EP2215285B1 - Zirconiumphosphatierung von metallischen bauteilen, insbesondere eisen - Google Patents

Zirconiumphosphatierung von metallischen bauteilen, insbesondere eisen Download PDF

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Publication number
EP2215285B1
EP2215285B1 EP08853163.7A EP08853163A EP2215285B1 EP 2215285 B1 EP2215285 B1 EP 2215285B1 EP 08853163 A EP08853163 A EP 08853163A EP 2215285 B1 EP2215285 B1 EP 2215285B1
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Prior art keywords
ppm
zirconium
less
treatment solution
hollow body
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German (de)
English (en)
French (fr)
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EP2215285A1 (de
Inventor
Maximilian SCHÖNHERR
Jerzy-Tadeusz Wawrzyniak
Eva Wiedemann
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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
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4935—Heat exchanger or boiler making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]

Definitions

  • the present invention relates to a process for the corrosion-protective pretreatment of metallic components, which at least partially comprise metallic iron surfaces, with a chromium-free aqueous treatment solution containing fluorocomplexes of zirconium and / or titanium and phosphate ions in a specific ratio range to each other, and a metallic component, which has been pretreated accordingly, and its use for the application of further anti-corrosive coatings and / or paint systems.
  • the method is particularly suitable as a pretreatment for an electrodeposition coating of metallic components, which are in the form of non-closed hollow bodies.
  • the present invention therefore also relates to a process for coating a non-closed metallic hollow body, which comprises both the pretreatment with the chromium-free aqueous treatment solution and a subsequent electrodeposition coating, and a metallic hollow body, which is coated according to the inventive method, and its use for the production of radiators.
  • the passivation of metallic materials is ensured primarily by the zinc or iron phosphating.
  • zinc or iron phosphating mostly crystalline inorganic coatings are produced on the metallic base material, which have a layer thickness of several micrometers and, due to their surface topography, have excellent adhesion to organic cover layers, especially to coating systems applied in the electrocoating process.
  • non-film-forming iron phosphating the conversion becomes the metal surface is typically made in a phosphoric acid medium also in the presence of accelerators and wetting agents at elevated bath temperature.
  • Such iron phosphate layers rarely have layer weights of more than 1 g / m 2 and, in contrast to phosphations with high layer weights, are amorphous.
  • the classical phosphating is a multi-step process consisting of a cleaning step to degrease the component, an activation process and ultimately the actual phosphating, wherein for decoupling the process baths in continuous operation rinsing steps are installed.
  • a rinsing process is obligatory, at least after the cleaning step, so that the phosphating is composed of at least four individual processes which have to be monitored and controlled in terms of process technology in individual baths.
  • Additional alternative methods for standard phosphating which provide coating weights of significantly more than 1 g / m 2 , are, in addition to the non-layering iron phosphating, conversion treatments of the metallic surfaces to form purely amorphous, inorganic passive layers with much lower coating weights of the order of magnitude less as 200 mg / m 2 .
  • Any pretreatment processes that produce such "non-film-forming" (non-crystalline) phosphating and / or metal surface conversion have the advantage of rendering surface activation unnecessary and can thus be saved in the process chain of pretreatment.
  • Another advantage over the layer-forming zinc phosphating is the reduction of phosphate sludge in the phosphating baths.
  • the DE 1933013 also discloses phosphate-free treatment baths with a pH above 3.5, in addition to complex fluorides of boron, titanium or zirconium in amounts of 0.1 to 15 g / l, based on the metals, in addition 0.5 to 30 g / l Contain oxidizing agent, in particular sodium m-nitrobenzenesulfonate.
  • oxidizing agent sodium m-nitrobenzenesulfonate comes according to the teaching of DE 1933013 the function to vary the treatment time of the metal surfaces in a particularly large extent.
  • the disclosed WO 03/002781 Pretreatment solutions containing not only phosphoric acid but also fluorocomplexes of zirconium and / or titanium and a homo- or copolymer of vinylpyrrolidone.
  • Such a pretreatment solution provides low mass mixed amorphous mixed organic / inorganic passivations which may be provided with an electrodeposition paint.
  • DE 2715292 discloses treatment baths for chromium-free pretreatment of aluminum cans containing at least 10 ppm of titanium and / or zirconium, between 10 and 1000 ppm of phosphate and a sufficient amount of fluoride to form complex fluorides of the existing titanium and / or zirconium, but at least 13 ppm, and pH Values between 1.5 and 4.
  • the WO 2009/045872 discloses, as a post-published prior art under Art. 54 (3) EPC, methods for anticorrosive treatment of iron surfaces comprising aqueous compositions having a pH in the range of 4 to 5.5, containing essentially one metal compound selected from Group IIIB and Group IIIB elements or IVB and phosphate ions wherein the weight ratio of metal compounds to phosphate ions is at least 2: 1, contacted with the iron surfaces and then coated with a film-forming resin-containing agent.
  • the WO 2009/045872 The embodiments in particular those methods for pretreatment in the context of the present invention, in which steel sheets first cleaned with an alkaline cleaner, then rinsed twice with city water, then with a bath, which is composed at a pH of 5 so that about 10 ppm Iron ions containing either 80 ppm zirconium and 55 ppm phosphate ions or 150 ppm zirconium and 100 ppm phosphate ions, treated and then rinsed with city water.
  • the DE 10 2005 059314 A1 discloses a conversion treatment for steel surfaces which are electrocoated.
  • the one used for this aqueous conversion solution has a pH of 2.5 to 5 and contains 10-500 ppm of Ti or Zr as Hexafluorokomplex.
  • the solution may contain 10 to 500 ppm of phosphate and 50 to 500 ppm of silica having an average particle size of less than 1 ⁇ m and 10 to 1000 ppm of aromatic hydroxycarboxylic acids and 500 to 2000 ppm of nitrobenzenesulfonic acid.
  • the WO 03/100130 A discloses a conversion process for steel surfaces which are electrocoated.
  • the conversion solutions include phosphate, a Group IVB metal compound, and an accelerator, which may be selected from nitrobenzenesulfonic acid.
  • the US-A-4017335 discloses a method for phosphating pretreatment of iron surfaces prior to subsequent application of an organic coating.
  • the concentrates for use in such a process may contain, in addition to phosphate, also fluoro acids of the elements Zr and Ti, a surfactant and an accelerator which may be nitrobenzenesulfonic acid.
  • the object of the present invention is therefore to provide a conversion treatment of metallic components consisting at least partially of iron, which compared to the non-layer-forming treatment methods known in the prior art at least comparable or improved results in terms of corrosion protection and electrodeposition paint consumption provides, without, however, having to resort to the complex and energy-intensive process steps of the layer-forming phosphating.
  • the alternative method is to provide a corrosion-protected metallic surface, in particular iron surface, in as few and easily controllable process steps as possible and, on the other hand, to be as resource-efficient as possible, avoiding residues which are difficult to work up, for example phosphate sludges.
  • such an alternative method must ensure the subsequent electrocoating of the treated metallic component, preferably in the form of a non-closed hollow body, with an optimal Lackumgriff generally the lowest possible paint consumption is sought.
  • the metallic component is preferably made entirely of iron and / or an iron alloy containing more than 50 at.% Of iron or surfaces whose iron content is greater than 50 at.%.
  • the treatment solution does not require any additions of chromium compounds and is therefore chromium-free for ecological reasons and to ensure a high level of occupational safety.
  • ions of chromium in a low concentration enter the pretreatment solution from the container material or from the surfaces to be treated, for example steel alloys.
  • concentration of chromium in the ready-to-use processing solution is not higher than about 10 ppm, preferably not higher than 1 ppm.
  • the pH of the treatment solution can be arbitrarily adjusted by adding dilute nitric acid or ammoniacal solution in the specified range.
  • the pH of the treatment solution is particularly preferably below 5.5, in particular below 5.0.
  • the performance of the pretreatment with regard to corrosion resistance of the treated components and the throw-over behavior in a subsequent electrodeposition coating can be adjusted.
  • excessively high ratios of zirconium and / or titanium to the phosphate present in the treatment solution as well as excessively low relative zirconium and / or titanium contents have a significantly negative effect on the throwing behavior.
  • An optimum result, that is to say maximum permeation in the paint deposition, is achieved if the molar ratio of zirconium and / or titanium to phosphate ions is set to not less than 1: 1.
  • zirconium compounds in the different embodiments of the present invention gives technically better results than the use of titanium compounds and is therefore preferred.
  • complex fluoro acids or their salts can be used.
  • treatment solutions which contain as component (i) at least 150 ppm, preferably at least 200 ppm, but not more than 350 ppm, preferably not more than 300 ppm of zirconium in the form of a fluorocomplex.
  • the phosphate content of the treatment solution according to the invention is extremely low in comparison with zinc or iron phosphating baths described in the prior art.
  • a low concentration of phosphate ions of at least 10 ppm in combination with the fluorocomplexes of zirconium and or titanium leads to the formation of a thin amorphous zirconium and / or titanium phosphate layer and thus to the desired passivation of the metal surface, in particular the iron surface.
  • a homogeneous passivation takes place already at phosphate contents of preferably 30 ppm, more preferably at least 60 ppm.
  • the phosphate content should not exceed 1000 ppm and preferably not more than 180 ppm, particularly preferably not more than 120 ppm phosphate ions.
  • accelerators known from zinc and iron phosphating promote the formation of a homogeneous passivation.
  • Such accelerators are oxidizing agents that perform the task of a "hydrogen scavenger" in the phosphating process by eliminating the hydrogen produced by the acid attack on the metallic surface oxidize directly and thereby reduce itself.
  • the inhibition of massive hydrogen evolution on the material surface facilitates the formation of the crystalline phosphate layer with several micrometers layer thickness during the layer-forming phosphating.
  • the accelerators known in the prior art are also able to support the homogeneous formation of an amorphous passive layer based on zirconium and / or titanium phosphate, which comprises only a few nanometers.
  • the activity of the accelerators in the treatment bath is to be set much lower than is the case, for example, in zinc phosphating, so that typical oxidizing agents have to be used in amounts of not more than 1000 ppm, but at least 10 ppm must be present in the treatment solution promote zirconium- and / or titanium-based passivation of the ferrous metal surface.
  • Typical representatives of the oxidizing agents are chlorate ions, nitrite ions, nitroguanidine, N-methylmorpholine N-oxide, m-nitrobenzoate ions, p-nitrophenol, m-nitrobenzenesulfonate ions, hydrogen peroxide in free or bound form, hydroxylamine in free or bound form, reducing Sugar.
  • the m-nitrobenzenesulfonate as the accelerator at the contents of not less than 20 ppm, preferably not less than 50 ppm and not more than 500 ppm, preferably not more than 300 ppm, significantly improved passivation properties of the treatment solution are achieved.
  • a further improvement of the passive layer properties and the adhesion to subsequently applied lacquer layers results when adding particulate inorganic, water-insoluble compounds of the elements silicon, aluminum, zinc, titanium, zirconium, iron, calcium and / or magnesium, the content of these compounds in the treatment solution based on the element is at least 10 ppm, but should not exceed 200 ppm in order not to destabilize the treatment solution by agglomeration and sedimentation of the particulate components.
  • the oxidic compounds of said elements used in nanoparticulate form.
  • German patent application DE 100 05 113 based on the finding that homopolymers or copolymers of vinylpyrrolidone have an excellent corrosion protection effect.
  • polymers having hydroxyl and / or carboxyl functionalities are often added in substantial amounts (> 1 g / l) to the passivation baths in order to act as binders in the inorganic passive layer to act as further binders to subsequently applied organic coatings.
  • the addition of other polymers significantly increases the process cost, since depending on the transfer ("drag over") of the polymeric components from the pretreatment solution in the dip coating the stability of the dip bath or the quality of the paint coating itself can be adversely affected.
  • the process of the present invention should be adjusted to phosphate ion ratios with respect to molar ratios of zirconium and / or titanium to reduce the rinse time and rinse water level be that of a polymer addition can be waived entirely. Therefore, the present invention relates only to those methods in which the amount of organic polymers in the processing solution is not larger than 1 ppm.
  • the inventive method requires no further inorganic additives selected from oxo anions of vanadium, tungsten and / or molybdenum, in order to produce a sufficient passivation of the metal surface, in particular iron surface.
  • oxoanions in particular vanadates and molybdates
  • small amounts of these oxoanions, in particular vanadates and molybdates may be present as an additional constituent in the treatment solution in the process according to the invention in order to detect defects in the zirconium- and / or titanium-based phosphate layer already during the passivation heal. Because of Process economics, however, the proportion of these compounds in the treatment solution of the method according to the invention based on the respective element is less than 50 ppm, preferably less than 10 ppm.
  • the treatment solution may additionally contain chelating substances.
  • chelating substances in particular those based on ⁇ -hydroxycarboxylic acids, stabilizes the pickling rate in the treatment bath for a longer service life of a bath, so that largely independent of the content of the metal ions, the by pickling the metal surface into the Bad, constant coating conditions of the zirconium and / or titanium-based phosphate layer result.
  • the sludge formation consisting of sparingly soluble metal hydroxides can be significantly minimized.
  • the chelating substances are added as an additive to the treatment solution in the process according to the invention selected from ⁇ -hydroxycarboxylic acids, more preferably selected from polyhydroxy acids having not more than 8 carbon atoms, in particular gluconic acid is preferred.
  • the content of chelating substances in the treatment solution of the process according to the invention is preferably at least 0.01% by weight, more preferably at least 0.05% by weight, but preferably not more than 2% by weight, more preferably not more than 1 wt .-%.
  • the metallic component to be treated in the process according to the invention is optionally previously freed of superficial impurities, in particular lubricants and / or corrosion protection oils, in a cleaning step. If such a cleaning is omitted, a passivation homogeneously formed over the entire metal surface of the component can not be achieved in the method according to the invention.
  • the acidic treatment solution of the process according to the invention may additionally contain at least one surface-active substance, so that the effective Cleaning the metal surfaces of the component and their passivation associated with each other.
  • the use of surface-active substances in passivating pretreatment solutions is not self-evident and thus surprising in the process according to the invention.
  • nonionic surfactants in phosphate-free treatment baths according to the DE 1933013 (Bonderite NT ® ) no adequate passivation of the metal surface.
  • surface-active substances it is possible in principle to use all customary surfactants, preferably nonionic surfactants, which are stable in the treatment solution of the process according to the invention and have a low critical micelle formation concentration below 10 -3 mol / l, preferably below 10 -4 mol / l.
  • the passivating pretreatment process according to the invention is preferably carried out at bath temperatures of the treatment solution of not more than 40.degree. If the pretreatment solution additionally contains surface-active substances, then the bath temperature for sufficient cleaning of the metal surfaces of the component to be treated is preferably at least 30 ° C., wherein higher bath temperatures than 80 ° C. are not required and have a negative effect on the energy efficiency of the process.
  • the metal surfaces may be brought into contact with the pretreatment solution by either dipping or spraying.
  • the present invention also encompasses a process for the corrosion-protective coating of non-closed metallic hollow bodies, which at least partially comprise metallic iron surfaces, wherein the above-described inventive process for corrosion-protective pretreatment is followed by an electrodeposition coating with or without intermediate rinsing step.
  • the resulting after the pretreatment according to the invention amorphous and extremely thin zirconium and / or titanium-based phosphate passivation after Electrocoating an acceptable corrosion resistance and paint adhesion compared to electrocoated crystalline phosphate coatings.
  • such non-closed metallic hollow bodies are to be at least partially coated with iron surfaces in which the ratio of the inner surface area of the non-closed hollow body to the opening area of the same is not less than 5, that is, for example, at least cube-shaped.
  • the Umgriff so the deposition of the dip paint on the opposite sides of the counter electrode electrode or on the inner regions of the metallic hollow body, which are almost field-free due to their Faraday shielding at the beginning of the deposition and therefore only accessible via the resistance structure of the depositing paint layer for film formation is determined decisively by the passivating pretreatment according to the invention and can therefore also be used as a characterizing feature of the pretreatment according to the invention or of the coating according to the invention.
  • the process-specific limitation of the layer thickness of the electrodeposition paint is crucial for the encirclement of the paint, as with the same amount of charge, but lesser limited or maximum film thickness, inevitably a better throwing takes place.
  • a specific layer thickness limitation as the ratio of the layer thickness of Electrocoating paint on the outer surface of a hollow body according to the invention coated to the thickness of the electrodeposition paint after identical, but only electrocoating without prior pretreatment on the identical outer surface of an identical untreated, but cleaned and degreased hollow body. This should not be greater than 0.95, preferably not greater than 0.9, and more preferably not greater than 0.8 according to the present invention.
  • the method according to the invention for coating a metallic hollow body can be carried out in such a way that a rinsing step takes place between the method steps of the pretreatment according to the invention and the electrocoating step, preferably with deionized water or city water.
  • no drying of the metallic hollow body takes place after the pretreatment according to the invention and before the electrocoating process step.
  • the present invention likewise relates to the metallic components and non-closed metallic hollow bodies treated directly with the method according to the invention for the pretreatment and coating, wherein the metallic components and hollow bodies to be treated at least partially have metallic iron surfaces.
  • the present invention encompasses the use of a metallic component whose entire surface, which consists at least partly of metallic iron surfaces, has been pretreated with the chromium-free aqueous treatment solution in accordance with the method according to the invention for the application of further corrosion-protective coatings and / or organic coating systems.
  • the present invention comprises the use of a non-closed metallic hollow body whose entire surface, which at least partially consists of metallic iron surfaces, according to the inventive method first pretreated with the chromium-free aqueous treatment solution and then electrocoated with or without intervening rinsing step, for the production of radiators.
  • Embodiments according to the invention and comparative examples for the pretreatment of steel sheets (CRS: cold rolled steel) including their subsequent electrodeposition coating are mentioned below.
  • CRS sheets are treated by immersion for 5 min at 50 ° C in an aqueous solution composed of 3 wt .-% Ridoline 1562 ® and 0.3 wt .-% Ridosol 1270 ® while stirring the cleaning solution.
  • CRS sheets are first cleaned in the immersion process according to the comparative example "alkaline cleaning", after which the cleaned sheet is rinsed for 1 minute under running demineralized water (k ⁇ 1 ⁇ Scm -1 ). Subsequently, the treatment with Bonderite NT-1 ® (Henkel KGaA) of a zirconium-containing, but phosphate-free aqueous solution is carried out by immersion for 1 min at 20 ° C. The thus pretreated sheet is then rinsed for 1 min under running demineralised water (k ⁇ 1 ⁇ Scm -1 ).
  • Bonderite NT-1 ® Heenkel KGaA
  • CRS sheets are first cleaned in the immersion process according to the comparative example "alkaline cleaning", after which the cleaned sheet is rinsed for 1 minute under running demineralized water (k ⁇ 1 ⁇ Scm -1 ).
  • the treatment with the commercial product Granodine 958 ® (Messrs. Henkel KGaA) according to the instructions Subsequently, the dipping method. This treatment includes an activation step before the actual phosphating.
  • the thus pretreated sheet is then rinsed for 1 min under running demineralized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
  • CRS sheets are first cleaned in the immersion process according to the comparative example "alkaline cleaning", after which the cleaned sheet for 1 min rinsed with running demineralised water (k ⁇ 1 ⁇ Scm -1 ). Subsequently, in the spraying process, the treatment is carried out with an aqueous solution according to the invention composed of 300 ppm Zr as H 2 ZrF 6 , 100 ppm PO 4 as H 3 PO 4 , 100 ppm Sodium m-nitrobenzenesulfonate (m-NBS) and 3000 ppm Ridosol 2000 ® (cleaner Fa. Henkel KGaA) for 2 min at 50 ° C, wherein the pH is adjusted to pH 4.5 with ammoniacal solution. The thus pretreated sheet is then rinsed for 1 min under running demineralized water (k ⁇ 1 ⁇ Scm -1 ).
  • an aqueous solution according to the invention composed of 300 ppm Zr as H 2 ZrF 6 , 100 ppm PO
  • All pretreated sheets are then coated with a cathodic immersion coating Cathogard 500 from BASF and baked at 180 ° C for 30 min.
  • the average coating thickness is determined by means of the Coating Thickness Gauge PosiTector 6000 (DeFelsko Ltd., Canada) by multiple measurements at different points on the anode-facing side of the sheet.
  • the layer thickness of the zinc phosphate layer is first determined by multiple measurement before the electrodeposition coating and subtracted from the determined layer thickness after painting.
  • the pretreatment according to the invention has the lowest layer thickness compared to the "non-layer-forming" pretreatments with identical electrodeposition coating time. Only the layer-forming phosphated CRS sheet has an even lower coating thickness after the electro-dip coating.
  • the infiltration values are so similar and even better than those that adapt to the corrosive infiltration after an iron phosphating after 504 hours and typically be 1.5 mm, and slightly larger than after pretreatment with Bonderite NT-1 ®, the infiltration levels of 0.9 mm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
EP08853163.7A 2007-11-26 2008-11-25 Zirconiumphosphatierung von metallischen bauteilen, insbesondere eisen Active EP2215285B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007057185A DE102007057185A1 (de) 2007-11-26 2007-11-26 Zirconiumphosphatierung von metallischen Bauteilen, insbesondere Eisen
PCT/EP2008/066144 WO2009068523A1 (de) 2007-11-26 2008-11-25 Zirconiumphosphatierung von metallischen bauteilen, insbesondere eisen

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EP2215285A1 EP2215285A1 (de) 2010-08-11
EP2215285B1 true EP2215285B1 (de) 2016-05-25

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US (1) US8663443B2 (ko)
EP (1) EP2215285B1 (ko)
JP (1) JP2011504550A (ko)
KR (1) KR20100102619A (ko)
DE (1) DE102007057185A1 (ko)
ES (1) ES2584937T3 (ko)
WO (1) WO2009068523A1 (ko)

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IT1397902B1 (it) 2010-01-26 2013-02-04 Np Coil Dexter Ind Srl Processi di pretrattamento alla verniciatura, a basso impatto ambientale, alternativi ai trattamenti tradizionali di fosfatazione.
TWI482879B (zh) * 2010-09-15 2015-05-01 Jfe Steel Corp 容器用鋼板及其製造方法
US20120094130A1 (en) * 2010-10-15 2012-04-19 Universidade Estadual De Campinas Coating Compositions With Anticorrosion Properties
KR101263086B1 (ko) 2010-12-28 2013-05-09 주식회사 포스코 판상형 지르코늄포스페이트 및 그의 제조 방법
DE102016206417A1 (de) 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Fördergestellbehandlung zur unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung
DE102016206418A1 (de) 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung
EP3569743A1 (de) 2018-05-16 2019-11-20 Henkel AG & Co. KGaA Fördergestellreinigung in einer prozessfolge zur elektrotauchlackierung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009045872A1 (en) * 2007-09-28 2009-04-09 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1933013C3 (de) 1969-06-28 1978-09-21 Gerhard Collardin Gmbh, 5000 Koeln Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels komplexe Fluoride enthaltender Lösungen
US4017335A (en) * 1975-10-30 1977-04-12 Economics Laboratory, Inc. Liquid phosphatizing composition and use thereof
CA1098253A (en) 1976-04-05 1981-03-31 Timm L. Kelly Zirconium/titanium coating solution for aluminum surfaces
JPS5983775A (ja) * 1982-11-02 1984-05-15 Nippon Paint Co Ltd 金属表面の化成処理方法
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
US5356490A (en) 1992-04-01 1994-10-18 Henkel Corporation Composition and process for treating metal
DE19933189A1 (de) * 1999-07-15 2001-01-18 Henkel Kgaa Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
US6758916B1 (en) * 1999-10-29 2004-07-06 Henkel Corporation Composition and process for treating metals
DE10005113A1 (de) 2000-02-07 2001-08-09 Henkel Kgaa Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen
DE10131723A1 (de) 2001-06-30 2003-01-16 Henkel Kgaa Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen
US6869513B2 (en) * 2001-11-08 2005-03-22 Ppg Industries Ohio, Inc. Photodegradation-resistant electrodepositable coating compositions with improved throw power and processes related thereto
US6805756B2 (en) * 2002-05-22 2004-10-19 Ppg Industries Ohio, Inc. Universal aqueous coating compositions for pretreating metal surfaces
US7063735B2 (en) * 2003-01-10 2006-06-20 Henkel Kommanditgesellschaft Auf Aktien Coating composition
AU2003300475B2 (en) 2003-01-10 2009-07-16 Henkel Ag & Co. Kgaa A coating composition
DE102005059314B4 (de) * 2005-12-09 2018-11-22 Henkel Ag & Co. Kgaa Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen
US7815751B2 (en) 2005-09-28 2010-10-19 Coral Chemical Company Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009045872A1 (en) * 2007-09-28 2009-04-09 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate

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US20100293788A1 (en) 2010-11-25
DE102007057185A1 (de) 2009-05-28
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WO2009068523A1 (de) 2009-06-04
ES2584937T3 (es) 2016-09-30
US8663443B2 (en) 2014-03-04
KR20100102619A (ko) 2010-09-24

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