentially of polymeric components. It is therefore preferred according to the invention if the acidic aqueous composition (B) contains a total of less than 1 g/kg, particularly preferably less than 0.2 g/kg, of organic polymers.
  • Organic polymers in this sense have a molecular weight of at least 1,000 g/mol, determined using molecular weight distribution curves measured using gel permeation chromatography (GPC) with an RI detector after calibration using polystyrene standards after elution with tetrahydrofuran at an eluate temperature in the detector of 40 °C .
  • GPC gel permeation chromatography
  • the acidic aqueous composition (B) in process step (II) is “chromium-free”.
  • cathodic electrocoating preferably being based on an aqueous dispersion of an amine-modified film-forming polyepoxide, which preferably also contains blocked and/or unblocked isocyanate groups-containing organic compounds as hardeners and, if appropriate, small amounts of in the aqueous Phase contains dissolved compounds of the elements yttrium and / or bismuth.
  • a process sequence according to the invention for pretreatment (A2a-B1-B2-A3) comprising the cleaning conversion treatment A2 followed by the phosphating A3 with a conventional process sequence (A1-B1-B2-A2b) comprising alkaline cleaning and compared to conversion treatment.
  • the conventional pretreatment produces a layer thickness of about 20 ⁇ m in the dip coating, whereas with the pretreatment according to the invention a dip coating layer thickness of 8 ⁇ m resulted in homogeneous coverage.
  • a conventional phosphating according to process step A3 without prior conversion treatment requires a comparatively longer phosphating time to achieve similarly low layer thicknesses and causes a significantly higher load with phosphate sludge in the technical implementation in series production.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (15)

  1. Procédé de prétraitement de protection contre la corrosion des surfaces métalliques d'un composant constitué au moins partiellement d'un matériau métallique composé principalement d'un ou de plusieurs des éléments fer, zinc et/ou aluminium, comprenant les étapes de procédé successives suivantes :
    I) mise en contact du composant avec une composition aqueuse acide (A) contenant au moins un composé hydrosoluble des éléments Zr et/ou Ti ;
    II) mise en contact du composant avec une composition aqueuse acide (B) contenant des ions phosphate et un accélérateur dont la teneur totale en composés dissous de l'élément Ni est inférieure à 100 ppm,
    un revêtement comportant des phosphates et conduisant à un poids de couche de plus de 1 g/m2 calculé comme PO4 n'étant obtenu sur aucune des surfaces métalliques du composant.
  2. Procédé selon la revendication 1, caractérisé en ce que la composition (A) contient au moins 0,05 mmol/kg, de préférence au moins 0,1 mmol/kg, de manière particulièrement préférée au moins 0,2 mmol/kg, mais de préférence pas plus de 1,5 mmol/kg, de manière particulièrement préférée pas plus de 1,0 mmol/kg, de composés hydrosolubles des éléments Zr et/ou Ti par rapport auxdits éléments.
  3. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que le pH de la composition (A) est inférieur à 5,8, de préférence inférieur à 5,2, mais de préférence non inférieur à 3,9, de manière particulièrement préférée non inférieur à 4,2.
  4. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (A) contient en outre une source hydrosoluble d'ions fluorure en une quantité telle que la proportion de fluorure libre est d'au moins 1 mg/kg, de préférence d'au moins 10 mg/kg, mais de préférence ne dépasse pas 100 mg/kg.
  5. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (A) contient en outre un composé aliphatique comportant plus de deux groupes hydroxyle, de préférence contient plus de trois groupes hydroxyle, de préférence au moins deux groupes hydroxyle étant liés l'un à l'autre par l'intermédiaire de pas plus de deux atomes de carbone, de manière tout particulièrement préférée un alditol comportant de préférence pas plus de 6 atomes de carbone.
  6. Procédé selon la revendication 5, caractérisé en ce que la composition (A) en outre au moins un diol aliphatique, lequel présente de préférence au moins 4 atomes de carbone, mais de manière particulièrement préférée pas plus de 10 atomes de carbone.
  7. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (B) contient au moins 0,5 g/kg, de préférence au moins 1 g/kg, d'ions phosphate, mais de préférence pas plus de 10 g/kg, de manière particulièrement préférée pas plus de 4 g/kg, d'ions phosphate.
  8. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'accélérateur dans la composition (B) est choisi parmi au moins un composé organique ou inorganique hydrosoluble dont le potentiel standard de réduction est supérieur à +0,2 V (SHE).
  9. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'accélérateur dans la composition (B) est choisi parmi les composés organiques ou inorganiques contenant au moins un atome non métallique choisi parmi l'azote, le phosphore, l'oxygène, le soufre, le chlore et/ou le brome à un degré d'oxydation qui ne correspond pas au plus bas degré d'oxydation possible de l'élément respectif, ou au moins un oxoanion d'un élément du sous-groupe VIB ou VIIB du tableau périodique
  10. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la composition (B) contient au total au moins 0,1 mmol/kg, de préférence au total au moins 0,2 mmol/kg, de manière particulièrement préférée au total au moins 0,4 mmol/kg, d'accélérateurs, mais de préférence au total pas plus de 5 mmol/kg, de manière particulièrement préférée au total pas plus de 2 mmol/kg, de manière tout particulièrement préférée au total pas plus de 1 mmol/kg, d'accélérateurs.
  11. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que le pH de la composition (B) est inférieur à 6,0, de préférence inférieur à 5,2, mais de préférence non inférieur à 4,0, de manière particulièrement préférée non inférieur à 4,4, et de manière tout particulièrement préférée non inférieur à 4,8.
  12. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la proportion de composés hydrosolubles libérant des ions fluorure dans la composition (B) est inférieure à 10 mg/kg, de préférence inférieure à 5 mg/kg, de manière particulièrement préférée inférieure à 1 mg/kg, et de préférence la proportion totale de fluorure est inférieure à 100 mg/kg, de manière particulièrement préférée inférieure à 50 mg/kg, de manière tout particulièrement préférée inférieure à 10 mg/kg.
  13. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la proportion d'ions zinc dans la composition (B) est inférieure à 1 g/kg, de préférence inférieure à 0,5 g/kg, de manière particulièrement préférée inférieure à 0,2 g/kg.
  14. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que l'étape de procédé II) est suivie d'un vernissage à base d'un agent filmogène organique, de préférence d'un vernissage par électrodéposition, de manière extrêmement préférée d'un vernissage par électrodéposition cathodique.
  15. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que le composant est au moins partiellement constitué d'un matériau ferreux et est de préférence fabriqué en tant que structure composite comportant un matériau composé principalement de l'un ou des deux des éléments zinc et/ou aluminium.
EP18812172.7A 2017-12-20 2018-12-06 Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques Active EP3728693B1 (fr)

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PCT/EP2018/083761 WO2019121036A1 (fr) 2017-12-20 2018-12-06 Procédé de prétraitement anticorrosion et nettoyant de pièces métalliques

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DE4417965A1 (de) * 1994-05-21 1995-11-23 Henkel Kgaa Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
US6723178B1 (en) * 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
DE10131723A1 (de) * 2001-06-30 2003-01-16 Henkel Kgaa Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen
DE102006052919A1 (de) * 2006-11-08 2008-05-15 Henkel Kgaa Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen
DE102009047523A1 (de) * 2009-12-04 2011-06-09 Henkel Ag & Co. Kgaa Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zinnoberflächen
DE102009047522A1 (de) * 2009-12-04 2011-06-09 Henkel Ag & Co. Kgaa Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen
US20130230425A1 (en) * 2011-09-02 2013-09-05 Ppg Industries Ohio, Inc. Two-step zinc phosphating process
CN105324517B (zh) * 2013-06-20 2017-10-27 汉高股份有限及两合公司 用于电沉积的多步方法
DE102014225237B3 (de) * 2014-12-09 2016-04-28 Henkel Ag & Co. Kgaa Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie
DE102015209909A1 (de) * 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Konditionierung vor einer Konversionsbehandlung von Metalloberflächen
US10435806B2 (en) * 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions

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WO2019121036A1 (fr) 2019-06-27
EP3502311A1 (fr) 2019-06-26
EP3728693A1 (fr) 2020-10-28
CN111527238A (zh) 2020-08-11
US11408078B2 (en) 2022-08-09
ES2958039T3 (es) 2024-01-31

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