EP2458032A1 - Schwermetallfreies Vorbehandlungsverfahren für vorlackierte, galvanisierte Stahlblechrollen - Google Patents

Schwermetallfreies Vorbehandlungsverfahren für vorlackierte, galvanisierte Stahlblechrollen Download PDF

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Publication number
EP2458032A1
EP2458032A1 EP11187843A EP11187843A EP2458032A1 EP 2458032 A1 EP2458032 A1 EP 2458032A1 EP 11187843 A EP11187843 A EP 11187843A EP 11187843 A EP11187843 A EP 11187843A EP 2458032 A1 EP2458032 A1 EP 2458032A1
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EP
European Patent Office
Prior art keywords
treatment
ppm
free
metal
galvanised steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11187843A
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English (en)
French (fr)
Inventor
Ernesto Caldana
Emanuele Magistrelli
Matteo Damiani
Angelo Grandini
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NP Coil Dexter Industries SRL
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NP Coil Dexter Industries SRL
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Publication of EP2458032A1 publication Critical patent/EP2458032A1/de
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Classifications

    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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

Definitions

  • the present invention relates to a heavy metal such as cobalt and nickel-free pre-treatment process for pre-painted galvanised steel coils, characterised by an alkaline conversion treatment in the presence of ferric ions, trivalent chromium ions, zirconium salts and suitable complexing agents.
  • the treatment of flat laminates in the form of coils can consist of hot laminates (carbon and stainless steels) pickling to eliminate the oxides that cover them, or of their (steels, galvanised steels and aluminium) surface conversion treatment, generally to prepaint, but also with direct protective purposes.
  • Flat painted laminates are said to be prepainted because painting precedes the subsequent operations required for the manufacture of the finished product.
  • the paint In order to withstand these mechanical operations without damage, the paint must have excellent "mechanical" properties of adhesion, flexibility and elongation, which must not be jeopardised in any way by the pre-treatment. Pre-treatment is obviously also required to give the paint suitable resistance to the propagation of subcorrosion.
  • Solution-surface contact is facilitated by the planar geometry of the metal strip, but must take account of the very short reaction times (about 10 seconds at most).
  • reaction times about 10 seconds at most.
  • the different types of plant found on the market are generally one of three models, called “spray coating”, “reaction cell” and “roll coating”.
  • Spray coating is a spray application lasting about two seconds, generally with fairly high pressures and strong spraying, followed by a flash-off time (or "reaction zone”) lasting 5-10 seconds.
  • the reaction cell is an immersion application wherein a high volume of solution is pumped into an auxiliary container which can take the form of an approximately parallelepipedal tank, with or without a lid, lacking two opposite long, narrow sides through which the metal strip runs; the solution is pumped into the container in the opposite direction to the advance of the metal strip, and exits from the strip entry and exit areas, which act as overflow.
  • an auxiliary container which can take the form of an approximately parallelepipedal tank, with or without a lid, lacking two opposite long, narrow sides through which the metal strip runs; the solution is pumped into the container in the opposite direction to the advance of the metal strip, and exits from the strip entry and exit areas, which act as overflow.
  • the roll coater is a system of two cylinders whose rotation is induced by the advance of the metal strip: the first collects the solution and transfers it to the rubber applicator roller, which in turn deposits it on the metal strip in the form of a thin, even film.
  • the spray coater and reaction cell are normally used in standard treatments which involve rinsing after surface conversion.
  • the roll coater is used for "dry-in-place” applications, followed by heat treatment at a moderate temperature (generally ⁇ 100°C) to allow water evaporation and chemical reactions with the metal surface, without rinsing.
  • a coil-coating line can treat up to 200 m of sheet metal a minute, and must never stop.
  • galvanised steel treatment obtained by hot or electrolytic galvanisation
  • crystalline phosphating obtained by hot or electrolytic galvanisation
  • alkaline passivation or oxidation
  • chromating which is much more rare and tending to fall out of use for environmental and safety reasons, but is preferred when the zinc is alloyed with aluminium.
  • Preliminary degreasing is generally unnecessary when galvanising and painting are performed in the same factory but on different lines.
  • the use of strongly alkaline solutions (which are very effective but corrosive) is preferable in view of the very short contact times, and brushing is widespread.
  • Crystalline phosphating is widely used not only immediately before a painting treatment, but also when the galvanised sheet metal is to be subsequently cut, formed and assembled as part of a structure (such as vehicle bodywork or the casing of a household appliance) which is to be painted after assembly.
  • Chromating can performed on galvanised steel for pre-painting purposes, especially if aluminium is also treated in the same unit.
  • Alkaline passivation is an oxidation process which takes place in alkaline solution, in the presence of metals such as iron, nickel and cobalt kept in solution by complexing agents.
  • the coating formed, based on mixed Zn, Fe, Ni and Co oxides, must be further passivated in order to protect against corrosion.
  • the passivating product, once based on chromium and today replaced for years by chromium-free products based on titanium, zirconium, vanadium, molybdenum and/or silica, is designed to protect the surface against oxidation before painting.
  • the coating formed gives the surface a slightly brown colour, and is very thin: the cobalt deposited on the surface is generally between 3 and 20 mg/m 2 .
  • Alkaline passivation is a process which has been known for decades, and is well established. See, for example, US 3,444,007 and US 3,515,600 (1970s ) and US 4,381,203 (1983 ).
  • EP 1 484 432 again refers to alkaline passivation but introduces new elements, disclosing the use of chelating agents such as tartaric, malic, oxalic, malonic, succinic, citric, adipic and glyoxylic acids, alone or combined with one another, and indicates that the pH of the process must be between 0.5 and 4, preferably between 2 and 3.
  • chelating agents such as tartaric, malic, oxalic, malonic, succinic, citric, adipic and glyoxylic acids
  • EP 1,995,348 which relates to surface treatment of zinc with aqueous solutions containing trivalent chromium ions, chelating agents able to form water-soluble complexes of trivalent chromium, zinc ions, a sulphated compound and phosphite ions.
  • the pH of the solution must be acid: between 0.5 and 4, preferably between 1 and 3.
  • the chelating agents are the same as those described in EP 1,484,432 , in particular oxalic acid.
  • US 2009/0020185 describes surface treatment of zinc with aqueous solutions similar to the preceding ones but containing phosphoric or phosphorous esters instead of phosphites.
  • the pH of the solution must be between 0.5 and 4, preferably between 1 and 3.
  • the invention relates to a process of prepaint surface conversion on galvanised steel coils, as an alternative to the conventional alkaline passivation treatment.
  • the process according to the invention therefore produces a significant reduction in operating costs and greater operational safety, and is more environment-friendly.
  • the process according to the invention is characterised by a conversion treatment in an aqueous solution containing ferric ions, trivalent chromium ions, zirconium salts, a complexing agent and a base.
  • the complexing agent is preferably sodium gluconate, and the base is preferably sodium hydroxide.
  • the pH of the solution is between 11 and 13, preferably 12 ⁇ 0.5.
  • the concentration of ferric ions can range between 100 and 300 ppm, and that of trivalent chromium ions between 100 and 600 ppm.
  • the corresponding nitrates will preferably be used.
  • Zirconium ions can range between 100 and 300 ppm.
  • the conversion treatment according to the invention is preferably preceded by a step of degreasing with alkaline aqueous solution and by one or more washing steps.
  • the coils are usually washed with demineralised water before undergoing the final no-rinse chromium-free and heavy metal-free passivation treatment.
  • the degreasing step serves to eliminate all trace of oils, fats, cleaning paste, oxides and any other impurities from the coil surface, to ensure that the metal surface is perfectly clean before the subsequent treatments.
  • said degreasing is performed with aqueous solution at an alkaline pH (10-14).
  • the use concentration is between 1% and 10%, and the temperature of the working bath is between 60°C and 80°C, for a treatment time of between 5 and 20 seconds, with spray pressures of between 1 and 4 bars.
  • Table 1 Compound Concentration KOH or NaOH 2 - 20 g/l P 2 O 5 2 - 20 g/l Surfactants 200 - 3000 ppm Sequestering additives 1 - 10 g/l P 2 O 5 is present as orthophosphates (monosodium, disodium or trisodium phosphate) or polyphosphates (tripolyphosphate or neutral pyrophosphate), all in the form of sodium or potassium salts.
  • orthophosphates monosodium, disodium or trisodium phosphate
  • polyphosphates tripolyphosphate or neutral pyrophosphate
  • the surfactants most commonly used belong to the chemical families of ethoxylated fatty alcohols with alcohol chain C9-C 11, C12-C13 or C12-C18 with different degrees of ethoxylation, ie. containing different numbers of ethylene oxide moles.
  • the sequestering additives are organic compounds chosen from nitriloacetic acid, sodium gluconate, gluconic acid, ethylenediaminetetraacetic acid disodium, ethylenediaminetetraacetic acid trisodium, phosphonates, acrylates and polyacrylates.
  • Washing with water serves to eliminate all trace of the preceding step; the temperature is usually between 30°C and 60°C, with times ranging between 2 and 20 seconds, and the application is by spraying, with water renewal.
  • the conversion treatment according to the invention is the decisive step of the pre-treatment process, and serves to ensure good anchorage to the subsequent coat of paint, which must maintain excellent "mechanical” characteristics of adhesion, flexibility and elongation, together with good resistance to the propagation of subcorrosion.
  • solutions of ferric ions, trivalent chromium and zirconium salts can be used according to the invention in concentrations of between 1% and 10%.
  • the temperatures of the working bath are between 60°C and 80°C, with a treatment time of between 5 and 20 seconds and spray pressures of between 1 and 4 bars.
  • the sequestering additives are organic compounds selected from nitriloacetic acid, sodium gluconate, gluconic acid, phosphonates, acrylates and polyacrylates, preferably sodium gluconate.
  • the coils are usually washed with demineralised water to eliminate all trace of undesirable deposits from the surface of the material; as in the preceding cases, the temperature is generally between 30°C and 60°C, with times ranging between 2 and 20 seconds, and application is by spraying.
  • the final passivation step is designed to protect the surface temporarily against oxidation during transport and storage periods.
  • solutions containing hexavalent chromium whereas aqueous solutions of chromium-free products with an acid pH (2 - 4) are used today.
  • the use concentration is between 1% and 10%, and the temperature of the working bath is between 30°C and 50°C, for a treatment time of between 5 and 20 seconds, with spray pressures of between 1 and 4 bars.
  • the application is the no-rinse type.
  • Table 3 Compound Concentration Zirconium and/or titanium salts 0.3 - 2 g/l, for each metal Vanadium 100 mg/l Colloidal silica 200 mg/l Al (from alumina) 50 mg/l NH 3 50 ppm Modified acrylic or phenolic organic polymer 1000 mg/l
  • the zirconium salts are preferably chosen from fluozirconic acid, ammonium zirconium carbonate and potassium fluozirconate.
  • the titanium compounds comprise, for example, fluotitanic acid, titanium oxalate, titanium oxide and potassium fluotitanate.
  • the vanadium is inserted as ammonium vanadate, while the colloidal silica is a normal silica in dispersion.
  • Trivalent iron from iron nitrate
  • Trivalent chromium from chromium nitrate
  • Zirconium from zirconium nitrate
  • Sodium gluconate as complexing agent 6 - 10 g/l NaOH 12 - 18 g/l
  • the articles were dried with hot air at a temperature of between 60 and 80°C.
  • Table 4 summarises the test conditions used, with the codes of the corresponding strips: Table 4 PROCESS pH METALS COMPLEXING AGENT CODE ALKALINE PASSIVATION TRADITIONAL PROCESS alkaline nickel, cobalt, iron sodium gluconate N NOVEL PROCESS, NaOH-FREE acid chromium oxalic acid AC/C/O sodium gluconate AC/C/G chromium, iron, zirconium oxalic acid AC/CFZ/O sodium gluconate AC/CFZ/G NOVEL PROCESS, WITH NaOH alkaline chromium oxalic acid AL/C/O sodium gluconate AL/C/G chromium, iron, zirconium oxalic acid AL/CFZ/O sodium gluconate AL/CFZ/G
  • Hot-dip galvanised (HDG) steel strips were used; after the cycles had been performed, the strips were painted with 2 types of paint according to the normal conditions of industrial application.
  • Table 6 shows the evaluations compared with the conventional alkaline passivation process.
  • Table 6 PROCESS POLLUTION TEST * QUANTITY OF SLUDGE ** N OK up to Zn 1 g/l 100 AL/CFZ/O OK up to Zn 1.5 g/l 70 AL/CFZ/G OK up to Zn 2 g/l 30 * In this case, only mechanical adhesion tests were conducted ** Not absolute but relative values

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)
EP11187843A 2010-11-26 2011-11-04 Schwermetallfreies Vorbehandlungsverfahren für vorlackierte, galvanisierte Stahlblechrollen Withdrawn EP2458032A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT002198A ITMI20102198A1 (it) 2010-11-26 2010-11-26 Processo di pretrattamento su coil in acciaio zincato preverniciato esente da metalli pesanti

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EP2458032A1 true EP2458032A1 (de) 2012-05-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3070186A4 (de) * 2013-11-14 2017-07-26 Nisshin Steel Co., Ltd. Behandlungslösung zur chemischen umwandlung und chemisch umgewandeltes stahlblech
IT201800009491A1 (it) 2018-10-17 2020-04-17 Condoroil Chemical Srl Trattamento di conversione per coil zincati a caldo esente da cobalto.

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444007A (en) 1967-03-13 1969-05-13 Hooker Chemical Corp Process of forming paint-base coatings on zinc and zinc alloy surfaces
US3515600A (en) 1966-10-19 1970-06-02 Hooker Chemical Corp Metal treating process and composition
US4381203A (en) 1981-11-27 1983-04-26 Amchem Products, Inc. Coating solutions for zinc surfaces
EP0240943A2 (de) * 1986-04-08 1987-10-14 Metallgesellschaft Ag Verfahren zur Erzeugung von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen
EP0459549A1 (de) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Erzeugung von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen
EP1484432A1 (de) 2002-03-14 2004-12-08 Dipsol Chemicals Co., Ltd. Behandlungslösung zur herstellung eines schwarzen, kein sechswertiges chrom enthaltenden chemischen überzugs auf mit zink oder zinklegierung plattiertem substrat und verfahren zur herstellung eines schwarzen, kein sechswertiges chrom enthaltenden chemischen überzugs auf mit zink oder zinklegierung plattiertem substrat
EP1995348A1 (de) 2006-02-17 2008-11-26 Dipsol Chemicals Co., Ltd. Behandlungslösung zur bildung einer schwarzen chemischen beschichtung von dreiwertigem chrom auf zink oder zinklegierung und verfahren zur bildung einer schwarzen chemischen beschichtung von dreiwertigem chrom auf zink oder zinklegierung
US20090020185A1 (en) 2006-03-03 2009-01-22 Dipsol Chemicals Co. Ltd. Aqueous treating solution for forming black trivalent-chromium chemical conversion coating on zinc or zinc alloy and method of forming black trivalent-chromium chemical conversion coating

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515600A (en) 1966-10-19 1970-06-02 Hooker Chemical Corp Metal treating process and composition
US3444007A (en) 1967-03-13 1969-05-13 Hooker Chemical Corp Process of forming paint-base coatings on zinc and zinc alloy surfaces
US4381203A (en) 1981-11-27 1983-04-26 Amchem Products, Inc. Coating solutions for zinc surfaces
EP0240943A2 (de) * 1986-04-08 1987-10-14 Metallgesellschaft Ag Verfahren zur Erzeugung von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen
EP0459549A1 (de) * 1990-05-29 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Erzeugung von Konversionsüberzügen auf Zink- oder Zinklegierungsoberflächen
EP1484432A1 (de) 2002-03-14 2004-12-08 Dipsol Chemicals Co., Ltd. Behandlungslösung zur herstellung eines schwarzen, kein sechswertiges chrom enthaltenden chemischen überzugs auf mit zink oder zinklegierung plattiertem substrat und verfahren zur herstellung eines schwarzen, kein sechswertiges chrom enthaltenden chemischen überzugs auf mit zink oder zinklegierung plattiertem substrat
EP1995348A1 (de) 2006-02-17 2008-11-26 Dipsol Chemicals Co., Ltd. Behandlungslösung zur bildung einer schwarzen chemischen beschichtung von dreiwertigem chrom auf zink oder zinklegierung und verfahren zur bildung einer schwarzen chemischen beschichtung von dreiwertigem chrom auf zink oder zinklegierung
US20090020185A1 (en) 2006-03-03 2009-01-22 Dipsol Chemicals Co. Ltd. Aqueous treating solution for forming black trivalent-chromium chemical conversion coating on zinc or zinc alloy and method of forming black trivalent-chromium chemical conversion coating

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3070186A4 (de) * 2013-11-14 2017-07-26 Nisshin Steel Co., Ltd. Behandlungslösung zur chemischen umwandlung und chemisch umgewandeltes stahlblech
IT201800009491A1 (it) 2018-10-17 2020-04-17 Condoroil Chemical Srl Trattamento di conversione per coil zincati a caldo esente da cobalto.

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