EP3044348A1 - Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion - Google Patents

Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion

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Publication number
EP3044348A1
EP3044348A1 EP14771781.3A EP14771781A EP3044348A1 EP 3044348 A1 EP3044348 A1 EP 3044348A1 EP 14771781 A EP14771781 A EP 14771781A EP 3044348 A1 EP3044348 A1 EP 3044348A1
Authority
EP
European Patent Office
Prior art keywords
treatment solution
iii
chromium
ions
coating layer
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
EP14771781.3A
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German (de)
English (en)
Other versions
EP3044348B1 (fr
Inventor
Thomas Nitzsche
Julian Hoffmann
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Hillebrand Chemicals GmbH
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Hillebrand Chemicals GmbH
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Publication date
Application filed by Hillebrand Chemicals GmbH filed Critical Hillebrand Chemicals GmbH
Priority to HRP20220130TT priority Critical patent/HRP20220130T1/hr
Publication of EP3044348A1 publication Critical patent/EP3044348A1/fr
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Publication of EP3044348B1 publication Critical patent/EP3044348B1/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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention relates to a processing solution for a method for producing a corrosion-protective coating layer, a concentrate of such a processing solution, and a method for producing a corrosion-protective coating layer.
  • Practical methods for producing a corrosion-protective coating layer on a metallic surface are known in which the surface to be treated is brought into contact with a treatment solution.
  • multi-stage processes which include a passivation, rinsing steps (cascade rinsing) and optionally a subsequent sealing.
  • the passivation is followed by at least one rinsing step, in which the salt load required for producing an insoluble conversion layer, which would otherwise lead to reduced corrosion protection, is removed from the surface of the workpiece to be treated.
  • Heavy metal contaminated wastewater is the result here, which must be clarified with the appropriate cost.
  • the subsequent sealing is usually carried out in a separate system and is therefore costly.
  • a pH of the treatment solution of less than 3 is implicit.
  • the skilled person was in fact no other way available to prevent the undesirable precipitation of chromium ions as chromium hydroxides.
  • Such a low pH strongly activates the surface of the metal substrate which will continue to react even after the termination of dipping.
  • salts form, some of which contain water of crystallization. It comes after a short time to corrosion losses.
  • WO 201 1/000969 A1 discloses a method for corrosion treatment for surfaces of zinc and zinc alloys.
  • an aqueous treatment solution of chromium (III) ions and phosphate is used.
  • silanes of a specifically defined type are used. It is to be assumed that the treatment solution contains micro- or even macroscopic organic particles which shorten the service life of the coating bath and / or lead to a reduction in quality on the surface of the workpiece.
  • EP 2 014 793 A2 for corrosion treatment is based on the use of a conversion layer on which the coating layer is produced.
  • JP-2005-023372 A discloses a method for producing a chromium (III) -containing protective layer. This, too, is based on the use of a conversion layer on which the coating layer is produced.
  • a versatile applicable method is to be made available, which preferably in one stage - ie without subsequent rinsing steps and optionally separate Verrisonlung - and in a Variety of metallic surfaces containing, for example, aluminum, magnesium, nickel, cadmium, zinc, tin, manganese, magnesium and / or their alloys, can be used.
  • a treatment solution for such a method should be proposed and a concentrate of such a treatment solution.
  • the invention is based on the recognition that the avoidance of the silanes specifically described in WO 2011/000969 A1 in the treatment solution also prevents their entry into the coating layer to be produced. It has been recognized that silanes of this type can lead to pores and defects in the coating layer and thus reduce the quality of the coating layer to be produced. Because the use of silanes of WO 2011/000969 A1 is dispensed with, the dried corrosion-protective coating layer has a more homogeneous structure and, through improved barrier action, inhibits the diffusion of attacking agents to an increased extent.
  • the corrosion-protective coating layer produced by the process according to the invention has a low degree of redissolution in aqueous media when dried. Furthermore, it shows a surprisingly high degree of flexibility, which avoids cracks and breaks in movements of the metallic surface.
  • disadvantages of the conventional passivation processes can be avoided, namely that insufficient sagging properties are achieved during drying and thus the salts (containing water of crystallization) greatly reduce the corrosion protection and contaminate any subsequent solvent-based coating media and irreversibly damage them.
  • a sealing layer can be achieved which makes subsequent rinsing steps unnecessary, so that excellent corrosion protection can be achieved and negative effects on subsequent coating media, in particular water entry in solvent-containing coating media, can be avoided.
  • the corrosion-protective coating layer applied according to the invention combines the functionalities of a passivation layer containing chromium (III) ions and a high-grade sealing layer.
  • the inventive method allows passivation and sealing in a treatment step without subsequent rinsing steps. It has been found that the appearance of the treated metallic surface does not change or only to a slight extent during long-term corrosive loading. Since silanes, as well as those mentioned in WO 2011/000969 A1 in the neutral or alkaline pH range show a strong tendency to coagulation, the storage stability of the treatment solution is significantly improved by dispensing with the silanes of WO 2011/000969 A1. The stability in the alkaline also allows the use of a base solution according to the invention as an alkaline assistant in coating compositions.
  • the invention also allows the abandonment of the use of toxic and environmentally hazardous chromium (VI) ions. It has also been found that the treatment solution according to the invention is stable to friction-adjusting additives, ie lubricants, and other functionally required components.
  • a “treatment solution” may be an aqueous solution, ie one which predominantly contains water as solvent
  • the treatment solution may also be a nonaqueous one, which contains predominantly at least one organic solvent as solvent.
  • the proportion of water in the total solvent is preferably more than 50% by weight, preferably more than 65% by weight, more preferably more than 80% by weight and more preferably more than 90% by weight
  • the proportion of water in the total solvent is less than 5% by weight, preferably 1 to 3% by weight.
  • a "chromium (III) ion source” in the present invention means at least one compound which releases chromium (III) ions, preferably in complexed form, in the treatment solution.
  • the term "phosphate source” in the sense of the present invention is at least a compound which releases phosphate in the treatment solution.
  • a “zinc ion source” in the context of the present invention is at least one compound which liberates zinc ions in the treatment solution, preferably in complexed form.
  • “citrate source” means at least one compound that releases citrate in the treatment solution.
  • phosphate in particular stands for unprotonated ortho-phosphate, monoprotic ortho-phosphate (hydrogen phosphate) as well as doubly protonated orthophosphate (dihydrogen phosphate) and ortho-phosphoric acid.
  • citrate includes in particular unprotonated, singly protonated and doubly protonated citrate and citric acid.
  • a “lubricant” in the sense of the present invention describes a dispersion of micronized particles which reduce the frictional resistance of two contact surfaces which move relative to one another and preferably can set a defined coefficient of friction, in particular the lubricant has no filming properties.
  • metal surface in the present invention also encompasses those surfaces of metal to which one or more non-metallic organic and / or inorganic coatings, in particular a conversion layer, have already been applied.
  • silanes of WO 2011/000969 A1 in the present invention, those polymers are understood which by reaction
  • R 4-x Si (OR 1 ) x wherein the radicals R are the same or different and each represents a substituted or unsubstituted hydrocarbon group having 1 to 22 hydrocarbon atoms, x is 1, 2 or 3 and R is 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, and
  • Me (OR 2 ) n One or more alkoxides of the formula Me (OR 2 ) n wherein Me is Ti, Zr, Hf, Al, Si and n is the oxidation state of Me and R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, are available ,
  • R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms
  • the treatment solution according to the invention contains a chromium (III) ion source, a phosphate source, a zinc ion source and a citrate source.
  • the molar ratio of chromium (III) ions to zinc ions is 1: at least 1.65 and the molar ratio of chromium (III) ions to citrate is 1: at least 1.4.
  • the molar ratio of chromium (III) ions to zinc ions is at most 0.61 and the molar ratio of chromium (III) ions to citrate is at most 0.72.
  • the mole fraction of zinc ions over the mole fraction of chromium (III) ions by at least 1.65 times and the mole fraction of citrate over the mole fraction of chromium (III) ions outweighs at least 1.4 times.
  • the treatment solution is also substantially free of silanes of WO 2011/000969 A1.
  • “Substantially free of silanes of WO 2011/000969 A1” means that the treatment solution is less than 10 g / l, preferably less than 5 g / l, more preferably less than 1 g / l and particularly preferably less than 0.1 contains g / l of silanes of WO 2011/000969 A1 Particularly preferably, the treatment solution contains no silanes of WO 2011/000969 A1.
  • the chromium (III) ion source contained in the treatment solution is preferably selected from the group consisting of inorganic chromium (III) salts, chromium (III) salts of organic acids and chromium (VI) compounds, from which chromium ( III) ions, preferably in complexed form, can be generated in situ, and mixtures of these. Particular preference is given to using chromium (VI) compounds.
  • Suitable inorganic chromium (III) salts are, for example, basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, chromium (III) nitrate, potassium chromium (III) Sulfate and mixtures of these. Preference is given to using chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) nitrate or potassium chromium (III) sulfate.
  • Suitable chromium (III) salts of organic acids are, for example, chromium (III) -
  • chromium (III) citrate chromium (III) tartrate
  • chromium (III) acetate chromium (III) acetate
  • Suitable chromium (VI) compounds for the in situ generation of chromium (III) ions are, for example, chromium (VI) oxide, chromates such as potassium or sodium chromate, dichromates such as potassium or sodium dichromate, and mixtures of these.
  • Suitable reducing agents for generating chromium (III) ions in situ are, for example, sulfites such as sodium sulfite, sulfur dioxide, phosphites, hypophosphites such as sodium hypophosphite, phosphorous acid, hydrogen peroxide, alcohols such as methanol, hydroxycarboxylic acids, hydroxydicarboxylic acids such as gluconic or malic acid, citric acid, and mixtures of this.
  • the phosphate source contained in the treatment solution is selected from the group consisting of ortho-phosphoric acid, pyrophosphoric acid, meta-phosphoric acid, polyphosphoric acid and their salts in all possible protonation stages, oV-phosphorus pentoxide and mixtures of these.
  • Ortho-phosphoric acid is particularly preferably used.
  • the zinc ion source contained in the treatment solution is preferably a zinc salt.
  • Suitable zinc salts are, for example, zinc sulfate, zinc chloride, zinc phosphate, zinc oxide, zinc hydroxide, zinc citrate and mixtures of these. Zinc oxide or zinc phosphate is particularly preferably used.
  • the citrate source contained in the treatment solution is preferably selected from the group consisting of citric acid and salts of citric acid, ie salts with unprotonated, singly or doubly protonated citrate.
  • Suitable salts of citric acid are monosodium urate, disodium citrate, trisodium citrate, ammonium citrate and potassium citrate.
  • the phosphate concentration in the treatment solution is preferably between 1 g / l and 110 g / l, more preferably between 5 g / l and 50 g / l and particularly preferably between 10 g / l and 35 g / l (calculated as orthophosphate).
  • the treatment solution preferably has a molar ratio of chromium (III) ions to phosphate of between 1: 1, 5 and 1: 5, preferably between 1: 2 and 1: 4.5 and more preferably between 1: 3 and 1: 4.
  • the molar ratio of chromium (unions to zinc ions in the treatment solution is between 1: 1, 65 and 1: 2.35, preferably between 1: 1, 75 and 1: 2.25, more preferably between 1: 1, 85 and 1: 2.15 and more preferably about 1: 2.
  • the molar ratio of chromium (III) ions to citrate is in the treatment solution between 1: 1, 4 and 1: 1, 8, preferably between 1: 1, 45 and 1: 1, 75, more preferably between 1: 1, 5 and 1: 1, 7 and particularly preferably at about 1: 1, 6th More preferably, the molar ratio of chromium (III) ions to zinc ions in the treatment solution is adjusted to the molar ratio of chromium (III) ions to citrate, such that the molar ratio of chromium (III) ions to zinc ions is between 1: 1.65 and 1: 2.35 and that of chromium (III) ions to citrate is between 1: 1, 4 and 1: 1.8, preferably the molar ratio of chromium (III) ions to zinc ions is between 1: 1, 75 and 1: 2.25 and that of chromium (III) ions to citrate is between 1: 1, 45 and 1: 1, 75, more preferably the molar ratio of chrom
  • the concentration of the citrate in the treatment solution is calculated from the concentrations of the chromium (III) ions and the zinc ions in the treatment solution according to the following formula 2:
  • Figure 1 is illustrative of the concentration ratios resulting from the use of formula (1) and formula (2).
  • the concentration ratios correspond to the length ratios of the respective lines of the triangle shown.
  • the concentration of the chromium (III) ions in the treatment solution is preferably between 0.2 g / l and 27 g / l, preferably between 0.2 g / l and 20 g / l, more preferably between 0.5 g / l and 15 g / l, and more preferably between 1 g / l and 10 g / l.
  • the concentration of zinc ions in the treatment solution is between 0.5 and 66 g / l, preferably between 0.5 and 49 g / l, more preferably between 1, 2 and 37 g / l and particularly preferably between 2.5 and 25 g / l.
  • the concentration of citrate in the treatment solution is between 1.1 and 154 g / l, preferably between 1.1 and 14 g / l, more preferably between 2.8 and 85 g / l and particularly preferably between 5.7 and 57 g / l.
  • the concentrations of the chromium (III) ions, the zinc ions and the citrate in the treatment solution are coordinated so that the concentration of chromium (III) ions is between 0.2 and 27 g / l, that of the zinc ions between 0.5 and 66 g / l and that of the citrate is between 1.1 and 154 g / l, preferably the concentration of the chromium (III) ions between 0.2 and 20 g / l, that of the zinc ions between 0, 5 and 49 g / l and that of the citrate is between 1.1 and 114 g / l, more preferably the concentration of chromium (III) ions between 0.5 and 15 g / l, that of the zinc ions between 1.2 and 37 g / l and that of the citrate is between 2.8 and 85 g / l and particularly preferably the concentration of the chromium (III) ions between 1 and 10 g / l, that
  • the treatment solution additionally contains at least one surfactant, preferably at least one nonionic, anionic or amphoteric surfactant, or more preferably a combination thereof, such as a combination of a nonionic with an anionic surfactant, a combination of a nonionic with an amphoteric surfactant, a combination of an anionic with an amphoteric surfactant or a combination of a nonionic, an anionic and an amphoteric surfactant.
  • the addition of surfactants can promote film formation of the treatment solution on the metallic surface to be treated.
  • the total concentration of surfactant is preferably between 0.01 and 30 g / l, preferably between 0.1 and 15 g / l, more preferably between 0.2 and 8 g / l and more preferably between 0.3 and 3 g / l.
  • the term "total concentration of surfactant” is understood to mean the ratio of the sum of the weights of the surfactants present in the treatment solution to the volume of the treatment solution.
  • the treatment solution contains at least one nonionic and at least one anionic surfactant in a mass ratio of 4: 1 to 1: 8, preferably from 2: 1 to 1: 6, more preferably from 1: 1 to 1: 4, and most preferably from 1: 1 to 1: 2.
  • the treatment solution contains at least one nonionic, at least one anionic and at least one amphoteric surfactant in a mass ratio of 1: 1: 1 to 1: 5: 1, preferably from 1: 2: 1 to 1: 4: 1 and more preferably from about 1: 3: 1.
  • Preferred nonionic surfactants Alkyloxethylates such as Lutensol® ON 50 (BASF), alkyl polyglucosides such as Triton TM CG-110 (Dow Chemicals), polyalkylene glycol ethers, Guerbet alcohol alkoxylates such as Lutensol® XL 40 (BASF), Fe t-aminoethoxylates and mixtures of these.
  • Preferred anionic surfactants are fatty alcohol poly (oxyethylene) sulfonates such as Ralufon® F 11-13 (Raschig), arylsulfonates such as K-Na cumene sulfonate, fatty alcohol sulfates, alkyl carboxylates, alkylbenzenesulfonates and mixtures of these.
  • Preferred amphoteric surfactants are alkyl betaine, dipalmitoyl lecithin and mixtures of these.
  • Alkyloxethylate + fatty alcohol poly (oxy- - 1: 1, 2
  • the aqueous treatment solution additionally contains at least one organophosphate and / or organophosphonate. This can lead to a higher degree of crosslinking of the corrosion-protective coating layer produced and thus to improved corrosion-protecting properties.
  • the aqueous treatment solution preferably contains at least one organophosphonate, preferably at least one amino phosphonate.
  • Preferred aminophosphonates here are aminotris (alkylphosphonic acid) having a chain length of C1 to C8 for the alkyl group, dimethylaminoethanediphosphonic acid (DMAEDP), 1-aminoethanediphosphonic acid (AEDP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), ethylenediamine-tetra (methylenephosphonic acid) (EDTMP) , Hydroxyethyl-amino-di (methylenephosphonic acid) (HEMPA) and mixtures of these.
  • DMAEDP dimethylaminoethanediphosphonic acid
  • AEDP 1-aminoethanediphosphonic acid
  • DTPMP diethylenetriaminepenta
  • ETMP ethylenediamine-tetra
  • HEMPA Hydroxyethyl-amino-di (methylenephosphonic acid)
  • the total concentration of aminophosphonate is preferably between 0.05 g / l and 8 g / l, preferably between 0.1 g / l and 5 g / l and more preferably between 0.3 g / l and 3 g / l and am most preferably between 0.4 g / l and 1.5 g / l.
  • the incorporation of polymers into the anticorrosive coating layer leads to a reduced barrier effect and thus also to a reduced corrosion protection of the coating layer.
  • the latter is also due to the fact that the cathodic partial reaction of corrosion is less inhibited.
  • the passivation step is usually followed by a sealing step.
  • a corrosion-protective coating layer which is substantially free of polymers.
  • This can be achieved by using a treatment solution which is substantially free of certain polymers and copolymers soluble in water and / or organic solvents.
  • “Substantially free of” means that the treating solution is less than 10 g / l, preferably less than 5 g / l, more preferably less than 1 g / l, and most preferably less than 0.1 g / l of the corresponding polymers or copolymers contains.
  • These polymers and copolymers are in particular so-called film-forming polymers, ie those which promote the film formation of the corrosion-protective coating layer and therefore also incorporate into the layer under the selected reaction conditions, which leads to barrier imperfections in the latter. They are usually directly applied to the treatment solution added as a powder or as a preliminary solution.
  • the treatment solution is substantially free of filming polymers.
  • the treatment solution is preferably not only substantially free of silanes of WO 201/000969 A1 but also substantially free of silanes in general.
  • the treatment solution is substantially free of silanes, more preferably substantially free of silanes, polyvinylpyrrolidone, polyvinyl alcohol and their copolymers, and more preferably free of silanes, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycols, polyitaconic acids, polyacrylates and their copolymers.
  • the anti-corrosive coating layer is a tribologically functional coating layer.
  • the treatment solution in this case additionally contains 0.01 to 50 wt .-%, preferably 0.05 to 30 wt .-% and particularly preferably 0.1 to 15 wt .-% of at least one lubricant.
  • Preferred lubricants are those substances which are insoluble in water and / or organic solvents, ie insoluble in the treatment solution used, and, for example, have no filming properties due to the high melting temperatures.
  • the at least one lubricant is preferably selected from the group consisting of polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), perfluorinated polyethers (PFPE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoroethylene copolymer (FEP), perfluoroalkoxy copolymer (PFA) , Polysulfones, MoS2, WS2, TiS2, BN graphite and mirco-encapsulated lubricants.
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-tetrafluoroethylene
  • PFPE perfluorinated polyethers
  • PVDF polyvinylidene fluoride
  • FEP tetrafluoroethylene / hexafluoroethylene copolymer
  • PFA perfluoroalkoxy copolymer
  • the pH of the treatment solution can be adjusted in a range of 2 to 11, 5 and is to be adapted to the requirements, depending on the field of application and the condition of the surface. In parts to be treated with optical demands on the metal surface and to achieve the best possible Corrosion protection is preferably set a mildly acidic pH of the treatment solution. If the treatment solution is used to produce an intermediate layer for topcoat layer combinations, a lower pH below 4 lowers the application time. In case of application as anti-corrosive additive or with the addition of alkaline lubricant additives for the functionalization of the dry layer, a pH value above 7 must be set.
  • the treatment solution can be prepared by diluting a concentrate, that is to say a correspondingly higher concentration of base solution.
  • the mass fraction of the base solution in the finished treatment solution is preferably 1 to 100%, more preferably 1 to 50%, further preferably 1 to 25%, more preferably 1 to 15% and most preferably 3 to 12%.
  • the concentrate of a treatment solution of the present invention for a method for producing a corrosion-protective coating layer on a metallic surface in which the surface to be treated is brought into contact with a treatment solution is obtainable by withdrawing at least a part of the solvent from the treatment solution of the present invention.
  • the inventive method for producing a corrosion-protective coating layer on a metallic surface provides that the surface to be treated is brought into contact with the treatment solution according to the invention.
  • the process parameters such as treatment temperature, treatment time, drying temperature and total drying time must be adapted to the requirements, depending on the field of application and the design or condition of the surface.
  • the treatment temperature that is, the temperature during the contact of the treatment solution with the surface before drying, is preferably in the range of 10 to 90 ° C, preferably 15 to 80 ° C, and more preferably 25 to 60 ° C.
  • the treatment time ie the time during which the treatment solution is in contact with the surface before drying, is preferably in the range from 1 s to 60 min, preferably from 5 s to 40 min, more preferably from 10 s to 30 min and particularly preferably from 20 s to 15 min.
  • the drying temperature ie the temperature during the subsequent drying of the treated surface, is preferably in the range from 20 (room temperature) to 250 ° C, preferably from 50 to 200 ° C and particularly preferably from 80 to 180 ° C. It can be dried passively and / or actively. An active drying can be done by induction, infrared or hot air.
  • the total drying time ie the time for active and passive drying, can vary between 10 s and 96 h.
  • Rinsing steps are not required according to the invention.
  • the drying can thus take place after the treatment of the metallic surface with the treatment solution without previous rinsing steps.
  • the anticorrosive coating layer produced according to the invention can serve both as a cover layer and on the other hand as an intermediate layer (intermediate barrier or vapor barrier and / or adhesion-promoting layer) both on metal-containing layers protecting the substrate cathodically and on full metal ware. In addition, it can also act as a modification of the surface of m-scaled metal particles.
  • the metallic surface can be suitably preconditioned in this case.
  • a suitable preconditioning is in particular the activation of the metallic surface by contacting it with a highly dilute acid by water acid, coordinated acid combinations or salts of suitable acids.
  • the metallic surface may have a conversion layer.
  • a conversion layer is preferably understood as meaning a layer which is formed by a chemical reaction of a (especially aqueous) treatment solution with a metal substrate
  • the conversion layer is preferably a chromium (III) -containing conversion layer
  • Such conversion layers can be produced, for example, with GC Multipass and DDPass (both products of Hillebrand Chemicals GmbH).
  • the treatment solution according to the invention is used as a night dip solution and the process according to the invention thus leads to a further improved corrosion protection.
  • the corrosion-protective coating layer according to the invention serves in this case as a seal with post-passivation properties and can also act as an additional primer for further layer structures.
  • the metallic surface does not have a conversion layer.
  • the aggressiveness of the mechanism of action, as opposed to a passivation is much lower, prolonged contact of the metallic surface with the treatment solution does not lead to overpassivation (redissolution of the passivation layer) and thus to loss of corrosion protection.
  • the salt load on the surface dries to a barrier dense layer and is therefore not disturbing.
  • the present invention thus also provides a process for producing a corrosion-protective coating layer on a metallic surface, wherein the surface to be treated has no conversion layer, the passivation and sealing of the surface to be treated takes place in one step and without rinsing step between them, and the coating layer formed in Essentially free of silanes of WO 2011/000969 A1.
  • the metallic surface to be treated is a material applied to a steel substrate which has a base electrochemical potential relative to the steel substrate.
  • the surface to be treated is a cathodic protective metallic surface.
  • the metallic surface to be treated is one selected from the group consisting of
  • a galvanically deposited layer containing zinc or a zinc alloy preferably ZnFe, ZnCd, ZnSn, ZnSnCu or ZnNi, with or without already implemented conversion layer,
  • hot-dip galvanized surfaces preferably containing zinc or a zinc alloy
  • a flame-sprayed layer preferably containing zinc, a zinc alloy, aluminum or an aluminum alloy, the surface of a layer produced by thermal diffusion method (sheradizing),
  • a zinc die-cast surface preferably containing a zamak alloy, preferably ZL0400, ZL0410 or ZL0430,
  • a clad aluminum surface a full metal surface, preferably containing zinc, aluminum, magnesium or an alloy of zinc, aluminum or magnesium with preferred trace elements
  • pm-scaled metal particles preferably containing zinc, aluminum, magnesium, manganese, tin, nickel, iron, molybdenum, vanadium,
  • MDTS metal dispersion dry layers
  • a metal dispersion dry layers preferably containing zinc, aluminum, manganese, copper, tin, nickel, iron, molybdenum, vanadium and / or magnesium, as well as silicon, titanium and / or zirconium.
  • a metal dispersion dry layers preferably containing zinc, aluminum, manganese, copper, tin, nickel, iron, molybdenum, vanadium and / or magnesium, as well as silicon, titanium and / or zirconium.
  • zinc and aluminum, as well as titanium, silicon and zirconium Preferably containing zinc and aluminum, as well as titanium, silicon and zirconium.
  • the metallic surface is the surface of a tape product.
  • Exemplary applications on such cathodically protective metallic surfaces and the process parameters used are listed below: i) Galvanically deposited zinc or zinc alloy layers
  • the treatment solution is preferably adjusted to a pH of 4 to 5 and the product is preferably dried actively at 80 ° C for 10 min.
  • the cover layer produced has no adhesion tendency, which leads to very good coating results, in particular when applied to bulk goods. Surface areas with extreme wet film thickness of the processing solution will dry without the appearance of feed to a flexible film.
  • the pH can be lowered to values up to pH 3, resulting in a shorter treatment time and / or a greater passivation effect.
  • the treatment solution according to the invention is preferably adjusted to a pH of 3 to 6. Due to a lower pH of the treatment solution, the Treatment temperature can be reduced to room temperature, which can be saved especially in large bath surfaces energy. If the hot, already quenched hot-dip galvanized product is brought into contact with the treatment solution, forms by reactivity of the active substances, a closed layer which dries by residual heat of the part body without additional energy. iii) flame spray coatings
  • Zinc or aluminum surfaces applied by flame spraying can preferably be treated with the treatment solution according to the invention at pH values between 3 and 6.
  • the process-related residual heat can also be used here for complete drying of the aftertreatment layer.
  • thermodiffusion-galvanized surfaces Another field of application of the treatment solution according to the invention is the coating of thermodiffusion-galvanized surfaces. Due to the combination of passivation and sealing, there is the advantage that, despite the high iron content of the diffusion layer, the punctual red rust breakthroughs, which typically occur early, can be prevented for a long time. Bulk products can be easily treated because of the universal applicability of the passivation solution.
  • thermodiffusion zinc Over a particularly wide pH value interval for setting the process chemistry, different layer properties on thermodiffusion zinc are made possible. For example, by setting a mild pH of 4 to 5, the original surface coloration can be maintained whereas a pH of 2.5 to 3.5 produces dark layers. v) Mechanical galvanizing
  • the method according to the invention is also suitable for the treatment of metal goods which have metal dispersion dry layers (MDTS).
  • MDTS typically have a layer thickness of 5 to 25 pm.
  • MDTS can be produced on metallic surfaces by bringing the surface to be treated into contact with a special dispersion and then drying.
  • the dispersion contains an organic and / or inorganic binding matrix and pm-scaled metal particles in spherical and / or lamellar form.
  • the ⁇ -scaled metal particles are zinc, aluminum, magnesium, manganese, tin, nickel, iron, molybdenum and / or vanadium and / or particles, which consist of an alloy of said metals.
  • the pm-scaled metal particles can also contain the least amounts of rare earths or their alloys.
  • the treated metal goods preferably consist of materials which have an electrochemically nobler potential than the MDTS surrounding them.
  • Modern MDTS can be present as a metallic silver as well as a dark gray to black surface.
  • the treatment solution can be applied to an untreated, clean MDTS.
  • the coating layer obtained after drying then acts at the same time as a layer-forming passivation and anticorrosive covering layer, preferably with sealing properties. Tribological properties can also be adjusted by lubricants integrated in the anti-corrosive coating layer.
  • An optional black colored treatment solution supports the look of black MDTS.
  • the treatment solution should not be applied at a pH below 4.4. In the case of use as a passivating top layer, the treatment solution therefore has a mild pH, preferably between 4 and 1.5, preferably between 4.5 and 10 and particularly preferably between 5 and 7.5.
  • the anticorrosive coating layer can also be used as adhesion-promoting intermediate layer, in particular as passivation and vapor barrier for further organic and / or inorganic topcoats.
  • a lower pH of the treatment solution in this case reduces the treatment time.
  • the treatment solution thus has an acidic pH preferably between 2 and 7, preferably between 3 and 6 and particularly preferably between 3.5 and 5.
  • the temperature is preferably in the range of 15 to 80 ° C, preferably 25 to 60 ° C.
  • the treatment time is preferably in the range of 1 second to 5 minutes, preferably 5 seconds to 3 minutes, more preferably 10 seconds to 2 minutes and more preferably from 20 to 90 seconds.
  • the drying temperature is preferably in the range of 80 to 180 ° C.
  • the total drying time is preferably in the range from 5 minutes to 96 hours, preferably from 5 minutes to 3 hours and particularly preferably from 10 minutes to 30 minutes.
  • the treatment solution according to the invention is used for coating metallic materials preferably consisting of zinc, aluminum, manganese, magnesium, tin, silicon and their alloys to increase the corrosion protection, optimize the overall process and / or adjust the functional properties.
  • the metallic surface is preferably selected from the group consisting of solid metal surfaces, preferably containing zinc, aluminum, magnesium or an alloy of zinc, aluminum and / or magnesium with preferred trace elements, zinc die-cast surfaces, preferably containing a zamak alloy, preferably ZL0400, ZL0410 or ZL0430, surfaces of ⁇ scaled metal particles and clad aluminum surfaces.
  • the treatment solution according to the invention is used, for example, on fully metallic surfaces of zinc or zinc alloys, of aluminum or aluminum alloys with silicon, manganese, magnesium and / or copper and of magnesium or magnesium alloys with aluminum, zinc, manganese, silicon and / or zirconium for optical and / or surface modification.
  • the treatment solution is preferably used with a pH below 3.5.
  • the treatment solution is adjusted to a preferred pH of just over 4.
  • Zinc die-castings preferably of zamak alloys such as ZL0400, ZL0410 and ZL0430, both as drumware and in basket application, are dipped in the treatment solution and either dried or dried at room temperature.
  • a pH of 3.5 to 4.2 and a temperature of over 45 ° C a darkening of the layer can be achieved without destroying the cast skin of the component, which extreme corrosion protection loss would result.
  • a milder pH of 4.4 to 5 and a lower temperature of the treatment solution are set below 40 ° C, the pre-existing surface color may be retained.
  • basket application there is an advantage in drying over-coated areas to flexible, non-feeding films.
  • the coating layer produced by means of the treatment solution according to the invention serves as a passivation and adhesion promoter. If metal particles pretreated in this way are used in the production of a metal dispersion, there are highly positive effects with regard to the service life of the dispersion, the bonding of the modified metal particles in the binder matrix and the course of the layer corrosion.
  • the treatment solution is preferably adjusted to a pH of 2.5 to 6.
  • a mild pH of about 5 in combination with a longer treatment time of over 4min leads to a significant improvement in terms of anchoring with the binder system used, the optics of the metal particle surface is changed in only a very small extent.
  • a pH of the treatment solution in the range of 2.5 to 6.5 for the purpose of enhancing corrosion resistance or other functional properties such as heat distribution or reflectance.
  • optical characteristics for finalizing the surface treatment are obtained in particular by higher pH values.
  • lower pH values and thus a stronger attack of the sealing passivation offer the advantage of increased adhesion for further coatings such as e.g. Industrial coatings.
  • a concentrate according to the invention is used as an additive for sealants and topcoats.
  • sealants and topcoats are liquid and contain water and / or organic solvent as a solvent.
  • a metallic surface By treating a metallic surface with a seal modified in this way or a topcoat modified in this way, it is possible to produce a more adhesive and barrier-resistant cover layer, which additionally has a passivating effect.
  • seals are organic and / or inorganic coatings having a dry film thickness of less than 2 ⁇ m and their solutions for the production. Topcoats form the counterpart with dry film thicknesses of over 2 pm.
  • a concentrate according to the invention preferably an aqueous concentrate, is rendered alkaline, preferably added to a pH of 7.5 to 11.5, and in small amounts, preferably to 1 to 3% by volume, of a seal or a top coat. These then constitute a treatment solution in the sense of the present invention and can be used to produce a more adhesive, barrier-resistant layer with passivating properties.
  • the treated metallic surfaces are protected by passivation and barrier action, resulting in increased corrosion protection.
  • the addition also increases the adhesion of the topcoat to the treated metallic surfaces.
  • strip products with galvanically deposited layers or solid metal surfaces such as zinc, aluminum, magnesium, tin and alloys of these main constituents are finished with the treatment solution. Due to the reactive properties of the treatment solution only very short treatment times are necessary, so that at high flow speeds of the bands through the baths effective corrosion protection can be achieved.
  • the corrosion protection values in the following exemplary embodiments relate to production goods which have undergone conventional mechanical stresses.
  • WR stands for the time until the occurrence of white rust (zinc corrosion)
  • RR stands for the time until the occurrence of red rust (iron corrosion of the base metal).
  • aqueous solution of the following composition was used:
  • DTPMP 5 was added to an acrylic sealant as a 1% additive. This gave a treatment solution which had the following concentrations:
  • aqueous solution of the following composition was used:
  • Zinc die-cast wicker was first degreased hot, rinsed twice, activated and rinsed twice again. Subsequently, the product was at 35 ° C and a pH dipped on 4.6 for 75 s in the treatment solution and dried at room temperature.
  • the NSS gave the following corrosion protection result:
  • aqueous solution of the following composition was used:
  • the goods were first hot-dip galvanized, then quenched and dipped with a residual heat of about 70 ° C for 50 s and at a pH of 4.2 in a non-heated bath with the above treatment solution.
  • the drying was carried out by the object temperature of the treated part.
  • the NSS gave the following corrosion protection results:
  • Example 5 rescaled metal particles
  • aqueous solution of the following composition was used:
  • aqueous solution of the following composition was used:
  • a blasted steel surface with a 7 pm thick MDTS (lamellar zinc and aluminum particles and a titanium oxide / silica binder system) was subjected to a dip / spin application without subsequent rinse step.
  • the steel surface was wetted for 50 s at 40 ° C and a pH of 4.4 with the treatment solution and then dried at 80 ° C for 10 min.
  • aqueous solution of the following composition was used:
  • a blasted steel surface with a 7 pm thick MDTS (lamellar zinc and aluminum particles and a titanium oxide / silica binder system) was subjected to a dip / spin application without subsequent rinse step.
  • the steel surface was wetted with the treatment solution for 50 s at 35 ° C. and a pH of 5.5, and then dried at 80 ° C. for 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une solution de traitement destinée à un procédé de production d'une couche de revêtement de protection anticorrosion sur une surface métallique dans lequel la surface à traiter est mise en contact avec une solution de traitement contenant une source d'ions de chrome (III), une source de phosphate, une source d'ions de zinc et une source de citrate. Le ratio quantitatif des ions de chrome (III) sur les ions de zinc est égal à 1 pour au moins 1,65 et le ratio quantitatif des ions de chrome (III) sur le citrate est égal à 1 pour au moins 1,4. La solution de traitement est pratiquement dépourvue de polymères résultant de la réaction d'un ou plusieurs alcoxysilanes de formule : R4-xSi(OR1)x, où les restes R sont identiques ou différents et représentent chacun un groupe hydrocarbure substitué ou non substitué contenant 1 à 22 atomes de carbone, x vaut 1, 2 ou 3, et R1 représente un groupe hydrocarbure substitué ou non substitué contenant 1 à 8 atomes de carbone, et d'un ou plusieurs alcoxydes de formule : Me(OR2)n, où Me représente les éléments Ti, Zr, Hf, Al, Si et n le degré d'oxydation de Me, et R2 est un groupe hydrocarbure substitué ou non substitué contenant 1 à 8 atomes de carbone.
EP14771781.3A 2013-09-13 2014-09-15 Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion Active EP3044348B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
HRP20220130TT HRP20220130T1 (hr) 2013-09-13 2014-09-15 Otopina za obradu koja sadrži krom (iii) za postupak za proizvodnju antikorozivnog premaznog sloja, koncentrata takve otopine za obradu, i postupak za proizvodnju antikorozijskog premaznog sloja

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013015113.9A DE102013015113A1 (de) 2013-09-13 2013-09-13 Behandlungslösung für ein Verfahren zum Erzeugen einer korrosionsschützenden Überzugsschicht, Konzentrat einer solchen Behandlungslösung und Verfahren zum Erzeugen einer korrosionsschützenden Überzugsschicht
PCT/EP2014/002486 WO2015036124A1 (fr) 2013-09-13 2014-09-15 Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion

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EP3044348A1 true EP3044348A1 (fr) 2016-07-20
EP3044348B1 EP3044348B1 (fr) 2021-12-08

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CY (1) CY1124966T1 (fr)
DE (2) DE202013010956U1 (fr)
DK (1) DK3044348T3 (fr)
ES (1) ES2905136T3 (fr)
HR (1) HRP20220130T1 (fr)
HU (1) HUE058902T2 (fr)
PT (1) PT3044348T (fr)
WO (1) WO2015036124A1 (fr)

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US10190162B2 (en) 2014-10-23 2019-01-29 Complete Genomics, Inc. Signal confinement sequencing (SCS) and nucleotide analogues for signal confinement sequencing
EP3569734A1 (fr) * 2018-05-18 2019-11-20 Henkel AG & Co. KGaA Composition de passivation à base de chrome trivalent
CN111996522B (zh) * 2020-08-03 2022-08-16 鞍钢股份有限公司 一种锌铝镁钢板环保钝化剂及制备使用方法
EP3964609A1 (fr) 2020-08-28 2022-03-09 Coventya SAS Produit électroplaqué et procédé de préparation de tels produits par traitement à haute température

Citations (1)

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DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen

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DE19615664A1 (de) * 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
DE19638176A1 (de) 1996-09-18 1998-04-16 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
JP4625244B2 (ja) 2003-07-02 2011-02-02 ディップソール株式会社 ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法
ES2444406T3 (es) 2007-06-14 2014-02-24 Atotech Deutschland Gmbh Tratamiento anti-corrosión para capas de conversión
EP2281923A1 (fr) 2009-07-03 2011-02-09 ATOTECH Deutschland GmbH Traitement de protection anticorrosion pour surfaces en zinc et alliages de zinc
TWI555880B (zh) * 2011-04-01 2016-11-01 迪普索股份有限公司 ３價鉻化學轉換被膜用整理加工劑及黑色３價鉻化學轉換被膜之整理加工方法

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Publication number Priority date Publication date Assignee Title
DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen

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Title
See also references of WO2015036124A1 *

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CY1124966T1 (el) 2023-01-05
HRP20220130T1 (hr) 2022-04-15
PT3044348T (pt) 2022-02-03
DE202013010956U1 (de) 2014-12-17
WO2015036124A1 (fr) 2015-03-19
HUE058902T2 (hu) 2022-09-28
DK3044348T3 (da) 2022-02-07
EP3044348B1 (fr) 2021-12-08
ES2905136T3 (es) 2022-04-07
DE102013015113A1 (de) 2015-03-19

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