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EP3218531A1 - 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

Info

Publication number
EP3218531A1
EP3218531A1 EP15797897.4A EP15797897A EP3218531A1 EP 3218531 A1 EP3218531 A1 EP 3218531A1 EP 15797897 A EP15797897 A EP 15797897A EP 3218531 A1 EP3218531 A1 EP 3218531A1
Authority
EP
European Patent Office
Prior art keywords
zinc
bath solution
ion exchange
ions
exchange resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15797897.4A
Other languages
German (de)
English (en)
Other versions
EP3218531B1 (fr
Inventor
Jan-Willem Brouwer
Fernando Jose Resano ATALEJO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL15797897T priority Critical patent/PL3218531T3/pl
Publication of EP3218531A1 publication Critical patent/EP3218531A1/fr
Application granted granted Critical
Publication of EP3218531B1 publication Critical patent/EP3218531B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • 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

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 portion of the respective alkaline bath solution is brought into contact with an ion exchange resin, the functional groups selected from -OP03X2 n and / or -P03X2 n, where X is either a hydrogen atom or an 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.
  • Prior to further processing such as, in particular, anticorrosion treatment (e.g., 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 state of the 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 detail in DE 102010001686.
  • 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 heating the metallic surfaces.
  • impurities such as fats
  • surface activation by heating 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 refreshing the alkalinity is described in EP 1051672. 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.
  • WO 2014/0675234 therefore teaches a maximum concentration of free zinc ions which should not be exceeded in order to maintain the quality of subsequent processes.
  • the metered addition of sodium sulfide is described in WO2014 / 0675234.
  • 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 to zinc (II) - both aluminum (III) - and iron (III) ions, reducing the amount of free HEDP that is required to form 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.
  • This object is achieved according to the invention initially by a method for the selective removal of zinc ions from an alkaline aqueous bath solution stored in a system tank for the surface treatment of metallic components having surfaces of zinc in series, the alkaline aqueous bath solution
  • either a hydrogen atom or an alkali and / or alkaline earth metal atom having the respective valence n contains;
  • compounds are water-soluble if their solubility in deionized water having a conductivity of not more than 1 ⁇ 8 ⁇ 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 system tank according to the invention a container understood that stores a bath solution for contacting Bring with the metallic components.
  • the metallic component can be passed through a system tank for contact with the bath solution by immersion, 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 pickled from the metallic components is therefore based on a preparation by means of a specific ion exchange resin. Surprisingly, only zinc ions are removed, while the iron (III) ions remain in the bath in the presence of the complexing agent Y in 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 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 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.
  • the organic complexing agents Y are selected from water-soluble organic compounds which additionally in the position ⁇ or ⁇ to an -OPO 3 X 2 n and / or PO 3 X 2 n functionality are 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 exhibit.
  • a particularly preferred representative of an organic complexing agent Y is 1-hydroxyethane-1, 1-diphosphonic acid (HEDP).
  • HEDP 1-hydroxyethane-1, 1-diphosphonic acid
  • the ion exchange resin preferably has at least 1.0 mol, more 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 -P03X2 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 by a factor of 10, more weakly than the complexing agents contained in the alkaline bath solution.
  • the bond strength refers in particular to the complex formation constant KA 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 KA 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-CH 2 -PO 3 X 2 / n, where X is either a hydrogen atom or an exchanged alkali and / or Is alkaline earth metal atom of respective valence n and R is a hydrogen atom or an alkyl, cycloalkyl or aryl radical preferably having not more than 6 carbon atoms each.
  • the matrix of the ion exchange resin may be the known polymers.
  • the matrix may be, for example, 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.
  • ion exchange resins are described in detail in US Pat. No. 4,002,564 (column 2, line 12 - column 3, line 41) and are preferred within the scope 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 having 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. It is further preferred that the ion exchange resin loaded with zinc ions is regenerable, that is, the zinc ions are not irreversibly bound. 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 iron (III) 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.
  • the present invention relates to a method optimized for the effectiveness and quality of the corrosion protection achieved for wet-chemical surface treatment of metallic components in series comprising zinc and aluminum surfaces, in which alkaline bath solutions are used for freezing and the concentration of zinc ions below one predetermined threshold is maintained.
  • the present invention relates to a process for wet-chemical surface treatment of metallic components comprising surfaces of zinc and aluminum or in one component surfaces of zinc and another component surfaces of aluminum, in series by contacting with an alkaline Bath solution stored in a system tank and
  • a complexing agent Y in the form of water-soluble condensed phosphates and / or in the form of water-soluble organic compounds which have at least one functional group selected from -COOXi / n, -O.sub.3.sup.2 and / or -PO.sub.3 N.sub.2n, where X is either a hydrogen atom or an alkali metal and / or alkaline earth metal atom with the respective valency n, where the complex image is in particular HEDP, and
  • iron (III) ions preferably at least 50 mg / kg, more preferably at least 100 mg / kg, more preferably at least 200 mg / kg of iron (III) ions, but preferably not more than 2 g / kg, especially preferably not more than 1 g / kg of iron (III) ions, be pretreated wet-chemically, wherein the pH of the alkaline bath solution in the wet chemical pretreatment is greater than 10 and the free alkalinity at least 0.5 points, but less than 50 points, wherein the following maximum value Zn ma x for the concentration of dissolved zinc in the alkaline bath solution of the system tank is not exceeded:
  • Znmax maximum value for the dissolved zinc concentration in mmol / l
  • 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, preferred embodiments described herein with respect to the ion exchange resin are therefore 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 for this 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 DE 102010001686, after the wet-chemical pretreatment, a surface coverage of 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 comply with the maximum value Znmax is therefore preferably not solely 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 ma x or the need-based refreshing 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.
  • the wet-chemical surface treatment of the metallic components in series at least for such a number of metallic components that a total area on zinc surfaces of the metallic components in square meters with the alkaline bath solution of the system tank is wet-chemically pretreated, which is greater than the following term:
  • Znmax maximum concentration of dissolved zinc in mmol / l
  • This number corresponds exactly to the theoretically required number of metallic components, which it is possible with serial pretreatment to exceed the maximum concentration Zn ma x of dissolved zinc in the alkaline bath solution by the Beizabtrag of the zinc surfaces of the components.
  • the maximum zinc oxide concentration Zn ma x in the alkaline bath solution can be determined solely by pickling processes not be exceeded. Of course, this only applies if not already dissolved zinc is contained in the alkaline bath solution at the beginning of the series.
  • the wet-chemical surface treatment process according to the invention is preferably carried out such that the maximum value Zn ma x of dissolved zinc in the alkaline bath solution does not exceed the following value:
  • Znmax maximum value for the dissolved zinc concentration in mmol / l
  • the maximum value Zn ma x 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 great 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 ma x as the upper limit for dissolved zinc, which are selected from water-soluble organic compounds which have at least one functional group selected from - ⁇ O 3 ⁇ 2 and / or PO 3 O 2 n, wherein X represents either a hydrogen atom or an alkali and / or alkaline earth metal atom with the respective valency n.
  • These organic complexing agents are therefore preferred in the process according to the invention.
  • the organic complexing agents Y in the surface treatment process be selected from water-soluble organic compounds which are additionally present in a - or ß-position to a -OP03X2 n and / or -P03X2 n functionality an amino, hydroxyl or carboxyl group, preferably a hydroxyl group, containing, and more preferably a hydroxyl group, but no amino group , and more preferably at least two such functional groups selected from -OP03X2 n and / or -P03X2 n have.
  • 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.
  • the alkaline bath solution contains:
  • Y selected from organic compounds which have at least one functional group selected from -OPO 3 X 2 n and / or -PO 3 X 2 n, where X is either a hydrogen atom or an alkali and / or alkaline earth metal atom with the respective valence n represents,
  • 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, after which the appropriately treated partial volumes of the alkaline bath solution are removed from the bath ion exchange resin are separated 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, 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.
  • first 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 ⁇ m, particularly preferably with an exclusion limit of 0.1 ⁇ 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 ⁇ , and removed before feeding the filtrate back 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 ma x.
  • 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 ⁇ , more preferably 0.1 ⁇ , filtered and then acidified, preferably to a pH of less than 3.0.
  • a filter with an exclusion limit of 0.5 ⁇ , more preferably 0.1 ⁇ 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, these are to be used with custom solutions of
  • Urtitersubstanzen is to calibrate.
  • 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.
  • the resin volume was 0, 1 I at a layer height of 30 cm.
  • the icebreaker was composed as follows:
  • the separation performance of various ion exchange resins was examined and is shown in Table 1.
  • concentration of the elements zinc and iron were investigated in run-off samples of the icing solution during a throughput of 10 BV (bed volume) of the icing solution at 20 ° C. by means of ICP-OES.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

La présente invention concerne un procédé de traitement de surface en série de composants métalliques qui ont des surfaces en zinc, le procédé comprenant un prétraitement alcalin et un procédé d'élimination sélective d'ions zinc d'une solution de bain alcaline pour le traitement de surface en série de surfaces métalliques qui comportent des surfaces en zinc. Selon l'invention, pour mettre en œuvre les procédés respectifs, une partie de la solution de bain alcaline respective est mise en contact avec une résine échangeuse d'ions, qui porte des groupes fonctionnels choisis parmi -OPO3X2/n et/ou -OPO3X2/n, où X est soit un atome d'hydrogène soit un atome de métal alcalin et/ou alcalino-terreux échangeable de valence respective n.
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)

Priority Applications (1)

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PL15797897T PL3218531T3 (pl) 2014-11-13 2015-11-11 Sposób selektywnego usuwania jonów cynku z alkalicznych roztworów do kąpieli w seryjnej obróbce powierzchni metalowych elementów

Applications Claiming Priority (2)

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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
PCT/EP2015/076282 WO2016075183A1 (fr) 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

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EP3218531B1 EP3218531B1 (fr) 2018-10-17

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JP (1) JP6670308B2 (fr)
KR (1) KR102330634B1 (fr)
CN (1) CN107109661B (fr)
BR (1) BR112017009858A2 (fr)
CA (1) CA2967714A1 (fr)
DE (1) DE102014223169A1 (fr)
ES (1) ES2701203T3 (fr)
HU (1) HUE042445T2 (fr)
MX (1) MX2017006225A (fr)
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JPS52139633A (en) * 1976-05-18 1977-11-21 Nisshin Steel Co Ltd Method of regenerating chromate treating solution
JPS5992028A (ja) * 1982-11-18 1984-05-28 Nippon Paint Co Ltd イオン交換処理法
JPH0774461B2 (ja) * 1989-04-07 1995-08-09 日本鋼管株式会社 亜鉛または亜鉛合金の表面処理方法
JPH05247665A (ja) * 1992-03-03 1993-09-24 Nippon Paint Co Ltd 燐酸塩処理された金属材表面の後処理洗浄方法
JP2968147B2 (ja) * 1993-04-07 1999-10-25 日本パーカライジング株式会社 亜鉛含有金属めっき鋼板用酸性置換めっき液組成物
JP3487471B2 (ja) * 1996-01-30 2004-01-19 日立金属株式会社 エッチング加工性に優れたＦｅ−Ｎｉ系合金薄板
JPH11140667A (ja) * 1997-11-13 1999-05-25 Dainippon Printing Co Ltd エッチング用基材、エッチング加工方法およびエッチング加工製品
DE19802725C1 (de) 1998-01-24 1999-11-11 Henkel Kgaa Automatische Kontrolle und Steuerung von Reinigerbädern durch Alkalitätsbestimmung
DE10056628B4 (de) * 2000-11-15 2004-07-22 Henkel Kgaa Fraktionierte Regenerierung eines mit Nickelionen beladenen schwach sauren Ionenaustauschers
DE10142933A1 (de) * 2001-06-08 2002-12-12 Henkel Kgaa Verhinderung von Membranverblockung bei der Abwasseraufbereitung bei der Phosphatierung
EP1392887B1 (fr) * 2001-06-08 2007-01-03 Henkel Kommanditgesellschaft auf Aktien Procede permettant d'empecher l'encrassement de la membrane lors du traitement des eaux usees resultant de la phosphatation
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DE102012215679A1 (de) * 2012-09-04 2014-05-15 Henkel Ag & Co. Kgaa Verfahren zur korrosionsschützenden Oberflächenbehandlung von metallischen Bauteilen in Serie

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Publication number Publication date
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
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
EP3218531B1 (fr) 2018-10-17
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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