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EP3218531B1 - Procédé d'élimination sélective d'ions zinc de solutions de bain alcalines dans le traitement de surface de composants métalliques en série - Google Patents

Procédé d'élimination sélective d'ions zinc de solutions de bain alcalines dans le traitement de surface de composants métalliques en série Download PDF

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Publication number
EP3218531B1
EP3218531B1 EP15797897.4A EP15797897A EP3218531B1 EP 3218531 B1 EP3218531 B1 EP 3218531B1 EP 15797897 A EP15797897 A EP 15797897A EP 3218531 B1 EP3218531 B1 EP 3218531B1
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EP
European Patent Office
Prior art keywords
bath solution
zinc
alkaline
ion exchange
ions
Prior art date
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EP15797897.4A
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German (de)
English (en)
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EP3218531A1 (fr
Inventor
Jan-Willem Brouwer
Fernando Jose Resano ATALEJO
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL15797897T priority Critical patent/PL3218531T3/pl
Publication of EP3218531A1 publication Critical patent/EP3218531A1/fr
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/77—Controlling or regulating of the coating 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
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C22/86—Regeneration of coating baths

Definitions

  • the present invention relates to a method for the serial surface treatment of metallic components having zinc surfaces, the method comprising an alkaline pretreatment and a method for the selective removal of zinc ions from an alkaline bath solution for the serial surface treatment of metallic surfaces having zinc surfaces.
  • a part of the respective alkaline bath solution is brought into contact with an ion exchange resin, the functional groups selected from -OPO 3 X 2 / n and / or -PO 3 X 2 / n , where X is either a hydrogen atom or a exchanged alkali and / or alkaline earth metal atom with the respective valence n represents carries.
  • the cleaning and surface conditioning of metal parts prior to their further processing is a standard task in the metalworking industry.
  • the metal parts may be contaminated, for example, with pigment dirt, dust, metal abrasion, corrosion protection oils, cooling lubricants or forming aids.
  • a corrosion protection treatment eg phosphating, chromating, reaction with complex fluorides, etc.
  • these impurities must be removed by a suitable cleaning solution.
  • the cleaning should also fulfill the task that the metal surfaces are preconditioned for the subsequent corrosion protection treatment.
  • the preconditioning is a type of activation of the metal surfaces, which leads in particular to a subsequent wet-chemical conversion treatment to homogeneous inorganic, corrosion-protective coatings with sufficient layer thickness.
  • Such preconditioning or activation is initiated by a pickling process and may further include occupying the metal surfaces with foreign metal elements.
  • a preconditioning known in the prior art which brings about an improvement in the corrosion protection properties in subsequent conversion treatment, is, for example, the alkaline icing of galvanized steel, which is described in US Pat DE 102010001686 is described in detail.
  • the industrial cleaners or activation baths such as the above-mentioned icing, are generally alkaline in wet-chemical pretreatment prior to a conversion treatment and have pH values in the range above 7, for example 9 to 12. Its basic components are in addition to dissolved iron ions, alkalis and complexing agents. Frequently, the cleaners contain nonionic and / or anionic surfactants as additional auxiliary components.
  • the alkalis in these baths contribute to its detergency by saponifying and solubilizing impurities such as fats, or by surface activation by pickling the metallic surfaces.
  • impurities such as fats
  • surface activation by pickling the metallic surfaces.
  • alkalinity is consumed, so that the cleaning effect decreases in a surface treatment of components in series with time. Therefore, it is common to check the alkalinity of the cleaning baths at certain times and, if necessary, supplement or completely renew the solution with new active ingredients.
  • Such a process for the refreshment of the alkalinity is in the EP 1051672 described. The same applies in the case of the alkaline icing of metallic components in series for the iron ions and complexing agents that are consumed or removed from the bath.
  • the WO 2014/0675234 therefore teaches a maximum concentration of free zinc ions, which should not be exceeded for the quality of subsequent processes.
  • To remove zinc (II) ions from industrial cleaning and icing solutions is described in the WO2014 / 0675234 described the addition of sodium sulfide. Although the addition of such agents can effectively stabilize and regulate zinc ion concentration, the use of sulfides to remove zinc ions in the form of zinc sulfide is often undesirable due to odor formation by the side-by-side reaction of hydrogen sulfide.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • complexing agents such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP; CAS No. 2809-21-4), which complex polyvalent metal cations, in particular zinc, iron and aluminum ions, and thereby the Accelerate pickling attack on the surface, but is only partially suitable to get to the process-related high content of zinc ions in solution.
  • HEDP binds nonspecifically in addition to zinc (II) - both aluminum (III) - and iron (III) ions, reducing the amount of free HEDP that is needed to both zinc and aluminum in the form of their complexes to be kept sufficiently in solution, must be drastically increased, which suffers both effectiveness and economy of the pickling and icing process.
  • the present invention is intended to provide a method, optimized in terms of effectiveness and quality of the corrosion protection achieved, for the wet-chemical surface treatment of metallic components in series comprising zinc surfaces, in which the components are set in a first step.
  • compounds are water-soluble if their solubility in deionized water having a conductivity of not more than 1 ⁇ Scm -1 at a temperature of 20 ° C. is at least 1 g / l.
  • the contacting of a plurality of metallic components with the alkaline bath solution stored in the system tank for wet-chemical pretreatment does not involve a complete replacement with a new batch of the alkaline bath solution of the system tank after each pretreatment of a single metallic component.
  • a container understood that stores a bath solution for bringing in contact with the metallic components.
  • the metallic component can be passed through a system tank so as to be brought into contact with the bath solution, or at least part of the bath solution for bringing into contact with the metallic component from the system tank is temporarily fed out, in order to Contacting, for example after spray application, at least partially to be fed back into the system tank.
  • the process for the selective removal of zinc ions from an alkaline bath solution containing iron (III) ions and complexing agent Y as active components and an amount of zinc ions etched out of the metallic components is therefore based on a preparation using a specific ion exchange resin. Surprisingly, only zinc ions are removed, while the iron (III) ions remain in solution in the presence of the complexing agent Y in solution in the bath.
  • the molar ratio of complexing agent Y relative to the element phosphorus to the total amount of iron (III) ions and zinc (II) ions in the bath solution is greater than 1, 5, preferably greater than 2.0, so that a molar excess of the functional groups of the complexing agent Y to the iron and zinc ions is ensured.
  • a much higher molar ratio in the bath solution is less efficient because it uses significantly more complexing agent than necessary to keep the iron and zinc ions homogeneously in solution at the prevailing alkalinity.
  • the aim is the most economical possible use of the complexing agent Y, which is ensured in the process according to the invention due to the selective removal of zinc ions by means of the ion exchange resin and the associated regression of unbound complexing agent in the bath solution.
  • the molar ratio of complexing agent Y relative to the element phosphorus to the total amount of iron (III) ions and zinc (II) ions in the bath solution of the method according to the invention for the selective removal of zinc ions is not greater than 5.0, more preferably not greater than 4.0, more preferably not greater than 3.0.
  • organic complexing agents Y being selected from water-soluble organic compounds which additionally have an ⁇ - or ⁇ -position to give -OPO 3 X 2 / n and / or -PO 3 X 2 / n functionality containing an amino, hydroxyl or carboxyl group, preferably containing one hydroxyl group, more preferably containing one hydroxyl group, but no amino group, and particularly preferably at least two such functional groups selected from OPO 3 X 2 / n and / or -PO 3 X 2 / n have.
  • a particularly preferred representative of an organic complexing agent Y is 1-hydroxyethane-1,1-diphosphonic acid (HEDP).
  • the organic complexing agents Y are not polymeric compounds, so that their molecular weight is preferably less than 500 g / mol.
  • the ion exchange resin preferably has at least 1.0 mol, particularly preferably at least 1.5 mol, more preferably at least 2.0 mol, of the functional groups selected from -OPO 3 X 2 / n and / or -PO 3 X 2 / n per kilogram of the ion exchange resin.
  • the ion exchange resin carries functional groups which bind zinc ions more strongly, in particular bind at least by a factor of 2, preferably more than 10, than the complexing agent Y contained in the alkaline bath solution. This makes it possible the ion exchange resin to remove complexed zinc ions from the bath solution and thus to regenerate, for example, the complexing agent contained in the bath solution.
  • the functional groups of the ion exchange resin must have a high affinity for zinc ions and at the same time a lower affinity for iron (III) ions.
  • the iron (III) content is an active component which should remain as completely as possible in the bath solution in the process according to the invention and should not be bound to the ion exchange resin.
  • the functional groups of the ion exchange resin bind iron (III) ions weaker, in particular bind at least by a factor of 2, preferably a factor of 10 weaker, than the complexing agents contained in the alkaline bath solution.
  • This allows the ion exchanger to be used specifically for depleting the Zn (II) ions in the bath solution without significantly affecting the concentrations of Fe (III) ions.
  • This is particularly advantageous in that it is possible to regulate the zinc ion concentration in a specific manner without substantially influencing the anti-icing properties of the solution.
  • the bond strength refers in particular to the complex formation constant K A of the complexing agents for the complexed metal ions.
  • the complexation constant is the product of the equilibrium constants of the individual elementary reactions for complex formation, ie the individual, successive steps of ligand binding. A binding that is stronger by a factor of 2 therefore means, for example, that the complex formation constant K A of the corresponding complexing agent is twice as large as the reference value.
  • the complex formation constants also refer to complexing agents, the according to the invention are bound to a solid substrate, always to the corresponding values of the complexing agent in solution.
  • the functional groups of the ion exchange resin are selected from aminoalkylphosphonic acid groups, preferably from aminomethylphosphonic acid groups, more preferably from the group -NR 1 -CH 2 -PO 3 X 2 / n , where X is either a hydrogen atom or a to be exchanged Alkali and / or alkaline earth metal atom having the respective valence n and R 1 is a hydrogen atom or an alkyl, cycloalkyl or aryl radical preferably having not more than 6 carbon atoms.
  • the matrix of the ion exchange resin may be the known polymers.
  • the matrix may, for example, consist of crosslinked polystyrene, for example polystyrene-divinylbenzene resin.
  • a polymer backbone based on the monomers styrene, divinylbenzene and / or based on phenol-formaldehyde condensates is preferred as the ion exchange resin, particularly preferably a polymer backbone based on the monomers styrene and / or divinylbenzene.
  • the ion exchange resin has chelating aminomethylphosphonic acid groups and a crosslinked polystyrene matrix.
  • Such ion exchange resins are in the US 4,002,564 (Column 2, line 12 - column 3, line 41) described in detail and preferred in the context of the present invention.
  • the ion exchange resins used are preferably water-insoluble solids, especially in particulate form, particularly preferably in the form of spherules with a preferred spherical diameter in the range of 0.2-2 mm, more preferably in the range of 0.4-1.4 mm.
  • the ion exchange resin may also be provided in a container through which the portion of the alkaline bath solution which is contacted with the ion exchange resin and subsequently returned to the system tank, and which retains it, is provided.
  • the ion exchange resin has a dissolved zinc resin capacity of at least 10 g / l, more preferably at least 20 g / l.
  • the zinc ion-loaded ion exchange resin be regenerable, i. the zinc ions are not bound irreversibly. Regeneration methods depend on the resin used and are well known in the art. By “regeneration” is meant the displacement of the zinc ions bound to the ion exchange resin by displaced ions in excess, whereby the ion exchange resin is again available as a complexing agent for the selective removal of dissolved zinc from the alkaline bath solutions.
  • bringing the alkaline bath solution into contact with the ion exchange resin can be carried out batchwise or continuously.
  • either a part of the bath solution is brought into contact with the ion exchanger for a predetermined time or continuously parts of the bath solution for a certain time.
  • bringing into contact in the process according to the invention is carried out continuously, for example by passing bath solution through a receptacle receiving the ion exchange resin.
  • such a selective zinc ion removal method is preferred in which a portion of the bath solution is contacted with the ion exchange resin in a container spatially separated from the system tank, and that portion of the bath solution is discontinuous upon contacting or continuously, in particular continuously, is fed back into the system tank.
  • the part of the bath solution for contact with the ion exchange resin is preferably fed through inlet openings in the container and is fed out after the contacting with the ion exchange resin through outlet openings, wherein the ion exchange resin remains in the container (so-called bypass method) ,
  • the content of iron (III) ions in the bath solution preferably does not exceed 2 g / kg, more preferably not more than 1 g / kg.
  • the content of iron (III) ions in the bath solution preferably does not exceed 2 g / kg, more preferably not more than 1 g / kg.
  • for the purpose of sufficient freezing of the zinc surfaces of the metallic components in a corresponding surface treatment preferably at least 100 mg / kg, more preferably at least 200 mg / kg of ferric ions in the alkaline bath solution in a method for the selective removal of the invention Zinc ions are included.
  • the free alkalinity of the alkaline bath solution for wet-chemical surface treatment is determined by titrating 10 ml of the bath solution with 0.1 N sodium hydroxide solution to a pH of 8.5.
  • the pH is determined potentiometrically with a calibrated glass electrode.
  • the volume of added titrant in milliliters then equals the free alkalinity score of the bath solution. This score, multiplied by a factor of 10, is equal to the free alkalinity in millimoles per liter.
  • active components are alkaline substances and preferably selected from alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates and organic amines, in particular alkanolamines.
  • the alkaline bath solutions preferably not more than 0.6 g / kg, more preferably not more than 0.4 g / kg of aluminum dissolved in water, since above these levels the surface conditioning achieved with the alkaline bath solution, in particular on metallic components which additionally have aluminum surfaces, is less effective with regard to the corrosion protection properties of a subsequent conversion coating.
  • a "zinc-binding ion exchange resin" according to this second aspect of the present invention is understood to mean the same ion exchange resin as used in the process of the present invention for selectively separating zinc ions from alkaline bath solutions for surface treatment of metallic components having surfaces of zinc, and according to this first aspect of the present invention has been described. Accordingly, preferred embodiments described herein with respect to the ion exchange resin are also preferred in view of the second aspect of the present invention.
  • a surface treatment process according to the invention comprising a pretreatment with alkaline bath solution and a subsequent conversion treatment, it is ensured that the formation of a high-quality corrosion protection layer in the surface treatment in a series, within the components with zinc surfaces and preferably also components with aluminum surfaces and preferably components in mixed construction are maintained, which have zinc and aluminum surfaces. This is especially true for maintaining the quality of the corrosion-protective coating on the surfaces of the component which are surfaces of aluminum.
  • concentration of dissolved zinc in alkaline bath solutions is decisive and thus becomes a control quantity to be controlled in the surface treatment according to the invention.
  • a process according to the second aspect of the present invention results in substantial pickling of the zinc surfaces of the components.
  • This pickling removal in the surface treatment according to the invention in series means that a high stationary content of dissolved zinc in the system tank of the wet-chemical pretreatment is present or is built up.
  • the dissolved zinc is removed from the bath solution by contacting at least a portion of the alkaline bath solution with a zinc-bonding ion exchange resin, or reducing its concentration.
  • This removal can be continuous or discontinuous, with continuous removal being preferred.
  • the removal of the dissolved zinc is not carried out solely by discarding a part of the alkaline bath solution of the system tank and adding another part of the alkaline bath solution containing only the active components of the alkaline bath solution to the system tank.
  • Active components in this context are understood to mean exclusively components which are essential for adjusting the alkalinity of the bath solutions or which cause significant surface coverage of the treated components with foreign elements or chemical compounds and are therefore consumed.
  • a significant surface coverage is present, for example, if the proportion of foreign elements on the metal surfaces or the proportion of chemical compounds on average greater than 10 mg / m 2 . This is the case, for example, if, as in the alkaline icing according to the DE 102010001686 after wet chemical pretreatment a surface coverage above 10 mg / m 2 based on the foreign element iron results, so that iron (III) ions in such an alkaline pretreatment represent an active component.
  • the same can be said for corrosion inhibitors, which have a high affinity for the metal surfaces to be treated and thus can cause a corresponding surface coverage.
  • the removal of dissolved zinc from the alkaline bath solution to maintain the maximum value Zn max is therefore preferably not alone by the compensation of Ausleppungs- or evaporation losses in the system tank by adding aqueous solutions that substitute only the active components of the alkaline bath solution of the system tank and bath volume.
  • Such a method of reducing the levels of dissolved zinc would be extremely uneconomical on the one hand, and on the other hand not suitable for an effective control of the proportion of dissolved Zinc in the pretreatment, since either the reduction of the zinc content below the maximum value Zn max or the need-based refreshment of the active components would have to be prioritized procedurally.
  • sulfides for the removal of dissolved zinc by the precipitation as zinc sulfide.
  • no sodium sulfide is used for the precipitation of dissolved zinc in the process according to the invention.
  • This number corresponds exactly to the theoretically required number of metallic components, which it is possible with serial pretreatment, to let the maximum concentration Zn max of dissolved zinc in the alkaline bath solution exceed by the pickling of the zinc surfaces of the components.
  • the maximum value Zn max of dissolved zinc in the process according to the invention for wet-chemical surface treatment depends on the alkalinity of the wet-chemical pretreatment and, to a considerable extent, on the concentration of specific complexing agents Y. In the presence of these complexing agents Y, the tolerance to dissolved zinc increases in proportion to their concentration. The presence of complexing agents Y is therefore preferred in alkaline bath solutions of the pretreatment in the inventive method.
  • the complexing agents Y in a total concentration of at least 0.5 mmol / l, more preferably in a total concentration of at least 5 mmol / l, but for economic reasons in a total concentration of preferably not more than 100 mmol / l, more preferably from not more than 80 mmol / l.
  • organic complexing agents Y provide a stable maximum concentration Zn max as the upper limit for dissolved zinc, which are selected from water-soluble organic compounds which have at least one functional group selected from -OPO 3 X 2 / n and / or PO 3 X 2 / n , wherein X represents either a hydrogen atom or an alkali and / or alkaline earth metal atom with the respective valence n.
  • organic complexing agents are therefore preferred in the process according to the invention.
  • the organic complexing agents Y in the surface treatment process are selected from water-soluble organic compounds which are additionally bonded in ⁇ - or ⁇ -position to a -OPO 3 X 2 / n and / or -PO 3 X 2 / n functionality an amino, hydroxyl or carboxyl group, preferably a hydroxyl group, and more preferably a hydroxyl group but do not contain an amino group, and more preferably at least two have such functional groups selected from -OPO 3 X 2 / n and / or -PO 3 X 2 / n .
  • a particularly preferred representative of an organic complexing agent Y is 1-hydroxyethane-1,1-diphosphonic acid (HEDP).
  • organic complexing agents Y are not polymeric compounds, so that their molecular weight is preferably less than 500 g / mol.
  • dissolved zinc is continuously removed from the alkaline bath solution of the wet chemical pretreatment by continuously withdrawing from the system tank partial volumes of the alkaline bath solution contacted with the zinc-binding ion exchange resins, followed by the corresponding treated partial volumes of the alkaline bath solution are separated from the ion exchange resin and then returned to the system tank.
  • a bypass method in which taken from the system tank partial volumes, processed and then returned to the system tank, is generally referred to in the art as a bypass method.
  • a higher proportion of dissolved aluminum can also build up due to pickling processes in the alkaline bath solutions of the wet-chemical pretreatment.
  • An increased proportion of dissolved aluminum can in turn have a negative effect on the activation of the aluminum surfaces, so that after the conversion treatment a reduced corrosion protection is observed.
  • a lighter deterioration of the corrosion protection properties in processes according to the invention is observed above an aluminum content of 0.4 g / L, whereas this deterioration becomes significant above 0.6 g / L.
  • the alkaline bath solutions of the wet-chemical pretreatment therefore contain aluminum dissolved in water, but a maximum value of 0.6 g / l, preferably 0.4 g / l, for the concentration of dissolved aluminum in the alkaline bath solution by not exceeding at least part of the alkaline bath solution of the system tank with a water-soluble compound which is a source of silicate anions and a precipitate forming in this part of the alkaline bath solution, optionally by filtration, from the alkaline bath solution is disconnected.
  • the reduction of the dissolved aluminum content in the alkaline bath solution is carried out by wet-chemical pretreatment by continuously withdrawing partial volumes from the bath solution of the system tank which are mixed with the water-soluble compound which is a source of silicate anions. according to which the solid fraction formed in these partial volumes of the alkaline bath solution is separated, preferably by filtration, from the alkaline bath solution and then the partial volumes of the alkaline bath solution freed from the solid, preferably as filtrate, are returned to the system tank.
  • the metered addition of the water-soluble compounds which is a source of silicate anions
  • the metered addition of the water-soluble compounds can be accomplished independently of contacting with the zinc-binding ion exchange resin.
  • a control of dissolved zinc and aluminum in the system tank can also be done independently.
  • the partial volumes of the alkaline bath solution removed from the system tank are first mixed with appropriate amounts of these precipitation reagents, and the solids content consisting essentially of aluminum silicate, preferably by filtration, is separated from the bath solution and then the partial volumes freed from this solids fraction the alkaline bath solution, preferably as a filtrate, contacted with the zinc-binding ion exchange resin and finally returned to the system tank.
  • the removal of the dissolved zinc by means of the zinc-binding ion exchange resin and then the precipitation of the aluminum.
  • alkali and alkaline earth metal silicates and / or silica are preferably used.
  • the filtration in the abovementioned preferred embodiments of the surface treatment process according to the invention is preferably carried out with an exclusion limit of 0.5 .mu.m, particularly preferably with an exclusion limit of 0.1 .mu.m.
  • the proportions of dissolved zinc and aluminum in the alkaline bath solution of the wet-chemical pretreatment are preferably determined processively, ie during the surface treatment of the metallic components according to the invention in series, analytically and directly or indirectly as a control variable for technical measures to reduce the proportion of dissolved zinc and / or Aluminum used in the system tank.
  • a volume flow is removed from the system tank, filtered, preferably with an exclusion limit of 0.1 .mu.m, and removed before returning the filtrate into the system tank, a sample volume and the proportion of dissolved zinc and aluminum, preferably determined photometrically, the determination value for the dissolved portions is then compared with the aforementioned preferred maximum values for dissolved aluminum and with the maximum value Zn max .
  • the proportion of dissolved zinc and / or aluminum by a post-precipitation of sparingly soluble hydroxides continue to decrease. It is therefore preferred for the determination of the actual and thus inventive concentration of dissolved zinc and aluminum that the sample immediately after its removal within 5 minutes, first via a filter with an exclusion limit of 0.5 .mu.m, more preferably 0.1 is filtered and then acidified, preferably to a pH of less than 3.0.
  • Such prepared samples can be measured analytically at any later time, since the proportion of dissolved zinc or aluminum in the acidic sample volume is invariable. For each method of determination of dissolved zinc and aluminum, it must be calibrated with custom solutions of parent substances.
  • a photometric determination of the proportions of dissolved zinc and aluminum can be carried out in the same sample volume or in separate parts of the sample volume taken. A determination by means of optical emission spectroscopy with inductively coupled argon plasma (ICP-OES) is preferred.
  • the wet-chemical pretreatment with the alkaline bath solution is preferably followed by a conversion treatment of the metallic components.
  • the conversion treatment according to the invention preferably represents a wet-chemical pretreatment without external power, in the course of which an inorganic coating is produced on the aluminum surfaces of the metallic components, which is at least partially composed of elements of the treatment solution which are not merely oxygen atoms.
  • Conversion treatments are well known in the art and have been widely described, for example, as phosphating, chromating, and chromium-free alternative processes, for example based on complex metal fluorides.
  • the surface treatment process according to the invention is particularly advantageous if the conversion treatment following the wet-chemical pretreatment with the alkaline bath solution is carried out with an acidic aqueous composition comprising water-soluble compounds of the elements Zr, Ti and / or Si.
  • acidic aqueous compositions which additionally contain compounds which are a source of fluoride ions.
  • the water-soluble compounds of the elements Zr, Ti and / or Si are preferably selected from hexafluoroacids of these elements and their salts, while compounds which are a source of fluoride ions are preferably selected from alkali metal fluorides.
  • the total content of water-soluble compounds of the elements Zr, Ti and / or Si in the acidic aqueous composition of the conversion treatment of the surface treatment of the present invention is preferably at least 5 ppm, more preferably at least 10 ⁇ m, but the acidic composition as a whole preferably contains not more than 1000 ppm of these compounds in each case based on the aforementioned elements.
  • the pH of the acidic aqueous composition is preferably in the range of 2-4.5.
  • the inventive method is particularly suitable for the serial surface treatment of metallic components, which are manufactured in mixed construction, as for Such components over the entire component substantially homogeneous corrosion-protective coating to minimize the contact corrosion due to the serial surface treatment according to the invention can be achieved permanently.
  • metallic components in mixed construction the surfaces of which consist of at least 2%, preferably at least 5% of surfaces of aluminum and at least 5%, preferably at least 10% of surfaces of zinc
  • the inventive method for serial surface treatment is successful .
  • the percentage of the surfaces of aluminum and zinc always refers to the total surface of the metallic component, which is brought into contact with the alkaline bath solution of the wet-chemical pretreatment.
  • metallic surfaces of alloys of these metals also apply as surfaces of zinc and aluminum as long as the proportion of elements to be added is below 50 at.%.
  • surfaces of zinc in the context of the present invention are also formed by galvanized or alloy-galvanized steel elements, which are assembled alone or with other metallic components to the metallic component.

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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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Claims (16)

  1. Procédé d'élimination sélective d'ions de zinc d'une solution de bain alcaline aqueuse stockée dans un réservoir de système et destinée au traitement de surface en série de composants métalliques ayant des surfaces en zinc, la solution de bain aqueuse alcaline contenant
    a) au moins 50 mg/kg d'ions ferrique ;
    b) au moins 50 mg/kg d'ions de zinc ; et
    c) un complexant Y se présentant sous la forme de phosphates condensés solubles dans l'eau, et/ou sous la forme de composés organiques solubles dans l'eau comportant au moins un groupe fonctionnel choisi parmi -OPO3X2/n et/ou -PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal de métal alcalin et/ou alcalino-terreux ayant la valence respective n ;
    le rapport molaire du complexant Y sur la base de l'élément phosphore à la quantité totale d'ions ferrique et d'ions de zinc étant supérieur à 1,0,
    caractérisé en ce qu'une partie de la solution de bain est amené en contact avec une résine échangeuse d'ions portant des groupes fonctionnels choisis parmi -OPO3X2/n et/ou -PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux à échanger ayant la valence n respective.
  2. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire du complexant Y sur la base de l'élément phosphore aux ions ferrique dans la solution de bain est supérieur à 1,5, de préférence supérieur à 2,0.
  3. Procédé selon l'une ou l'autre des revendications précédentes, caractérisé en ce que la teneur en ions ferriques dans la solution de bain est d'au moins 100 mg/kg, de préférence d'au moins 200 mg/kg, mais de préférence de pas plus de 2 g/kg, de manière particulièrement préférée de pas plus de 1 g/kg.
  4. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la solution de bain a une valeur de pH d'au moins 9, de préférence d'au moins 10, l'alcalinité libre étant de préférence d'au moins 0,5 point, mais de préférence de moins de 50 points.
  5. Procédé de traitement par voie chimique humide en série de surfaces de composants métalliques ayant des surfaces en zinc et en aluminium, par contact avec une solution de bain alcaline stockée dans un réservoir de système et contenant
    a) un complexant Y se présentant sous la forme de phosphates condensés solubles dans l'eau et/ou sous la forme de composés organiques solubles dans l'eau comportant au moins un groupe fonctionnel choisi parmi -OPO3X2/n et/ou -PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux ayant la valence respective n, et
    b) des ions ferriques,
    les composants étant prétraités par voie chimique humide, la valeur du pH de la solution de bain alcaline dans le prétraitement par voie chimique humide étant supérieur à 10 et l'alcalinité libre étant d'au moins 0,5 point, mais de moins de 50 points, la valeur maximale suivante Znmax de la concentration du zinc dissous dans la solution de bain alcaline du réservoir de système n'étant pas dépassée : Znmax = 0,0004 pH pH − 9 × FA + 0,6 × Y ,
    Figure imgb0008
    pH : valeur de pH
    Znmax : valeur maximale de la concentration de zinc dissous en mmol/l
    [FA] : alcalinité libre en mmol/l
    [Y] : concentration en mmol/l de complexants Y se présentant sous la forme de phosphates condensés solubles dans l'eau, calculée sous forme de P2O6 et/ou sous la forme de composés organiques solubles dans l'eau comportant au moins un groupe fonctionnel choisi parmi -COOX1/n, -OPO3X2/n et/ou -PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux ayant la valence respective n ;
    caractérisé en ce que
    un dépassement de la valeur maximale Znmax est empêchée pendant le prétraitement par voie chimique humide du fait que au moins une partie de la solution de bain alcaline du réservoir de système est amenée en contact avec une résine échangeuse d'ions comportant des groupes fonctionnels choisis parmi -OPO3X2/n et/ou -PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux à échanger ayant la valence n respective, et du fait que la partie de la solution de bain alcaline, qui a été amenée en contact avec la résine échangeuse d'ions en contact, étant ensuite ramenée dans le réservoir de système.
  6. Procédé selon la revendication 5, caractérisé en ce que la teneur en ions ferriques dans la solution de bain est d'au moins 50 mg/kg, de manière particulièrement préférée d'au moins 100 mg/kg, de manière notamment préférée d'au moins 200 mg/kg, mais de préférence de pas plus de 2 g/kg, de manière particulièrement préférée de pas plus de 1 g/kg.
  7. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la solution de bain respective contient de préférence pas plus de 0,6 g/kg, de manière particulièrement préférée pas plus de 0,4 g/kg d'aluminium dissous dans de l'eau.
  8. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce qu'une partie de la solution de bain respective est amenée en contact avec la résine échangeuse d'ions de manière discontinue ou continue, en particulier continue.
  9. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la mise en contact est effectuée dans un récipient spatialement séparé du réservoir de système et la partie de la solution de bain respective est ramenée dans le réservoir de système, après la mise en contact, de manière discontinue ou continue, en particulier continue.
  10. Procédé selon la revendication 8, caractérisé en ce que, pour effectuer la mise en contact avec la résine échangeuse d'ions, la partie de la solution de bain respective est introduite dans le récipient par des ouvertures d'entrée et, après la mise en contact avec la résine échangeuse d'ions, elle est évacuée par des orifices de sortie, la résine échangeuse d'ions restant dans le récipient.
  11. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la résine échangeuse d'ions comporte au total au moins 1,0 mole, de manière particulièrement préférée au total au moins 1,5 mole, de manière notamment préférée au total au moins 2,0 moles de groupes fonctionnels choisis parmi -OPO3X2/n et/ou -PO3X2/n, par kilogramme de résine échangeuse d'ions.
  12. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la résine échangeuse d'ions comprend un squelette de polymère à base de monomères styrène, divinylbenzène et/ou à base de produits de condensation phénol-formaldéhyde, de préférence à base de monomères styrène et/ou divinylbenzène.
  13. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que les groupes fonctionnels de la résine échangeuse d'ions sont choisis parmi des groupes acides aminoalkylphosphoniques, de préférence des groupes acide aminométhylphosphonique, de manière particulièrement préférée le groupe -NR1-CH2-PO3X2/n, X étant soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux à échanger ayant la valence respective n et chaque R1 étant un atome d'hydrogène ou un groupe alkyle, cycloalkyle ou aryle.
  14. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que le complexant Y de la solution de bain respective comporte e plus en position α ou β à d'un groupe - OPO3X2/n et/ou -PO3X2/n un groupe amino, hydroxyle ou carboxyle, de préférence un groupe hydroxyle, de manière particulièrement préférée un groupe hydroxyle, mais par de groupe amino.
  15. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la résine échangeuse d'ions est une matière solide, se présentant de préférence sous la forme de particules, de manière particulièrement préférée sous la forme de petites billes ayant un diamètre de préféré dans la gamme allant de 0,2 à 2 mm, de manière particulièrement préférée dans la gamme allant de 0,4 à 1,4 mm.
  16. Procédé selon une ou plusieurs des revendications 5 à 15, caractérisé en ce que le traitement de surface par voie chimique humide des composants métalliques en série est effectuée au moins pour un nombre de composants métalliques tel que la superficie totale seulement au niveau des surfaces de zinc des composants métalliques en mètres carrés est prétraitée par voie chimique humique avec la solution de bain alcaline du réservoir de système, laquelle superficie est supérieure à l'expression suivante : V B × Zn max × M Zn Δ m Zn
    Figure imgb0009
    VB : volume du bain en m3
    Znmax : concentration maximale de zinc dissous en mmol/l
    Mzn : masse molaire de zinc en g/mol
    Δmzn : décapage à surface normalisée rapporté aux surfaces de zinc des composants métalliques en g/m2.
EP15797897.4A 2014-11-13 2015-11-11 Procédé d'élimination sélective d'ions zinc de solutions de bain alcalines dans le traitement de surface de composants métalliques en série Active EP3218531B1 (fr)

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DE102014223169.8A DE102014223169A1 (de) 2014-11-13 2014-11-13 Verfahren zur selektiven Entfernung von Zink-Ionen aus alkalischen Badlösungen in der Oberflächenbehandlung von metallischen Bauteilen in Serie
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US10443134B2 (en) 2019-10-15
CN107109661B (zh) 2019-01-18
KR102330634B1 (ko) 2021-11-23
JP6670308B2 (ja) 2020-03-18
BR112017009858A2 (pt) 2017-12-19
ES2701203T3 (es) 2019-02-21
KR20170081695A (ko) 2017-07-12
EP3218531A1 (fr) 2017-09-20
WO2016075183A1 (fr) 2016-05-19
CN107109661A (zh) 2017-08-29
JP2017533997A (ja) 2017-11-16
US20170247799A1 (en) 2017-08-31
TR201821039T4 (tr) 2019-01-21
PT3218531T (pt) 2018-11-22
PL3218531T3 (pl) 2019-07-31
HUE042445T2 (hu) 2019-06-28
MX2017006225A (es) 2017-07-31
CA2967714A1 (fr) 2016-05-19
DE102014223169A1 (de) 2016-05-19

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