EP3392376A1 - 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
EP3392376A1
EP3392376A1 EP17167478.1A EP17167478A EP3392376A1 EP 3392376 A1 EP3392376 A1 EP 3392376A1 EP 17167478 A EP17167478 A EP 17167478A EP 3392376 A1 EP3392376 A1 EP 3392376A1
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EP
European Patent Office
Prior art keywords
zinc
activation
mmol
alkaline aqueous
aqueous dispersion
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.)
Withdrawn
Application number
EP17167478.1A
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German (de)
English (en)
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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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP17167478.1A priority Critical patent/EP3392376A1/fr
Priority to JP2019556846A priority patent/JP7287901B2/ja
Priority to EP18716514.7A priority patent/EP3612663B1/fr
Priority to PCT/EP2018/055871 priority patent/WO2018192709A1/fr
Priority to CN201880026262.1A priority patent/CN110582592B/zh
Publication of EP3392376A1 publication Critical patent/EP3392376A1/fr
Priority to US16/593,600 priority patent/US11486044B2/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18Inhibiting 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
    • C23F11/187Mixtures of inorganic inhibitors
    • C23F11/188Mixtures of inorganic inhibitors containing phosphates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • C23C22/36Chemical 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
    • C23C22/362Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • C23C22/36Chemical 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
    • C23C22/364Chemical 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
    • C23C22/365Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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 process for zinc phosphating components comprising zinc surfaces for suppressing the formation of insoluble phosphating components loosely adhering to the surfaces of zinc, and thus further improving the adhesion of post-applied dip coatings.
  • activation of the zinc surfaces by means of dispersions containing particulate hopeite, phosphophyllite, scholzite and / or hureaulite is resorted to, the proportion of particulate phosphates having to be adjusted in the activation of the amount of free fluoride and dissolved silicon in the zinc phosphating.
  • the zinc phosphating is initiated with an activation of the metal surfaces of the component to be phosphated.
  • the wet-chemical activation is carried out by contacting with colloidal dispersions of phosphates, which in this respect immobilized on the metal surface, serve in the subsequent phosphating as growth nuclei for the formation of a crystalline coating.
  • Suitable dispersions are colloidal, mostly alkaline aqueous compositions based on phosphate crystallites, which have only small crystallographic deviations in their crystal structure from the type of zinc phosphate layer to be deposited.
  • water-insoluble bi-and trivalent phosphates are also suitable as starting materials for providing a colloidal solution suitable for activating a metal surface for zinc phosphating. That's how it 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, wherein technically preferred phosphates of the metal zinc are used for activation for a subsequent zinc phosphating.
  • Each type of activation has its peculiarity with respect to the phosphating to be carried out in the subsequent step, which becomes particularly significant in the treatment of components composed 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, in the zinc phosphating bath, the proportion of dissolved aluminum exceeds a certain threshold value, for example in the case of components having a high aluminum content WO 98/39498 A1 must be avoided. Such activation also provides the advantage of being compared For activation with Jernstedt salts thinner and more corrosion-resistant phosphate coatings on the aluminum surfaces can be achieved.
  • This object is surprisingly achieved in that the proportion of contributing to the activation of particulate phosphates is adjusted to the amount of free fluoride and silicon in the zinc phosphating.
  • the treated according to the present invention components can be any arbitrarily shaped and designed spatial structures that originate from a fabrication process, in particular also semi-finished products such as strips, sheets, rods, tubes, etc. and composite structures assembled from the aforementioned semi-finished products, wherein the semi-finished products preferably by gluing, welding and / or flanging to the composite structure are connected together.
  • a component is metallic if its geometric surface is formed by at least 10% of metallic surfaces.
  • galvanized steel grades according to the invention form surfaces of zinc, whereas at the cutting edges and fürschliffstellen example, an automobile body, which is made solely of galvanized steel, according to the invention surfaces of iron can be exposed.
  • the components of the series which at least partially have surfaces of zinc, preferably at least 5%, based on the component surface surfaces of zinc.
  • Steel grades such as hot-formed steel may also be provided with a metallic coating of aluminum and silicon several microns thick to prevent scaling and forming.
  • Such a coated steel material although the base material is steel, has an aluminum surface in the context of the present invention.
  • Corrosion-preventing treatment of the components in series occurs when a plurality of components are brought into contact with each other in the treatment solution provided in the respective treatment steps and usually stored in system tanks, wherein the contacting the individual components one after the other and thus separated in time takes place.
  • the system tank is the container in which the pre-treatment solution is in series for the purpose of anti-corrosive treatment.
  • the treatment steps of activation and zinc phosphating are carried out for a component of the anticorrosive treatment in series then "successively", unless they are interrupted by any other than the respectively provided subsequent wet chemical treatment.
  • Wet-chemical treatment steps in the context of the present invention are treatment steps which take place by bringing the metallic component into contact with a composition consisting essentially of water and do not represent rinsing steps.
  • a rinsing step is used exclusively for the complete or partial removal of soluble residues, particles and active components, which are abducted adhering to the component from a previous wet-chemical treatment step, of the component to be treated, without active components based on metallic or semi-metallic elements being contained in the rinsing liquid itself. which consume already by the mere bringing into contact of the metallic surfaces of the component with the rinsing liquid. So the flushing liquid can only be city water.
  • the "pH" as used in the present invention corresponds to the negative decadic logarithm of the hydronium ion activity at 20 ° C and can be determined by means of pH-sensitive glass electrodes. Accordingly, a composition is acidic if its pH is below 7, and alkaline if its pH is above 7.
  • a coordination of the individual treatment steps of activation and zinc phosphating is implemented in such a way that closed coatings are formed on the zinc surfaces of the metallic components in the course of zinc phosphating, on which no finely divided constituents of the zinc phosphate coating are deposited. Accordingly, coatings are available in the subsequent dip coating, which adhere well to the zinc surfaces treated according to the invention.
  • the concentration of free fluoride in the acidic aqueous composition of zinc phosphating after calibration with fluoride-containing buffer solutions without pH buffering by means of a fluoride-sensitive measuring electrode potentiometric at 20 ° C in the respective acidic aqueous composition of zinc phosphating.
  • the concentration of silicon in the acidic aqueous composition of the zinc phosphating is to be determined in the filtrate by membrane filtration of the acidic aqueous composition made using a membrane having a nominal pore size of 0.2 ⁇ m by atomic emission spectrometry (ICP-OES).
  • the particulate constituent of the alkaline aqueous dispersion is that solid fraction which, after drying the retentate, remains an ultrafiltration of a defined partial volume of the alkaline aqueous dispersion with a nominal cutoff 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 remaining when the particulate component obtained from the drying of the ultrafiltration retentate remains in a reaction furnace at 900 ° C.
  • the phosphates contained in the inorganic particulate ingredient are determined after acid digestion thereof with aqueous 10 wt .-% HNO 3 solution at 25 ° C for 15 min as phosphorus content by 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 microns, otherwise only a very high and thus non-economic proportions of particulate components sufficient occupancy of the metal surfaces with particles, the crystallization nuclei for zinc phosphating represent, can take place.
  • the D50 value of the alkaline aqueous dispersion of the activation is therefore less than 2 .mu.m, more preferably less than 1 .mu.m, the D90 value being preferably less than 5 .mu.m, so that at least 90 vol. -% of the particulate components contained in the alkaline aqueous composition fall below this value.
  • the D50 value in this context refers to the volume-average particle diameter which does not exceed 50% by volume of the particulate constituents 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 composed predominantly of phosphates, which in turn are at least partially hopite, phosphophyllite, scholzite and / or hureaulite include.
  • phosphates which in turn are at least partially hopite, phosphophyllite, scholzite and / or hureaulite include.
  • such activation is preferred in which the phosphate fraction of the inorganic particulate constituents of the alkaline aqueous dispersion of the activation is calculated at at least 30% by weight, more preferably at least 35% by weight, particularly preferably at least 40% by weight PO 4 and based on the inorganic particulate component of the dispersion.
  • Activation in the context of the present invention is thus essentially based on the phosphates according to the invention in particulate form, wherein the phosphates are preferably at least partially composed of hopeite, phosphophyllite and / or scholzite, particularly preferably hopeite and / or phosphophyllite and particularly preferably hopite are.
  • the phosphites hopeite, phosphophyllite, scholzite and / or hureaulite may be dispersed into an aqueous solution to provide the alkaline aqueous dispersion as finely ground powders or as a powder paste triturated with a stabilizer.
  • Hopeite without consideration of water of crystallization, comprise stoichiometrically Zn 3 (PO 4 ) 2 as well as the nickel- and manganese-containing variants Zn 2 Mn (PO 4 ) 3 , Zn 2 Ni (PO 4 ) 3 , whereas phosphophyllite comprises Zn 2 Fe (PO 4 ) 3 , Scholzite consists of Zn 2 Ca (PO 4 ) 3 and Hureaulith consists of Mn 3 (PO 4 ) 2 .
  • the existence of the crystalline phases hopeite, phosphophyllite, scholzite and / or hureaulite in the alkaline aqueous dispersion may, after separation of the particulate component by ultrafiltration with a nominal cutoff limit of 10 kD (NMWC) as described above and drying of the retentate to constant mass at 105 ° C using X-ray diffractometric methods (XRD).
  • NMWC nominal cutoff limit of 10 kD
  • the alkaline aqueous dispersion of activation is at least 20% by weight, preferably at least 30% Wt .-%, particularly preferably at least 40 wt .-% of zinc in the inorganic particulate component of the alkaline aqueous dispersion based on the phosphate content of the inorganic particulate Bestanteils, calculated as PO 4 contains.
  • activation in the sense of the present invention should not be achieved by means of colloidal solutions of titanium phosphates, as otherwise the layer-forming zinc phosphating Surfaces of iron, especially steel, not reliable succeeds and the advantage of thin effectively effective against corrosion protective phosphate coatings on aluminum is not realized.
  • the proportion of titanium in the inorganic particulate component of the alkaline aqueous dispersion of the activation is preferably less than 5 wt .-%, more preferably less than 1 wt .-% 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, more preferably less than 1 mg / kg of titanium.
  • the proportion of the inorganic particulate components comprising phosphates should be adjusted accordingly.
  • the proportion of phosphates in the inorganic particulate constituent based on the alkaline aqueous dispersion of the activation is at least 40 mg / kg, preferably at least 80 mg / kg, more preferably at least 150 mg / kg calculated as PO 4 is.
  • the activation should be carried out with as dilute as possible colloidal solutions.
  • the proportion of the phosphates in the inorganic particulate constituent based on the alkaline aqueous dispersion of the activation is less than 0.8 g / kg, more preferably less than 0.6 g / kg, particularly preferably less than 0.4 g / kg calculated as PO 4 .
  • the metal surfaces are only slightly stained during activation.
  • the inorganic particulate constituents in particular the insoluble phosphates, should undergo only a slight degree of corrosion. Accordingly, it is preferred in the process according to the invention if the pH of the alkaline aqueous dispersion in the activation is greater than 8, more preferably greater than 9, but preferably less than 12, more preferably less than 11.
  • the second zinc phosphating treatment step is followed by activation with or without intermediate rinsing step, immediately, so that each component of the series successively undergoes activation followed by zinc phosphating without intervening wet chemical treatment step.
  • neither a rinsing nor a drying step takes place between the activation and the zinc phosphating for the components of the series.
  • a drying step in the context of the present invention refers to a process in which the surfaces of the metallic component having a wet film are to be dried with the aid of technical measures, for example by supplying thermal energy or passing an air stream.
  • the amount of phosphate ions comprises the orthophosphoric acid and the anions of the salts of orthophosphoric acid dissolved in water, calculated as PO 4 .
  • the preferred pH of the acidic aqueous composition of zinc phosphating in the process according to the invention is above 2.5, more preferably above 2.7, but preferably below 3.5, most preferably below 3.3.
  • the proportion of the free acid in points in the acidic aqueous composition of the zinc phosphating is preferably at least 0.4, but preferably not more than 3, more preferably not more than 2.
  • the proportion of free acid in points is determined by adding 10 ml sample volume of the diluted acidic aqueous composition to 50 ml and titrated with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of ml of sodium hydroxide gives the score of free acid.
  • the acidic aqueous composition of the zinc phosphating additionally contains cations of the metals manganese, calcium and / or iron.
  • the customary addition of zinc phosphating can also be carried out in an analogous manner according to the invention so that the acidic aqueous composition can contain the conventional accelerators such as hydrogen peroxide, nitrite, hydroxylamine, nitroguanidine and / or N-methylmorpholine-N-oxide.
  • the conventional 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 device selected from surfaces of zinc, iron and / or aluminum. If all surfaces of the metallic materials of the components to be treated in the series are to be provided with a phosphate coating, the amount of the particulate constituents in the activation must be adapted to the amount of free fluoride required for layer formation in the zinc phosphating. Should in addition to the zinc surfaces as well as the surfaces of iron, especially steel, 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.
  • concentration of free fluoride should not exceed values above which the phosphate coatings predominantly have adhesions that are easily wipeable, since these can not be avoided 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 the zinc phosphating is below 8 mmol / kg.
  • the amount of free fluoride is determined potentiometrically after calibration with fluoride-containing buffer solutions without pH buffering by means of a fluoride-sensitive measuring electrode at 20 ° C in the respective acidic aqueous composition.
  • Suitable sources of free fluoride are hydrofluoric acid and its water-soluble salts, such as ammonium bifluoride and sodium fluoride, as well as complex fluorides of the elements Zr, Ti and / or Si, in particular complex fluorides of the element Si.
  • the source of free fluoride is therefore selected from hydrofluoric acid and its water-soluble salts and / or complex fluorides of the elements Zr, Ti and / or Si.
  • Salts of hydrofluoric acid are water-soluble for the purposes of the present invention, if their solubility in deionized water ( ⁇ 1 ⁇ Scm -1 ) at 60 ° C is at least 1 g / L calculated as F.
  • 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.
  • speckling one skilled in the phosphating art understands 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 speckling is caused by a locally increased pickling rate of the substrate.
  • Such point defects in the phosphating can be the starting point for the corrosive delamination of subsequently applied organic coating systems, so that the occurrence of specks in practice is largely to be avoided.
  • the upper limits for the concentration of silicon are preferred because above these values Promote phosphate coatings that have predominantly such loose attachments that can not be avoided by a disproportionately increased amount of particulate phosphates in the alkaline aqueous dispersion of the activation.
  • the concentration of silicon in the acidic aqueous composition dissolved in water is determined in the filtrate by membrane filtration of the acidic aqueous composition made using a membrane having a nominal pore size of 0.2 ⁇ m by atomic emission spectrometry (ICP-OES).
  • Another advantage of the method according to the invention is that in the course of which 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 preferably also includes the treatment of components which have at least one surface of aluminum. It is irrelevant whether the surfaces of zinc and aluminum are realized in a component composed of corresponding materials or in different components of the series.
  • a good lacquer adhesion base for a subsequent dip coating in the course of which a substantially organic cover layer is applied, is realized.

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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)
EP17167478.1A 2017-04-21 2017-04-21 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série Withdrawn EP3392376A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP17167478.1A EP3392376A1 (fr) 2017-04-21 2017-04-21 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série
JP2019556846A JP7287901B2 (ja) 2017-04-21 2018-03-09 層を形成するための連続して金属部品をリン酸亜鉛処理するための方法
EP18716514.7A EP3612663B1 (fr) 2017-04-21 2018-03-09 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
CN201880026262.1A CN110582592B (zh) 2017-04-21 2018-03-09 对金属部件系列锌磷化以形成层的方法
US16/593,600 US11486044B2 (en) 2017-04-21 2019-10-04 Method for zinc phosphating metal components in series so as to form layers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17167478.1A EP3392376A1 (fr) 2017-04-21 2017-04-21 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série

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EP3392376A1 true EP3392376A1 (fr) 2018-10-24

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EP18716514.7A Active EP3612663B1 (fr) 2017-04-21 2018-03-09 Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série

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US (1) US11486044B2 (fr)
EP (2) EP3392376A1 (fr)
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WO (1) WO2018192709A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3964606A1 (fr) * 2020-09-04 2022-03-09 Henkel AG & Co. KGaA Procédé en une étape de phosphation du zinc
CZ309976B6 (cs) * 2022-10-31 2024-03-27 České vysoké učení technické v Praze Způsob předúpravy povrchu ocelových komponent

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039498A1 (fr) 1997-03-07 1998-09-11 Henkel Corporation Conditionnement de surfaces metalliques prealablement a la phosphatation
WO2001012341A1 (fr) * 1999-08-16 2001-02-22 Henkel Corporation Procede de realisation d'un revetement de conversion a base de phosphate sur du metal
EP1988189A1 (fr) * 2006-02-20 2008-11-05 Sumitomo Metal Industries Limited Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc
EP2343399A1 (fr) * 2008-10-31 2011-07-13 Henkel AG & Co. KGaA Solution de traitement par conversion chimique d un matériau métallique et procédé de traitement

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723178B1 (en) * 1999-08-16 2004-04-20 Henkel Corporation Process for forming a phosphate conversion coating on metal
PT1521863E (pt) 2002-07-10 2008-09-19 Chemetall Gmbh Processo para revestir superfícies metálicas
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
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
DE102010030697A1 (de) * 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion
US20120183806A1 (en) 2011-01-17 2012-07-19 Ppg Industries, Inc. Pretreatment Compositions and Methods For Coating A Metal Substrate
JP2012253317A (ja) 2011-05-09 2012-12-20 Kobe Steel Ltd 圧粉磁心の製造方法、および該製造方法によって得られた圧粉磁心
BR112017021409B1 (pt) * 2015-04-07 2023-02-28 Chemetall Gmbh Método para fosfatação de uma superfície metálica, e, superfície metálica revestida com fosfato

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039498A1 (fr) 1997-03-07 1998-09-11 Henkel Corporation Conditionnement de surfaces metalliques prealablement a la phosphatation
WO2001012341A1 (fr) * 1999-08-16 2001-02-22 Henkel Corporation Procede de realisation d'un revetement de conversion a base de phosphate sur du metal
EP1988189A1 (fr) * 2006-02-20 2008-11-05 Sumitomo Metal Industries Limited Procede de production d'une feuille d'acier galvanise par immersion a chaud ayant un revetement en phosphate de zinc
EP2343399A1 (fr) * 2008-10-31 2011-07-13 Henkel AG & Co. KGaA Solution de traitement par conversion chimique d un matériau métallique et procédé de traitement

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3964606A1 (fr) * 2020-09-04 2022-03-09 Henkel AG & Co. KGaA Procédé en une étape de phosphation du zinc
WO2022048963A1 (fr) * 2020-09-04 2022-03-10 Henkel Ag & Co. Kgaa Procédé en une étape pour la phosphatation du zinc
CZ309976B6 (cs) * 2022-10-31 2024-03-27 České vysoké učení technické v Praze Způsob předúpravy povrchu ocelových komponent

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US11486044B2 (en) 2022-11-01
EP3612663A1 (fr) 2020-02-26
US20200032403A1 (en) 2020-01-30
JP7287901B2 (ja) 2023-06-06
WO2018192709A1 (fr) 2018-10-25
CN110582592A (zh) 2019-12-17

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