US20050205166A1 - Method for coating metallic surfaces - Google Patents

Method for coating metallic surfaces Download PDF

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US20050205166A1
US20050205166A1 US10/519,006 US51900605A US2005205166A1 US 20050205166 A1 US20050205166 A1 US 20050205166A1 US 51900605 A US51900605 A US 51900605A US 2005205166 A1 US2005205166 A1 US 2005205166A1
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concentration range
range
sodium
process according
potassium
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Jurgen Specht
Peter Schubach
Rudiger Rein
Peter Claude
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Chemetall GmbH
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Individual
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Priority claimed from DE2002131279 external-priority patent/DE10231279B3/de
Priority claimed from DE2002136526 external-priority patent/DE10236526A1/de
Application filed by Individual filed Critical Individual
Assigned to CHEMETALL GMBH reassignment CHEMETALL GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: REIN, RUDIGER, CLAUDE, PETER, SCHUBACH, PETER, SPECHT, JURGEN
Publication of US20050205166A1 publication Critical patent/US20050205166A1/en
Priority to US13/080,974 priority Critical patent/US8349092B2/en
Abandoned legal-status Critical Current

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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
    • C23C22/364—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
    • C23C22/05—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

Definitions

  • the present invention relates to a process for the coating of metallic surfaces by zinc phosphating, and to the use of the substrates coated by the process according to the invention.
  • the coating of metallic surfaces with phosphate films can take place in many different ways. Phosphating solutions containing zinc, manganese and/or nickel ions are often used in the process. Some of the metallic substrates to be surface-coated in the baths or plants also have a proportion of aluminium or aluminium alloys, which may lead to problems.
  • the phosphate film(s), together with at least one coat of paint or paint-like coating applied subsequently, is generally intended to exhibit good corrosion protection and good paint adhesion.
  • the simultaneous phosphating of substrates-with different metallic surfaces has gained increasing importance. In particular, the proportion of aluminium-containing surfaces in these systems is growing, so that problems occur more readily and more frequently than in the past during phosphating in these systems.
  • an Al—F complex can form, which is dissolved in the solution but which can also lead to a precipitate with monovalent ions, such as e.g. sodium and/or potassium.
  • the precipitate can accumulate as sludge in the bath vessel and be removed from there, but can also cause problematic deposits on the aluminium-containing metallic surfaces.
  • EP-A1-0 452 638 teaches a process for the phosphating of surfaces of steel, galvanised steel together with aluminium-containing surface portions with a phosphating solution having a total content of sodium ions in the range of at least 2 g/l, a content of sodium and potassium ions together of 2 to 15 g/l and a content of manganese ions of at least 1 g/l.
  • EP-A2-0 434 358 describes a process for the phosphating of metallic surfaces in the presence of aluminium, in which the phosphating solution contains, as well as zinc, at least one complex fluoride and a so-called simple fluoride, in which the molar ratio of complex fluoride to simple fluoride is in the range of 0.01 to 0.5.
  • a dissociated and non-dissociated hydrofluoric acid is referred to here as simple fluoride.
  • at least one separate treatment vessel or separate precipitating vessel is used.
  • this publication mentions no concrete measures relating to monovalent cations which enable cryolite precipitates to be avoided except by using an additional separate vessel.
  • the value of the free acid FA is said to be 0.5 to 2 points, but was determined without the addition of KCl and would correspond to about 0.3 to 1.5 points FA-KCl.
  • EP-A2-0 454 361 contains a very similar teaching.
  • DE-A1-100 26 850 protects a phosphating process in which the deposition of problematic cryolite precipitates in the area of the metallic surfaces to be coated is avoided by a limitation of the aluminium content of the phosphating solution and by using an additional, separate precipitating vessel, through which the phosphating-solution has to circulate.
  • the object therefore existed of proposing a phosphating process for the coating of surfaces, including those containing aluminium, in which a separate precipitation area in the vessel for the phosphating solution or separate vessels for precipitation, and thus for avoiding precipitates on the metallic surfaces to be coated, are unnecessary.
  • the phosphate film should be continuous, of a good, fine-particle crystallinity, of sufficiently high corrosion resistance and of sufficiently good paint adhesion.
  • the process should be implementable as simply, reliably and inexpensively as possible.
  • the object is achieved by a process for the treatment or pre-treatment of parts, profiles, strips, sheets and/or wires with metallic surfaces, in which at least 5% of these surfaces consist of aluminium and/or at least one aluminium alloy and optionally the other metallic surfaces can consist in particular of iron alloys, zinc and/or zinc alloys, with an acidic, aqueous solution containing zinc, fluoride and phosphate, wherein the contents dissolved in the phosphating solution are as follows:
  • pre-treatment in contrast to the term “treatment”, is intended to indicate within the meaning of this application that at least one substantial coating, such as e.g. at least one coat of a paint and/or a paint-like material, is applied on to the pre-treatment coat.
  • At least 8% of these surfaces preferably consist of aluminium and/or at least one aluminium alloy, particularly preferably at least 12%, at least 18%, at least 24%, at least 30%, at least 40%, at least 50%, at least 60%, at least 75% or at least 90%.
  • the dissolved contents can often be present in a non-complexed and a complexed state together at the same time.
  • the contents dissolved in the phosphating solution can preferably be as follows:
  • the content of sodium and potassium together, calculated as sodium, is particularly preferably 0.08 to 2.2 g/l, especially preferably 0.2 to 2 g/l, particularly 0.3 to 1.8 g/l, especially up to 1.6 g/l.
  • the content of zinc is particularly preferably 0.3 to 3 g/l, of phosphate 6 to 40 g/l, of free fluoride at least 0.08 g/l or up to 0.3 g/l and/or of total fluoride 0.3 to 3 g/l, particularly at least 0.4 g/l or up to 2.5 g/l total fluoride.
  • the content of sodium, potassium and optionally other alkali metal ions, of ammonium and nitrate ions is kept as low as possible, particularly if an addition of only up to 1 g/l or virtually none of each is used, preferably of optionally up to 0.5 g/l or of up to 0.2 g/l in each case, an addition of nitrate advantageously being kept to at least 0.4 g/l but no more than 6 g/l, particularly advantageously only up to 4 g/l, especially preferably only up to 3.5 or 3 or 2.5 or 2 g/l.
  • cryolite and/or related compounds containing Al—F occurs, which can lead to paint defects in the subsequent paint film.
  • no bifluoride of sodium and/or potassium is added.
  • the content of dissolved, including complexed, zinc can be particularly 0.4 to 2.5 g/l, particularly preferably 0.5 to 2.2 g/l, with a content of 0.5 to 2.5 g/l and particularly 0.7 to 2.0 g/l being preferred for application of the phosphating solution by dip-coating and 0.3 to 2 g/l and particularly 0.5 to 1.5 g/l for spray application.
  • the phosphate content can be particularly 6 to 40 g/l PO 4 , especially at least 8 g/l or up to 36 g/l.
  • the phosphate film applied with the phosphating solution according to claim 1 can be applied either directly on to a metallic surface, on to an activated metallic surface, e.g. by activation based on titanium phosphate, or on to at least one previously applied preliminary coating, such as e.g. on to a first phosphate film which is not used, or not exclusively used, for activation, and/or on to at least one coating with a different type of chemical composition, such as e.g. on to a coating containing complex fluoride, silane and/or polymers.
  • a sample of the surface of an Al-containing surface is placed in a scanning electron microscope, optionally after breaking it down into a suitable sample format, and is examined there by means of energy-dispersive or wavelength-dispersive analysis for the presence of sodium or potassium, which are not generally incorporated into the crystal lattices of the zinc phosphates, as representatives of the other alkali or alkaline earth metals or ammonium, which can be precipitated together with the sodium and potassium.
  • the contents of dissolved aluminium in the phosphating solution can preferably be within the concentration range of 0.002 to 1 g/l, particularly of at least 0.005 g/l, particularly preferably 0.008 to 0.7 g/l, especially 0.01 to 0.4 g/l.
  • An aluminium content higher than 0.1 g/l is not harmful to the process according to the invention.
  • the total content of silicon complex fluoride and boron complex fluoride together in the phosphating solution can preferably be 0.01 to 8 g/l—optionally converted to SiF 6 on a molar basis, it being unnecessary for both groups of fluoride complexes to occur at the same time.
  • the sum of the contents of complex bound fluoride in silicon complex fluoride and boron complex fluoride is preferably 0.01 to 8 g/l, particularly preferably 0.02 to 5.3 g/l, especially preferably 0.02 to 4 g/l, in particular less than 3 or 2 g/l or even no more than 1.8 g/l. It is particularly preferred if the content of silicon complex fluoride does not exceed 1.8 g/l.
  • the contents of complex bound fluoride in the phosphating solution can preferably be 0.01 to 8 g/l, calculated as SiF 6 , converting on a molar basis.
  • the contents dissolved in the phosphating solution can be as follows:
  • the contents of silicon complex fluoride are preferably 0.01 to 2.5 g/l and/or of boron complex fluoride preferably 0.01 to 2.8 g/l.
  • Contents of sodium in the range of 0.05 to 2 g/l, potassium virtually none or in the range of 0.05 to 1 g/l, silicon complex fluoride in the range of 0.03 to 2.5 g/l and/or boron complex fluoride in the range of 0.03 to 2.8 g/l can especially be present here.
  • This variant particularly preferably contains more sodium than potassium.
  • the contents dissolved in the phosphating solution can preferably be as follows:
  • the contents dissolved in the phosphating solution can be as follows: sodium 0.05 to 1.9 g/l, potassium 0.05 to 4 g/l, silicon complex fluoride 0.03 to 0.8 g/l and/or boron complex fluoride 0.03 to 2.5 g/l or 0.03 to 1.8 g/l, the last of these calculated as SiF 6 and BF 4 respectively.
  • This variant particularly preferably contains more potassium than sodium. It is particularly preferred that the content of sodium and potassium together in the phosphating solution is in the concentration range of up to 1.8 g/l, especially preferably up to 1.5 g/l, in particular up to 1.1 g/l, quoted as sodium with potassium being converted to sodium on a molar basis.
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the phosphating solution can have the following contents:
  • the phosphating solution can have the following contents:
  • the zinc content in the phosphating solution is particularly preferred for the zinc content in the phosphating solution to be greater than its manganese content.
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the dissolved contents in the phosphating solution can preferably be as follows:
  • the phosphating solution can contain at least one accelerator selected from the group of compounds or ions based on
  • the phosphating solution particularly preferably has at least a certain nitrate content as accelerator, but an addition of at least one other accelerator is advantageous.
  • the contents of the respective nitrogen-containing compounds may advantageously be 0.01 to 2 g/l for m-nitrobenzenesulfonate, 0.001 to 0.400 g/l for nitrite and 0.01 to 3.5 g/l for nitroguanidine.
  • the content based on chlorate is preferably virtually none or in the range of 0.05 to 4 g/l, or particularly preferably in the range of 0.1 to 3 g/l or of 0.15 to 1.8 g/l.
  • the content based on hydroxylamine is preferably virtually none or in the range of 0.05 to 2 g/l, or particularly preferably in the range of 0.2 to 1.5 g/l.
  • the content based on m-nitrobenzenesulfonate is preferably virtually none or in the range of 0.05 to 1.5 g/l, or particularly preferably in the range of 0.15 to 1 g/l.
  • the content based on nitrite is preferably virtually none or in the range of 0.005 to 0.350 g/l, or particularly preferably in the range of 0.010 to 0.300 g/l.
  • the content based on guanidine is preferably virtually none or in the range of 0.1 to 3 g/l, or particularly preferably in the range of 0.3 to 2.5 g/l.
  • the content based on peroxide, including water-soluble organic peroxide, is preferably virtually none or in the range of 0.003 to 0.150 g/l, or particularly preferably in the range of 0.005 to 0.100 g/l.
  • the total content of all accelerators is preferably less than 5 g/l, particularly preferably less than 4 g/l, especially less than 3.5 g/l, less than 3 g/l or less than 2.5 g/l.
  • the total content of all cations in the phosphating solution can preferably lie within the concentration range of 0.35 to 80 g/l, calculated on a molar basis as Zn, and the total content of all anions, excluding accelerators but including nitrate, can preferably be within the concentration range of 4 to 120 g/l, calculated on a molar basis as PO 4 .
  • at least one accelerator other than those mentioned above can also be used, particularly one based on a nitro compound, such as e.g. based on nitrobenzoate and/or nitrophenol.
  • the phosphating solution preferably does not contain an accelerator based on hydroxylamine.
  • the content of magnesium in the phosphating solution can preferably be no more than 1 g/l, particularly preferably less than 0.5 g/l, especially preferably no more than 0.15 g/l.
  • no or almost no precipitation product based on aluminium fluorocomplexes of ammonium, alkali and/or alkaline earth metal is deposited on the metallic surface, below the phosphate film and/or between the zinc phosphate crystals in the phosphate film on surfaces of aluminium and/or at least one aluminium alloy phosphated in this way—or at least the quantities thereof should be sufficiently restricted that the precipitates do not give rise to paint defects in the subsequent paint film.
  • resins and that are optionally also substantially free from colloidal and other particles.
  • substantially means, in particular, without the intentional addition of these ions or compounds, so that contents of these substances, if present, are most likely to be brought about in a small amount by impurities, pickling reactions and entrainments. In many cases, it is also preferable for no copper to be added.
  • KCl is added to 10 ml of the phosphating solution without dilution for the purpose of shifting dissociation of the complex fluoride until saturation is achieved, and titration is performed with 0.1M NaOH using dimethyl yellow as an indicator until the colour changes from red to yellow.
  • the quantity of 0.1M NaOH consumed in ml gives the value of the free acid (FA-KCl) in points.
  • the so-called S value is obtained by dividing the value of the free acid determined with KCl by the value of the total acid according to Fischer.
  • the dilute total acid (TA dilute ) is the sum of the divalent cations contained together with free and bound phosphoric acids (the latter are phosphates). It is determined by the consumption of 0.1 molar sodium hydroxide solution using the indicator phenolphthalein on 10 ml of phosphating solution diluted with 200 ml of deionised water. This consumption of 0.1 molar NaOH in ml corresponds to the points value of the total acid.
  • the content of free acid determined with KCl can preferably be in the range of 0.3 to 6 points, the content of dilute total acid preferably in the range of 8 to 70 points and/or the content of total acid according to Fischer preferably in the range of 4 to 50 points.
  • the range of the free acid determined with KCl is preferably 0.4 to 5.5 points, particularly 0.6 to 5 points.
  • the range of the dilute total acid is preferably 12 to 50 points, particularly 18 to 44 points.
  • the range of the total acid according to Fischer is preferably 7 to 42 points, particularly 10 to 30 points.
  • the S value as a ratio of the number of points of the free acid determined with KCl to those of the total acid according to Fischer is preferably in the range of 0.01 to 0.40 points, particularly in the range of 0.03 to 0.035 points, especially in the range of 0.05 to 0.30 points.
  • the pH of the phosphating solution can be in the range of 1 to 4, preferably in the range of 2.2 to 3.6, particularly preferably in the range of 2.8 to 3.3.
  • substrates with a metallic surface predominantly containing aluminium, iron, copper, tin or zinc can be coated with the phosphating solution, with a minimum content of aluminium and/or at least one aluminium alloy always occurring, particularly surfaces of at least one of the materials based on aluminium, iron, copper, steel, zinc and/or alloys with a content of aluminium, iron, copper, magnesium, tin or zinc.
  • these are generally strips of aluminium and/or at least one aluminium alloy.
  • the phosphating solution can be applied on to the surface of the substrates by flow coating, lance application, roll coating, sprinkling, spraying, brushing, dipping, misting or roller application, it being possible for individual process steps to be combined together—particularly sprinkling, spraying and dipping—and spraying and squeegeeing or sprinkling and squeegeeing can particularly be used on a strip.
  • a slow-moving strip with an aluminium-containing surface can be coated according to the invention, e.g. even in a no-rinse process.
  • the phosphating solution is preferably applied on to the strip by roll-coating, spraying, sprinkling, dipping and/or squeegeeing.
  • the phosphate coating can preferably be applied at a temperature in the range of 20 to 70° C., particularly in the range of 32 to 65° C., particularly preferably in the range of 40 to 60° C.
  • the metallic substrates can be coated in a period of up to 20 minutes, strip preferably being coated in a period of 0.1 to 120 seconds and particularly preferably in a period of 0.3 to 60 seconds, and parts preferably being coated in a period of 1 to 12 minutes and particularly preferably in a period of 2 to 8 minutes.
  • the coating weight of the coating according to the invention is preferably in the range of 0.9 to 9 g/m 2 , particularly preferably at least 1.2 g/m 2 , or at least 1.6 g/m 2 , or no more than 8 g/m 2 , no more than 7.2 g/m 2 , no more than 6 g/m 2 or no more than 5 g/m 2 . It is preferred for phosphating to be performed in a so-called “coat-forming” way (cf. Werner Rausch: Die Phosphat réelle von Metallen, Saulgau, 1988), because this forms a continuous phosphate film readily visible to the naked eye.
  • the substrates coated by the process according to the invention can be used in the production of strip and parts, for the production of components or body parts or pre-assembled elements in the automotive or aircraft industry, in the construction industry, in the furniture industry, for the production of equipment and plant, particularly domestic appliances, measuring instruments, control devices, testing devices, structural elements, claddings and small parts; as wire; wire wrap, wire mesh, sheet, cladding, screening, a car body or part of a car body, as part of a vehicle, trailer, motorhome or aircraft, as an electronic or microelectronic component, as a cover, housing, lamp, light, traffic light element, a piece of furniture or a furniture part, part of a domestic appliance, stand, profile, moulded part with complicated geometry, crash barrier, radiator or fence element, bumper, part consisting of or with at least one pipe and/or a profile, window-, door- or bicycle frame or as a small part, such as e.g. a screw, nut, flange, spring or spectacle frame.
  • wire wire wrap
  • test sheets consisted of a mix of sheets, in a ratio of 1:1:1 in each case, a) of an aluminium alloy AA6016, approx. 1.15 mm thick, ground with abrasive paper 240, b) of a cold-rolled, continuously annealed sheet of unalloyed steel DC04B approx. 0.8 mm thick and c) thin sheet, electrolytically galvanised on both sides, automotive quality, grade DC05, ZE75/75, steel, each approx. 0.85 mm thick.
  • Rinsing was then first performed with tap water followed by a secondary rinse with an aqueous solution containing zirconium fluoride and a final rinse with deionised water.
  • the dry test sheets were provided with a cathodic electrodeposition paint and coated with the other coats of a paint structure conventional for bodies in the automotive industry.
  • composition of the respective phosphating solution is given in Table 1.
  • Table 1 Composition of the phosphating solutions in g/l and with data for the free acid (FA-KCl), dilute total acid (TA dilute ) and total acid according to Fischer (TAF) in points, the S value (ratio of FA-KCl:TAF), cryolite deposits on the sheets and the coating weight
  • Example Contents in g/l E 1 E 2 E 3 CE 4 E 5 E 6 CE 7 CE 8 E 9 E 10 CE 11 CE 12 E 13 E 14 CE 15 E 16 CE 17 Zn 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.0 1.0 Ni 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Na 0.1 1 1.8 5 0.1 1 2.5 5 0.1 1 3 5 — — — — — — — — — — — — — —
  • Fluorides or phosphates of Al, Fe, Zn and possibly other cations are found in the so-called “sludge”. These precipitation products are scarcely deposited on the surfaces of the sheets, however.
  • the data for “cryolite on sheet” refers to deposits on phosphated metal sheets with predominantly cube-like crystals, the morphology of which could be clearly seen using a scanning electron microscope and the composition of which was established by qualitative determination of the Na and/or K contents by EDX. In addition, F contents could also be detected using a microprobe. The precipitation products were visible as deposits beginning to form on surfaces of the aluminium alloy.
  • the phosphate films in the examples according to the invention were sufficiently finely crystalline and sufficiently continuous. Their corrosion resistance and adhesive strength corresponded to typical quality standards of similar zinc phosphate films. All the sheets according to the invention, unlike the sheets in the comparative examples, displayed no deposit of cryolite or chemically related phases. In the sheets in the comparative examples, because of these deposits on the phosphate film or between the zinc phosphate crystals in the phosphate film, there was a different surface finish compared with the sheets coated according to the invention. The surface finish of the coated substrates in the comparative examples can lead to paint defects as a result of painting, such as unacceptably rough paint surfaces or bubbles in the paint film and thus, necessarily, to subsequent work, e.g. by sanding the painted surface. With the process according to the invention, it was not necessary to use a separate area in the phosphating solution vessel for the precipitation, and it was even unnecessary to use a separate, additional precipitating vessel.
  • Table 2 Results of the outdoor weathering test according to VDA standard 621-414 on overpainted sheets of AA6016 in correlation with the Na and F free content Creepage in mm acc. to VDA Examples/ Na K F free standard 621-414 comparative content content content after 6 after 9 examples g/l g/l g/l months months E 1 0.1 0 0.1 0 0 E 2 1.0 0 0.1 0 0 E 3 1.8 0 0.1 0 0 CE 4 5.0 0 0.1 1.5 2.5 E 9 0.1 0 0.1 0 0 E 10 1.0 0 1.0 0 0 CE 11 3.0 0 3.0 2.0 3.0 CE 12 5.0 0 5.0 2.5 3.5 E 16 1.8 0 0.25 0 0 CE 17 3.0 0 0.25 2.5 3.0 CE 27 0.5 4.0 0.2 2.5 3.5 E 28 1.9 0 0.25 0 0 CE 29 3.5 0 0.25 1.5 2.5 CE 30 3.0 0 0.25 2.5 3.5

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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US10/519,006 2002-07-10 2003-07-09 Method for coating metallic surfaces Abandoned US20050205166A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/080,974 US8349092B2 (en) 2002-07-10 2011-04-06 Process for coating metallic surfaces

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10231279.6 2002-07-10
DE2002131279 DE10231279B3 (de) 2002-07-10 2002-07-10 Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate
DE2002136526 DE10236526A1 (de) 2002-08-09 2002-08-09 Verfahren zur Beschichtung von metallischen Oberflächen
DE10236326.1 2002-08-09
PCT/EP2003/007359 WO2004007799A2 (de) 2002-07-10 2003-07-09 Verfahren zur beschichtung von metallischen oberflächen

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US20110008645A1 (en) * 2008-03-11 2011-01-13 Mark Andre Schneider Process for coating metallic surfaces with a passivating agent, the passivating agent and its use
US20130202797A1 (en) * 2010-06-30 2013-08-08 Henkel Ag & Co. Kgaa Method for selectively phosphating a composite metal construction
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EP3392376A1 (de) 2017-04-21 2018-10-24 Henkel AG & Co. KGaA Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie
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US20080166575A1 (en) * 2005-05-19 2008-07-10 Chemetall Gmbh Method For Preparing Metallic Workplaces For Cold Forming
US8801871B2 (en) * 2006-11-08 2014-08-12 Henkel Ag & Co. Kgaa Zr-/Ti-containing phosphating solution for passivation of metal composite surfaces
US20090255608A1 (en) * 2006-11-08 2009-10-15 Henkel Ag & Co. Kgaa Zr-/ti-containing phosphating solution for passivation of metal composite surfaces
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US20110008645A1 (en) * 2008-03-11 2011-01-13 Mark Andre Schneider Process for coating metallic surfaces with a passivating agent, the passivating agent and its use
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US20130202797A1 (en) * 2010-06-30 2013-08-08 Henkel Ag & Co. Kgaa Method for selectively phosphating a composite metal construction
KR20140025479A (ko) * 2011-05-09 2014-03-04 크노르-브렘제 시스테메 퓌어 쉬에넨파쩨우게 게엠베하 레일 휠과 레일 휠 제조 방법
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US11248298B2 (en) 2015-11-30 2022-02-15 Baoshan Iron & Steel Co., Ltd. Chromium-free surface-treated tinplate, production method and surface treating agent therefor

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AU2003250917A8 (en) 2004-02-02
ATE399218T1 (de) 2008-07-15
CA2494559C (en) 2011-09-20
EP1521863A2 (de) 2005-04-13
EP1521863B1 (de) 2008-06-25
DE50310042D1 (de) 2008-08-07
PT1521863E (pt) 2008-09-19
WO2004007799A3 (de) 2004-04-08
WO2004007799A2 (de) 2004-01-22
US20110198000A1 (en) 2011-08-18
CN1665957A (zh) 2005-09-07
US8349092B2 (en) 2013-01-08
AU2003250917A1 (en) 2004-02-02
CN100374620C (zh) 2008-03-12

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