EP0907762B1 - Chrom(vi)-freie konversionsschicht sowie verfahren zu ihrer herstellung - Google Patents

Chrom(vi)-freie konversionsschicht sowie verfahren zu ihrer herstellung Download PDF

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Publication number
EP0907762B1
EP0907762B1 EP97925823A EP97925823A EP0907762B1 EP 0907762 B1 EP0907762 B1 EP 0907762B1 EP 97925823 A EP97925823 A EP 97925823A EP 97925823 A EP97925823 A EP 97925823A EP 0907762 B1 EP0907762 B1 EP 0907762B1
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EP
European Patent Office
Prior art keywords
chromium
ions
iii
zinc
acid
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EP97925823A
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German (de)
English (en)
French (fr)
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EP0907762A1 (de
Inventor
Patricia Preikschat
Rolf Jansen
Peter HÜLSER
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Surtec International GmbH
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Surtec Produkte und System fuer die Oberflaechenbehandlung GmbH
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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
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to chromium (VI) free, chromium (III) -containing essential coherent conversion layers according to Claim 1, a process for their preparation according to claim 4, as well as the use of passivation solutions according to claim 10.
  • Metallic materials are galvanized or cadaved to protect them from corrosive environmental influences.
  • the protection against corrosion of the zinc is based on the fact that it is even less noble than the base metal and therefore the corrosive attack first only draws attention, it acts as a sacrificial layer.
  • the base metal of the galvanized component in question remains intact, as long as it is continuously covered with zinc, and the mechanical one Functionality is maintained over longer periods of time than with non-galvanized Divide. Thick layers of zinc naturally grant a higher one Corrosion protection as thin layers - the corrosive removal of thick ones Shifts just take longer.
  • the corrosive attack on the zinc layer can be caused by the Applying a chromate can be greatly delayed, and thus base metal corrosion is also drawn further than by one Galvanizing alone. Corrosion protection through the layer system Zinc / chromating is considerably higher than just the same thickness Zinc coating. Chromating also improves the optical quality Impairment of a component due to environmental influences - The corrosion products of zinc, the so-called white rust, also work disturbing the appearance of a component.
  • the blue chromating layer is up to 80 nm thick, slightly blue in the inherent color and, depending on the layer thickness, has a light refraction produced golden, reddish, bluish, greenish or yellow iris color on. Very thin layers of chromate with almost no inherent color are considered Colorless chromatographies (group A) classified.
  • the Chromating solution can be both hexavalent in both cases as well as from trivalent chromates and mixtures of both, also consist of conductive salts and mineral acids. There are fluoride ones and fluoride-free variants.
  • the application of chromating solutions takes place at room temperature.
  • the corrosion protection of uninjured Blue chromating amounts to 10-40 h in the salt spray cabinet DIN 50021 SS until the first appearance of corrosion products.
  • the Minimum requirement for process groups A and B according to DIN 50961 Chapter 10 Table 3 is 8 hours for drum goods and 16 hours for Rack goods.
  • the yellow chromating layer is about 0.25-1 ⁇ m thick, golden yellow colored and often iridescent red-green.
  • the chromating solution consists essentially of hexavalent dissolved in water Chromates, conductive salts and mineral acids. The yellow color comes from the significant proportion (80-220 mg / m2) of hexavalent chromium, this in addition to that in the layer formation reaction by reduction generated trivalent chrome, is installed.
  • the application of the Chromating solutions take place at room temperature.
  • the Corrosion protection of undamaged yellow chromations amounts to 100-200 h in a salt spray cabinet according to DIN 50021 SS until the first Occurrence of corrosion products.
  • the minimum requirement for the Process group C according to DIN 50961 chapter 10 table 3 is 72 h for drum goods and 96 h for rack goods.
  • the typical olive chromating layer is up to 1.5 ⁇ m thick, opaque olive green to olive brown.
  • the chromating solution consists of essentially from hexavalent chromates dissolved in water, Conductive salts and mineral acids, especially phosphates or Phosphoric acid and may also contain formates. Be in the shift significant amounts of chromium (VI) (300-400 mg / m2) were stored. The The chromating solutions are used at room temperature. The corrosion protection of undamaged olive chromating amounts to 200-400 h in a salt spray cabinet according to DIN 50021 SS until the first Occurrence of corrosion products.
  • the minimum requirement for the Process group D according to DIN 50961 chapter 10 table 3 is 72 h for drum ware and 120 h for rack ware.
  • the black chromating layer is basically a yellow or Olive chromating, in which colloidal silver is embedded as a pigment.
  • the chromating solutions are about the same Composition such as yellow or olive chromate and contain additionally silver ions.
  • zinc alloy layers such as Zn / Fe, Zn / Ni or Zn / Co is deposited with a suitable composition of the Chromating solution iron, nickel or cobalt oxide as Black pigment in the chromate layer, so that in these cases silver is not required.
  • Significant amounts are deposited in the chromate layers Chromium (VI) installed, depending on whether a yellow or a Olive chromating is the basis between 80 and 400 mg / m2.
  • the chromating solutions are used at room temperature.
  • the green chromating on aluminum (also known as aluminum green) is matt green and not iridescent.
  • the chromating solution consists of essentially from hexavalent chromates dissolved in water, Conductive salts and mineral acids as well as in particular from phosphates and Silicofluoriden.
  • the chromate / phosphate layer that forms is like Iod / starch tests do not always show contrary to popular belief 100% chromium (VI) free.
  • thick chromate layers can be used high corrosion protection> 100 h in a salt spray cabinet according to DIN 50021 SS or ASTM B 117-73 until the appearance of the first Corrosion products according to DIN 50961 (June 1987) chapter 10, especially chapter 10.2.1.2, without sealing and others special after-treatment (DIN 50961, Chapter 9) only through Treatment with dissolved extremely toxic Establish chromium (VI) connections.
  • the Chromate layers with the specified requirements for corrosion protection nor those poisonous and carcinogenic Chromium (VI) compounds that are also not completely in the layer are immobilized.
  • the chromating with chromium (VI) compounds is problematic with regard to occupational safety.
  • the use of galvanized and chromations produced with chromium (VI) compounds e.g. the widespread yellow chromations e.g. sets on screws Potential of the population and increases the general Cancer risk.
  • Tetravalent cerium is an even stronger oxidizing agent than hexavalent chromium, which is why Ce (IV) from Cr (III) will produce the Cr (VI) to be avoided.
  • Cr (VI) has a very strong yellow color and is known as an anti-corrosion agent. The layer described in US 43 84 902 is therefore not free of hexavalent chromium.
  • the layer according to the invention is without an oxidizing agent manufactured and therefore free of hexavalent chromium. This is in particular to recognize that the layer according to the invention is not yellow.
  • GB-A-2 097 024 also discloses the treatment of Metal surfaces to improve corrosion protection on zinc and Zinc alloy surfaces with an aqueous acidic solution, a Oxidizing agent and at least one metal selected from the group consisting of cobalt, nickel, molybdenum, manganese, aluminum, lanthanum, Lanthanide mixtures or cerium ions or mixtures thereof or instead of iron and cobalt ions.
  • GB-A-2 097 024 also discloses the use of trivalent chromium ions and iron ions in Combination with an additional metal selected from the group consisting of the above or Cerions, however mainly combinations of chromium (III) in combination with one Oxidizing agents and cerium or lanthanum ions are described.
  • EP-A-337 411 discloses acidic chromium (III) -containing and fluoride-containing Passivation baths for surfaces made of zinc and zinc alloys Use of chromium fluorocomplexes, which is the Chromating according to EP-A-337 411 for blue chromating which uses fluoride ions.
  • DE-A-4 135 524 discloses a process for chromating zinc with a solution of pH 1.2-3 which contains 0.1-50 g / l chromium (III) -analate complex.
  • EP 00 34 040 A1 describes a large number of layers of their larger group (among those set out by Barnes / Ward Standard conditions) the color is not mentioned, but as clear referred to as. Describe two examples, nos. 16 and 17 a greenish borate-containing layer that is cloudy to dull is called opaque.
  • Example 14 describes a layer with a corrosion protection of only 4 hours.
  • the phases chrome / (chrome + zinc) were compared with each other.
  • the chromium index is the average chromium content in decimal percent (% / 100) in the layer> 1% Cr, multiplied by the layer thickness in nm (see Fig. 37).
  • the chrome index is proportional to the amount of chrome on the surface (mg / m 2 ).
  • the new greenish chromate layer had a layer thickness of approx. 800 nm and was generated free of chromium (VI) and was proven chrome (VI) free.
  • Example 1 The production method according to Example 1 for the new greenish Chromium (VI) free chromating is necessary for conventional plants relatively high temperature of the process solution is not very economical. Further theoretical considerations for chromium (VI) free chromating and further attempts eventually led to economic ones Manufacturing conditions.
  • the chromating of zinc happens through the formation of a so-called conversion layer on the zinc surface, d. H. the Zinc surface reacts chemically with the chromating solution and is converted into a chromate layer.
  • the training of Conversion layers is a dynamic process beyond chemical balance. To describe the underlying Processes must therefore use chemical kinetics. With The specially set up kinetic model offered starting points win to optimize the present invention.
  • the kinetic model must include differential equations for the concentration profiles of Zn 2 , H + , Cr (III) and for the thickness growth of the ZnCrO layer.
  • the reaction rate approaches the term 1 / (1 + p 1 ⁇ m ZnCrO) 2 was considered that reaction I is increasingly slowed down by the growing passive layer by insertion.
  • P1 is a measure of the tightness of the layer.
  • tanh p 2 ⁇ m ZnCrO is the mandatory requirement of the reverse reaction 11, namely the presence of ZnCrO.
  • the tanh function ensures a smooth transition from 0 to 1, which can be set with P2.
  • the system of differential equations was solved numerically by computer. As a result, the course of the layer thickness and the concentration course over time were obtained.
  • Figure 1 shows the layer thickness curves for different values of the speed constant kj .
  • the passive layer should be as thick and at the same time as compact as possible.
  • Fig. 38 (original image 1) shows a computer simulation of the kinetic Zinc chromate model for various rate constants.
  • Malonic acid is a ligand that is faster on chromium (III) Ligand exchange kinetics enabled as the fluoride from Example 1.
  • Cobalt is an element that after the model presentation the Catalyze ligand exchange and also by incorporating kinetic stable oxides in the chromate layer reduce the back reaction II could, so that the chromate layer should become thicker overall.
  • Model presentation supported by practice.
  • complex ligands in which the complexing functional group contains nitrogen, phosphorus or sulfur (-NR 2 , -PR 2 where R is independently an organic, in particular aliphatic radical and / or H, and / or -SR, where R is an organic, in particular aliphatic radical or H), it is possible to produce the layer properties shown within limits even at room temperature.
  • the new greenish chromium (VI) free chromate layer is therefore ever after manufacturing temperature between 100 and 1000 nm thick, weak green in its own color and red-green iridescent.
  • the chromating solution consists of trivalent chromates, as well as conductive salts and Mineral acids. The chromating solutions are used in usually at temperatures above 40 ° C.
  • the corrosion protection from uninjured greenish chromium (VI) free chromations amounts to after manufacturing temperature to 100-1200 h in a salt spray cabinet DIN 50021 SS until the first appearance of corrosion products.
  • DIN 50961 Chopent 10, Table 3
  • chromium (VI) neither at the Manufacturing still in the product.
  • the present invention makes it possible for the first time to be chromium (VI) -free Conversion layers or passive layers based on To provide chromium (III), which however protects against corrosion the yellow chromations customary in the prior art - that is Provide chromium (VI) -containing passive layers.
  • powdery greenish layers are known for the Applicant - one of the leading companies in the field of Surface technology - no practical applications are known.
  • the left screw pile in the illustration according to FIG. 1 was a classic blue chromating - as on page 2 of the description set out in section 1 - subjected.
  • the middle pile of screws shows the result when the screws be passivated by the method according to the invention.
  • the colors reproduced in FIG. 1 are also the real colors, which follows that for the purpose of neutral Color rendering on the one hand a color chart and on the other hand a gray wedge was photographed.
  • FIGS. 1 are scanning electron microscope (SEM) images of the Conversion layers of a yellow chromate and one Blue chromating according to the prior art compared to "Chromitation" shown in accordance with the present invention.
  • the layer samples originated from the lower half of the figure in FIG shown correspondingly passivated galvanized iron screws.
  • the color photo of Figure 3 also shows the range of iris color the passive layer according to the invention in practice.
  • the layers of the present invention as well as the methods for Production of this layer or the process for Passivation of metal surfaces thus fulfills the longest in technology existing need for conversion layers, which without toxic and carcinogenic chromium (VI) compounds, and yet the Have corrosion protection of the yellow chromates and usually even surpass.
  • VI toxic and carcinogenic chromium
  • EP 00 34 040 A1 describes a large number of layers of their larger group (among those set out by Barnes / Ward Standard conditions) the color is not mentioned, but as clear referred to as. Describe two examples, nos. 16 and 17 a greenish borate-containing layer that is cloudy to dull is called opaque.
  • Example 14 describes a layer with a corrosion protection of only 4 hours.
  • Examples 16 and 17 describe layers with a corrosion protection of 300 and 200 hours in the salt spray test, ie in the range claimed by the applicant.
  • the description on page 19, line 7 shows that layers of greater than 1000 nm are required for good corrosion protection. It is therefore understandable that these layers, which, moreover, have always been produced from solutions containing boric acid, are described as cloudy and rather opaque (page 14, line 10). According to page 15, lines 1-5, the increased corrosion protection is due to the incorporation of borate-containing species.
  • the layer according to the invention also offers this addition a high (and even higher) corrosion protection.
  • the present layers according to the invention are hard and smudge-proof even without a curing process. Wipeable, non-adhering corrosion protection layers are unusable in practice.
  • FIG. 4 A photo is shown in FIG. 4 as a comparative example are the result of comparative tests carried out by the applicant in Has performed comparison to EP 00 34 040.
  • galvanized steel sheets were inserted into the the solutions described in Examples 16 and 17 of EP 00 34 040 immersed and the appropriate treatment times observed.
  • FIG. 4 shows the layers obtained according to the prior art the substrate surfaces, from top to bottom first and second sheet, which are successively by immersion has been treated.
  • the photo in FIG. 4 shows from left to right in the upper half of the picture a lobule with which the layer, produced according to Example 16 - Stand der Kunststoff - was wiped, one treated according to Example 16 galvanized steel sheet, next to it according to example 17 - state of the Technology - treated galvanized steel sheet and also on the far right a cloth with which the layer from Example 17 was wiped.
  • the second line is on the left - next to the reference to example 16 and to the right of it (next to the reference to example 17) one according to State of the art - coated galvanized steel sheet shown.
  • a milky, white-greenish powdery coating is visible, which can be wiped off with a soft cloth without special pressure (see Figure 4, upper half of the picture).
  • the coating method of the prior art itself suggests that this layer is not a compact oxidic zinc / chromium conversion layer firmly adhering to the substrate sheet, but rather a loosely lying coating essentially consisting of chromium hydroxide.
  • the pH value for this coating must be so high that the precipitation limit for chromium hydroxides has already been exceeded (page 26, line 12 of EP 0034 040).
  • the precipitation of chromium hydroxide is kinetically inhibited and is promoted by immersing a more or less rough surface.
  • FIGS. 5 to 36 were carried out with a glow discharge spectrometer.
EP97925823A 1996-04-19 1997-04-18 Chrom(vi)-freie konversionsschicht sowie verfahren zu ihrer herstellung Revoked EP0907762B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE29723891U DE29723891U1 (de) 1996-04-19 1997-04-18 Chrom(VI)freie Konversionsschicht

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19615664A DE19615664A1 (de) 1996-04-19 1996-04-19 Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
DE19615664 1996-04-19
PCT/DE1997/000800 WO1997040208A1 (de) 1996-04-19 1997-04-18 Chrom(vi)-freie konversionsschicht sowie verfahren zu ihrer herstellung

Publications (2)

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EP0907762A1 EP0907762A1 (de) 1999-04-14
EP0907762B1 true EP0907762B1 (de) 2001-10-17

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EP97925823A Revoked EP0907762B1 (de) 1996-04-19 1997-04-18 Chrom(vi)-freie konversionsschicht sowie verfahren zu ihrer herstellung

Country Status (11)

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US (2) US6287704B1 (ja)
EP (1) EP0907762B1 (ja)
JP (2) JP3597542B2 (ja)
AT (1) ATE207135T1 (ja)
AU (1) AU3087397A (ja)
BR (1) BR9710954A (ja)
DE (2) DE19615664A1 (ja)
DK (1) DK0907762T3 (ja)
ES (1) ES2163776T3 (ja)
PT (1) PT907762E (ja)
WO (1) WO1997040208A1 (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
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DE10223022A1 (de) * 2002-05-22 2003-12-11 Christoph Schulz Konversionsschicht für aus Zink oder aus zinkhaltigen Legierungen bestehende Untergründe
DE102008044143A1 (de) 2008-11-27 2010-06-02 Atotech Deutschland Gmbh Konversionsschichten für zinkhaltige Oberflächen
US20100175792A1 (en) * 2003-02-24 2010-07-15 Basf Aktiengesellschaft Carboxylate-containing polymers for metal surface treatment
CN106757281A (zh) * 2016-12-29 2017-05-31 广东工业大学 一种保护剂组合物和抗腐蚀键合丝及其制备方法
EP2189551B1 (en) 2007-08-03 2017-07-05 Dipsol Chemicals Co., Ltd. Corrosion-resistant trivalent-chromium chemical conversion coating

Families Citing this family (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19615664A1 (de) * 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
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