EP3612663B1 - Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série - Google Patents

Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série Download PDF

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Publication number
EP3612663B1
EP3612663B1 EP18716514.7A EP18716514A EP3612663B1 EP 3612663 B1 EP3612663 B1 EP 3612663B1 EP 18716514 A EP18716514 A EP 18716514A EP 3612663 B1 EP3612663 B1 EP 3612663B1
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Prior art keywords
activation
zinc
particularly preferably
aqueous dispersion
alkaline aqueous
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German (de)
English (en)
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EP3612663A1 (fr
Inventor
Jan-Willem Brouwer
Frank-Oliver Pilarek
Fernando Jose RESANO ARTALEJO
Jens KRÖMER
Matthias Hamacher
Thibault LESEUR
Marc Balzer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors
    • C23F11/188—Mixtures of inorganic inhibitors containing phosphates
    • 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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
    • 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

Definitions

  • the present invention relates to a method for zinc phosphating of components comprising surfaces of zinc to suppress the formation of insoluble components of the phosphating that loosely adhere to the surfaces of zinc and therefore to further improve the adhesion of subsequently applied dip-lacquer coatings.
  • the process uses activation of the zinc surfaces using dispersions containing particulate hopeite, phosphophyllite, scholzite and/or hureaulite, whereby the proportion of particulate phosphates in the activation must be adjusted to the amount of free fluoride and dissolved silicon in the zinc phosphating.
  • zinc phosphating is initiated by activating the metal surfaces of the component to be phosphated.
  • the wet chemical activation is carried out by bringing it into contact with colloidal dispersions of phosphates, which, immobilized on the metal surface, serve as a growth nucleus for the formation of a crystalline coating in the subsequent phosphating.
  • Suitable dispersions are colloidal, mostly alkaline, aqueous compositions based on phosphate crystallites, which have only slight crystallographic deviations in their crystal structure from the type of zinc phosphate layer to be deposited.
  • bi- and trivalent phosphates are also suitable as starting materials for providing a colloidal solution that is suitable for activating a metal surface for zinc phosphating. That's how she teaches WO 98/39498 A1 In this context, in particular bi- and trivalent phosphates of the metals Zn, Fe, Mn, Ni, Co, Ca and Al, with technically preferred phosphates of the metal zinc being used for activation for subsequent zinc phosphating.
  • Each type of activation has its own characteristics in relation to the phosphating that takes place in the subsequent step, which is particularly important when treating components that are made up of a mix of different metallic materials. Closed crystalline zinc phosphate coatings can no longer be formed on steel surfaces of components activated with Jernstedt salts if the proportion of dissolved aluminum in the zinc phosphating bath exceeds a certain threshold value, for example in components with a high aluminum content, so that activation according to WO 98/39498 A1 must be avoided. Such activation also has the advantage that, compared to activation with Jernstedt salts, thinner and better corrosion-protecting phosphate coatings are achieved on the aluminum surfaces.
  • the dissolved phosphates carried over into the dip coating can, on the one hand, negatively influence the separation characteristics of the dispersed paint components and, on the other hand, reduce the effective concentration of essential catalysts/crosslinkers based on selected heavy metals through precipitation reactions.
  • a transfer of phosphates can therefore be the cause of increased baking temperatures, especially for dipping paints that contain water-soluble salts of yttrium and/or bismuth in addition to the dispersed resin.
  • the task is therefore to find suitable conditions for a process for zinc phosphating of metallic components that also tolerates high proportions of dissolved aluminum and is therefore based on activation based on a colloidal solution of bi- and/or trivalent phosphates Zinc phosphate coatings that are largely defect-free and free of loose adhesions are achieved on the zinc surfaces, resulting in excellent paint adhesion overall.
  • a method is to be provided in which metallic components can be treated to form a layer in the phosphating stage, the components having both surfaces of zinc and surfaces of aluminum and preferably also steel.
  • This task is surprisingly achieved by adapting the proportion of particulate phosphates contributing to activation to the amount of free fluoride and silicon in the zinc phosphating.
  • the components treated according to the present invention can be any spatial structure of any shape and design that comes from a manufacturing process, in particular semi-finished products such as strips, sheets, rods, pipes, etc. and composite structures assembled from the aforementioned semi-finished products, the semi-finished products preferably being made by gluing or welding and/or flanging to form a composite construction.
  • a component is metallic if at least 10% of its geometric surface is formed by metallic surfaces.
  • galvanized steel types form surfaces of zinc, whereas, according to the invention, surfaces of iron can be exposed on the cut edges and ground-through points, for example of an automobile body that is made solely of galvanized steel.
  • the components of the series which at least partially have surfaces of zinc, preferably have at least 5% surfaces of zinc based on the component surface.
  • Steel types such as hot-formed steel can also be provided with a metallic coating of aluminum and silicon several micrometers thick to protect against scaling and aid in forming.
  • a corrosion-protective treatment of the components in series occurs when a large number of components are brought into contact with the treatment solution provided in the respective treatment steps and usually kept in system tanks, the bringing into contact of the individual components one after the other and therefore separated from each other in time.
  • the system tank is the container in which the pre-treatment solution is located in series for the purpose of anti-corrosion treatment.
  • the treatment steps of activation and zinc phosphating are carried out in series "one after the other" for a component of the anti-corrosion treatment if they are not interrupted by a subsequent wet-chemical treatment other than the one intended.
  • Wet chemical treatment steps in the context of the present invention are treatment steps that are carried out by bringing the metallic component into contact with a composition consisting essentially of water and do not represent rinsing steps.
  • a rinsing step serves exclusively for the complete or partial removal of soluble residues, particles and active components that are carried over from a previous wet-chemical treatment step on the component from the component to be treated, without the rinsing liquid itself containing active components based on metallic or semi-metallic elements, which are consumed simply by bringing the metallic surfaces of the component into contact with the flushing liquid.
  • the flushing liquid can only be city water.
  • pH value corresponds to the negative logarithm of the hydronium ion activity at 20 ° C and can be determined using pH-sensitive glass electrodes. A composition is therefore acidic if its pH is below 7 and alkaline if its pH is above 7.
  • the individual treatment steps of activation and zinc phosphating are coordinated in such a way that closed coatings are created on the zinc surfaces of the metallic components as part of the zinc phosphating, on which no finely divided components of the zinc phosphate coating are deposited. Accordingly, in the subsequent dip-coating, coatings are available which adhere excellently to the zinc surfaces treated according to the invention.
  • the quotient of the concentration of the phosphates contained in the inorganic particulate component of the alkaline aqueous dispersion of the activation is in mmol/kg based on PO 4 to the sum of the concentration of free fluoride and the concentration Silicon in each case in the acidic aqueous composition of the zinc phosphating and in each case in mmol/kg greater than 0.6, particularly preferably greater than 0.7.
  • the concentration of free fluoride in the acidic aqueous composition of zinc phosphating is potentiometric at 20 °C in the respective acidic one using a fluoride-sensitive measuring electrode to determine the aqueous composition of zinc phosphating.
  • the concentration of silicon in the acidic aqueous composition of zinc phosphating is to be determined in the filtrate of a membrane filtration of the acidic aqueous composition, which is carried out using a membrane with a nominal pore size of 0.2 ⁇ m, by means of atomic emission spectrometry (ICP-OES).
  • the particulate component of the alkaline aqueous dispersion is the solid fraction that remains after drying of the retentate of an ultrafiltration of a defined partial volume of the alkaline aqueous dispersion with a nominal exclusion limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off).
  • the ultrafiltration is carried out with the addition of deionized water ( ⁇ 1 ⁇ Scm -1 ) until a conductivity below 10 ⁇ Scm -1 is measured in the filtrate.
  • the inorganic particulate component of the alkaline aqueous dispersion is in turn the one that remains when the particulate component obtained from drying the retentate of the ultrafiltration is in a reaction oven with the supply of a CO 2 -free oxygen stream at 900 ° C without the addition of catalysts or other additives is pyrolyzed until an infrared sensor in the outlet of the reaction furnace delivers a signal identical to the CO 2 -free carrier gas (blank value).
  • the phosphates contained in the inorganic particulate component are determined as phosphorus content using atomic emission spectrometry (ICP-OES) directly from the acid digestion.
  • ICP-OES atomic emission spectrometry
  • the alkaline aqueous dispersion has a D50 value of less than 3 ⁇ m, otherwise only very high and therefore uneconomical proportions of particulate components will ensure that the metal surfaces are sufficiently covered with particles, the crystallization nuclei for zinc phosphating represent, can be done. In addition, dispersions whose particles are larger on average tend to sediment.
  • the D50 value of the alkaline aqueous dispersion of the activation is therefore smaller than 2 ⁇ m, particularly preferably smaller than 1 ⁇ m, where the D90 value is preferably smaller than 5 ⁇ m, so that at least 90 vol. -% of the particulate components contained in the alkaline aqueous composition fall below this value.
  • the D50 value refers to the volume-average particle diameter which does not exceed 50% by volume of the particulate components contained in the alkaline aqueous composition.
  • the active components of the alkaline dispersion which effectively promote the formation of a closed zinc phosphate coating on the metal surfaces of the component in the subsequent phosphating and in this sense activate the metal surfaces, are primarily composed of phosphates, which in turn are at least partially hopeite, phosphophyllite, scholzite and / or hureaulite include.
  • phosphates which in turn are at least partially hopeite, phosphophyllite, scholzite and / or hureaulite include.
  • the phosphate content of the inorganic particulate components of the alkaline aqueous dispersion of the activation is at least 30% by weight, particularly preferably at least 35% by weight, particularly preferably at least 40% by weight, calculated as PO 4 and based on the inorganic particulate component of the dispersion.
  • Activation in the sense of the present invention is therefore essentially based on the phosphates contained according to the invention in particulate form, the phosphates preferably being at least partially composed of hopeite, phosphophyllite and/or scholzite, particularly preferably hopeite and/or phosphophyllite and particularly preferably hopeite are.
  • the phosphates hopeite, phosphophyllite, scholzite and/or hureaulite can be dispersed into an aqueous solution as finely ground powder or as a powder paste triturated with a stabilizer to provide the alkaline aqueous dispersion.
  • hopeite stoichiometrically comprises Zn 3 (PO4) 2 as well as the nickel and manganese-containing variants Zn 2 Mn(PO 4 ) 3 , Zn 2 Ni(PO 4 ) 3 , whereas phosphophyllite consists of Zn 2 Fe(PO 4 ) 3 , Scholzite consists of Zn 2 Ca(PO 4 ) 3 and Hureaulite consists of Mn 3 (PO 4 ) 2 .
  • the existence of the crystalline phases hopeite, phosphophyllite, scholzite and/or hureaulite in the alkaline aqueous dispersion can be determined after separation of the particulate component by means of ultrafiltration with a nominal exclusion limit of 10 kD (NMWC, Nominal Molecular Weight Cut Off) as described above and drying of the retentate up to constant mass at 105°C using X-ray diffractometry methods (XRD).
  • NMWC Nominal Molecular Weight Cut Off
  • the alkaline aqueous dispersion of the activation contains at least 20% by weight, preferably at least 30% % by weight, particularly preferably at least 40% by weight, of zinc in the inorganic particulate component of the alkaline aqueous dispersion based on the phosphate content of the inorganic particulate component, calculated as PO 4 .
  • the proportion of titanium in the inorganic particulate component of the alkaline aqueous dispersion of the activation is preferably less than 5% by weight, particularly preferably less than 1% by weight, based on the inorganic particulate component of the dispersion .
  • the alkaline aqueous dispersion of the activation contains a total of less than 10 mg/kg, particularly preferably less than 1 mg/kg, of titanium.
  • the proportion of inorganic particulate components containing phosphates should be adjusted accordingly.
  • the proportion of phosphates in the inorganic particulate component, based on the alkaline aqueous dispersion of the activation is at least 80 mg/kg, particularly preferably at least 150 mg/kg, calculated as PO 4 .
  • activation should be carried out with colloidal solutions that are as dilute as possible.
  • the proportion of phosphates in the inorganic particulate component be less than 0.8 g/kg, particularly preferably less than 0.6 g/kg, particularly preferably less than 0.4 g/kg kg calculated as PO 4 .
  • the metal surfaces are only slightly pickled during activation.
  • the inorganic particulate components especially the insoluble phosphates, should only be subject to minimal corrosion. Accordingly, in the process according to the invention, it is preferred if the pH of the alkaline aqueous dispersion during activation is greater than 8, particularly preferably greater than 9, but preferably less than 12, particularly preferably less than 11.
  • the second treatment step of zinc phosphating immediately follows activation with or without an intermediate rinsing step, so that each component in the series successively undergoes activation followed by zinc phosphating without an intermediate wet chemical treatment step.
  • neither a rinsing nor a drying step takes place for the components of the series between activation and zinc phosphating.
  • a drying step in the sense of the present invention refers to a process in which the surfaces of the metallic component that have a wet film are to be dried with the aid of technical measures, for example by supplying thermal energy or passing over an air stream.
  • the amount of phosphate ions includes the orthophosphoric acid and the anions of the salts of orthophosphoric acid dissolved in water, calculated as PO 4 .
  • the preferred pH value of the acidic aqueous composition of zinc phosphating in the process according to the invention is below 3.5, particularly preferably below 3.3.
  • the proportion of free acid in points in the acidic aqueous composition of zinc phosphating is preferably at least 0.4, but preferably not more than 3, particularly preferably not more than 2.
  • the proportion of free acid in points is determined by adding 10 ml sample volume of the Dilute the acidic aqueous composition to 50 ml and titrate with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of ml of caustic soda indicates the free acid score.
  • the acidic aqueous composition of zinc phosphating additionally contains cations of the metals manganese, calcium and/or iron.
  • the usual additives for zinc phosphating can also be carried out in an analogous manner according to the invention, so that the acidic aqueous composition can contain the usual accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and/or N-methylmorpholine-N-oxide.
  • the usual accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and/or N-methylmorpholine-N-oxide.
  • a source of free fluoride ions is essential for the process of layer-forming zinc phosphating on all metallic surfaces of the component, which are selected from surfaces of zinc, iron and/or aluminum. If all surfaces of the metallic materials of the components that are treated as part of the series are to be provided with a phosphate coating, the amount of particulate components in the activation must be adjusted to the amount of free fluoride required for the layer formation in zinc phosphating. In addition to the zinc surfaces, the surfaces of iron, especially steel, should also be included are provided with a closed and defect-free phosphate coating, it is preferred in the process according to the invention if the amount of free fluoride in the acidic aqueous composition is at least 0.5 mmol/kg.
  • the amount of free fluoride in the acidic aqueous composition is at least 2 mmol/kg.
  • the concentration of free fluoride should not exceed values above which the phosphate coatings predominantly have adhesions that can be easily wiped off, since these cannot be avoided even by a disproportionately increased amount of particulate phosphates in the alkaline aqueous dispersion of the activation. Therefore, it is also advantageous for economic reasons if, in the process according to the invention, the concentration of free fluoride in the acidic aqueous composition of zinc phosphating is below 8 mmol/kg.
  • the amount of free fluoride is to be determined potentiometrically at 20 °C in the respective acidic aqueous composition using a fluoride-sensitive measuring electrode.
  • Suitable sources of free fluoride are complex fluorides of the element.
  • the source of free fluoride is at least partially selected from complex fluorides of the element Si, in particular from hexafluorosilicic acid and its salts.
  • the expert in phosphating understands speck formation as the phenomenon of local deposition of amorphous, white zinc phosphate in an otherwise crystalline phosphate layer on the treated zinc surfaces or on the treated galvanized or alloy-galvanized steel surfaces.
  • the speck formation is caused by a locally increased pickling rate of the substrate.
  • Such point defects in phosphating can be the starting point for the corrosive debonding of subsequently applied organic paint systems, so that the occurrence of specks can largely be avoided in practice.
  • the concentration of silicon in dissolved form in water in the acidic aqueous composition of the zinc phosphating is at least 0.5 mmol/kg, particularly preferably at least 1 mmol/kg, but preferably less than 6 mmol/kg, particularly preferably less than 5 mmol /kg, particularly preferably less than 4.5 mmol/kg.
  • the upper limits for the concentration of silicon are preferred because they are above these values Phosphate coatings are favored, which predominantly have such loose adhesions that cannot be avoided even by a disproportionately increased amount of particulate phosphates in the alkaline aqueous dispersion of activation.
  • the concentration of silicon in the acidic aqueous composition in dissolved form in water is to be determined in the filtrate of a membrane filtration of the acidic aqueous composition, which is carried out using a membrane with a nominal pore size of 0.2 ⁇ m, by means of atomic emission spectrometry (ICP-OES).
  • a further advantage of the process according to the invention is that in the course of it, closed zinc phosphate coatings are also formed on surfaces of aluminum. Consequently, the series of components to be treated in the method according to the invention also includes the treatment of components that have at least one surface made of aluminum. It is irrelevant whether the surfaces of zinc and aluminum are realized in a component composed of corresponding materials or in various components in the series.
  • a good paint adhesive base for a subsequent dip-coating, during which a substantially organic top layer is applied is realized.
  • this is followed by an immersion coating, particularly preferably an electrocoating, particularly preferably a cathodic electrocoating.

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

Claims (11)

  1. Procédé permettant le traitement anticorrosion d'une série de composants métalliques comprenant des composants métalliques qui présentent au moins partiellement des surfaces en zinc et des composants métalliques qui présentent au moins une surface en aluminium, dans lequel les composants métalliques de la série sont successivement soumis aux étapes de traitement chimique par voie humide suivantes :
    (I) activation par mise en contact avec une dispersion aqueuse alcaline qui présente une valeur D50 inférieure à 3 µm et dont le constituant particulaire inorganique comprend des phosphates, dans lequel l'ensemble desdits phosphates est au moins partiellement composé d'hopéite, phosphophyllite, scholzite et/ou huréaulite et dans lequel la proportion de phosphates dans le constituant particulaire inorganique, par rapport à la dispersion aqueuse alcaline, est inférieure à 0,8 g/kg, calculée en tant que PO4 ;
    (II) phosphatation au zinc par mise en contact avec une composition aqueuse acide comportant un pH inférieur à 3,5 et contenant
    (a) 5 à 50 g/kg d'ions phosphate,
    (b) 0,3 à 3 g/kg d'ions zinc, et
    (c) au moins une source de fluorure libre, dans lequel des fluorures complexes de l'élément silicium sont contenus comme source de fluorure libre,
    dans lequel à la fois la concentration de silicium sous forme dissoute dans l'eau et la concentration de fluorure libre dans la composition aqueuse acide sont d'au moins 0,5 mmol/kg,
    caractérisé en ce que le quotient de la concentration des phosphates dans le constituant particulaire inorganique de la dispersion aqueuse alcaline de l'activation en mmol/kg par rapport à la somme de la concentration de fluorure libre et de la concentration de silicium, respectivement dans la composition aqueuse acide de la phosphatation au zinc et respectivement en mmol/kg, est supérieur à 0,5.
  2. Procédé selon la revendication 1, caractérisé en ce que la proportion de phosphates, par rapport aux constituants particulaires inorganiques de la dispersion aqueuse alcaline, est d'au moins 30 % en poids, de manière particulièrement préférée d'au moins 35 % en poids, de manière extrêmement préférée d'au moins 40 % en poids, calculée en tant que PO4.
  3. Procédé selon l'une des revendications précédentes ou les deux, caractérisé en ce que la proportion de zinc dans le constituant particulaire inorganique de la dispersion aqueuse alcaline dans l'activation est d'au moins 20 % en poids, préférentiellement d'au moins 30 % en poids, de manière particulièrement préférée d'au moins 40 % en poids.
  4. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la proportion de titane dans le constituant particulaire inorganique de la dispersion aqueuse alcaline dans l'activation est inférieure à 5 % en poids, de manière particulièrement préférée est inférieure à 1 % en poids, et de manière extrêmement préférée moins de 10 mg/kg de titane sont contenus dans la dispersion aqueuse alcaline de l'activation.
  5. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la quantité de phosphates provenant du constituant particulaire inorganique de la dispersion aqueuse alcaline dans l'activation est d'au moins 80 mg/kg, de manière particulièrement préférée d'au moins 150 mg/kg, calculée en tant que PO4 et par rapport à la dispersion.
  6. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le pH de la dispersion aqueuse alcaline dans l'activation est supérieur à 8, préférentiellement supérieur à 9, mais préférentiellement inférieur à 12, de manière particulièrement préférée inférieur à 11.
  7. Procédé selon la revendication 6, caractérisé en ce que la concentration de silicium sous forme dissoute dans l'eau est d'au moins 1 mmol/kg, mais est préférentiellement inférieure à 6 mmol/kg.
  8. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que l'acidité libre dans la composition aqueuse acide de la phosphatation au zinc est d'au moins 0,4 point, mais préférentiellement de pas plus de 3 points, de manière particulièrement préférée de pas plus de 2 points.
  9. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la concentration de fluorure libre dans la composition aqueuse acide de la phosphatation au zinc est d'au moins 2 mmol/kg, mais préférentiellement de moins de 8 mmol/kg.
  10. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que ni une étape de rinçage, ni une étape de séchage n'est effectuée entre l'activation et la phosphatation au zinc.
  11. Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la phosphatation au zinc avec ou sans étape intermédiaire de rinçage et/ou de séchage, mais préférentiellement avec étape de rinçage, mais sans étape de séchage, est suivie d'un laquage par immersion, préférentiellement d'un laquage électrophorétique par immersion, de manière particulièrement préférée d'un laquage électrophorétique par immersion cathodique.
EP18716514.7A 2017-04-21 2018-03-09 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série Active EP3612663B1 (fr)

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EP17167478.1A EP3392376A1 (fr) 2017-04-21 2017-04-21 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série
PCT/EP2018/055871 WO2018192709A1 (fr) 2017-04-21 2018-03-09 Procédé de phosphatation au zinc filmogène d'éléments métalliques en série

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CA3103058A1 (fr) 2018-06-11 2019-12-19 Henkel Ag & Co. Kgaa Dispersion aqueuse pour l'activation d'une surface metallique et son procede de phosphatation
EP3828307A1 (fr) 2019-11-26 2021-06-02 Henkel AG & Co. KGaA Procédé économe en ressources permettant d'activer une surface métallique avant une phosphatation
EP3954805A1 (fr) * 2020-08-11 2022-02-16 Henkel AG & Co. KGaA Procédé efficace dans l'utilisation des ressources destiné à la phosphatation au zinc d'une surface métallique
EP3964606A1 (fr) * 2020-09-04 2022-03-09 Henkel AG & Co. KGaA Procédé en une étape de phosphation du zinc
CN113233598A (zh) * 2021-05-21 2021-08-10 光大水务科技发展（南京）有限公司 一种连续循环水处理生化池及水处理方法
CZ309976B6 (cs) * 2022-10-31 2024-03-27 České vysoké učení technické v Praze Způsob předúpravy povrchu ocelových komponent
CZ310649B6 (cs) * 2025-02-12 2026-03-11 České vysoké učení technické v Praze Aktivační koncentrát a způsob aktivace pro tříkationtové fosfátování povrchu kovového substrátu

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US6723178B1 (en) * 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
JP3545974B2 (ja) * 1999-08-16 2004-07-21 日本パーカライジング株式会社 金属材料のりん酸塩化成処理方法
WO2004007799A2 (fr) 2002-07-10 2004-01-22 Chemetall Gmbh Procede de revetement de surfaces metalliques
DE10323305B4 (de) 2003-05-23 2006-03-30 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände
JP4065289B2 (ja) 2004-11-30 2008-03-19 本田技研工業株式会社 アルミニウム合金の表面処理方法
JP4645470B2 (ja) * 2006-02-20 2011-03-09 住友金属工業株式会社 潤滑性、接着性に優れた亜鉛系めっき鋼板及びその製造方法
EP1988189B1 (fr) * 2006-02-20 2014-03-12 Nippon Steel & Sumitomo Metal Corporation Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc
DE102008000600B4 (de) 2008-03-11 2010-05-12 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel, die hiermit erzeugte Beschichtung und ihre Verwendung
JP5462467B2 (ja) 2008-10-31 2014-04-02 日本パーカライジング株式会社 金属材料用化成処理液および処理方法
DE102010030697A1 (de) * 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion
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PL3612663T3 (pl) 2024-06-24
WO2018192709A1 (fr) 2018-10-25
JP2020517823A (ja) 2020-06-18
US11486044B2 (en) 2022-11-01
ES2980302T3 (es) 2024-09-30
CN110582592A (zh) 2019-12-17
EP3612663A1 (fr) 2020-02-26
US20200032403A1 (en) 2020-01-30
EP3392376A1 (fr) 2018-10-24
CN110582592B (zh) 2023-01-24

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