EP2712331B1 - Verfahren zur elektrolytischen verzinkung mit verbessertem korrosionsschutz - Google Patents

Verfahren zur elektrolytischen verzinkung mit verbessertem korrosionsschutz Download PDF

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Publication number
EP2712331B1
EP2712331B1 EP12716407.7A EP12716407A EP2712331B1 EP 2712331 B1 EP2712331 B1 EP 2712331B1 EP 12716407 A EP12716407 A EP 12716407A EP 2712331 B1 EP2712331 B1 EP 2712331B1
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EP
European Patent Office
Prior art keywords
range
seconds
water
protected
product
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.)
Not-in-force
Application number
EP12716407.7A
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English (en)
French (fr)
Other versions
EP2712331A1 (de
Inventor
David TRUDEN
Kristina SIMIC
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kovinoplastika Loz Industrija Kovinskih In Plasticnih Izdelkov dd
Original Assignee
Kovinoplastika Loz Industrija Kovinskih In Plasticnih Izdelkov dd
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Application filed by Kovinoplastika Loz Industrija Kovinskih In Plasticnih Izdelkov dd filed Critical Kovinoplastika Loz Industrija Kovinskih In Plasticnih Izdelkov dd
Publication of EP2712331A1 publication Critical patent/EP2712331A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • 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 refers to a process of electrolytic galvanizing, thick layer passivation and subsequent treatment in order to enhance anti-corrosive protection, wherein said process comprises a pretreatment and, respectively, cleaning of products to be protected against corrosion, galvanizing in an alkaline media and final treatment.
  • a process of electrolytic galvanizing of the aforementioned kind has been disclosed by the publication of a patent application No. EP 1 199 376 A1 .
  • a Zn coated steel material, a Zn coated steel sheet and a painted steel sheet that are excellent in corrosion resistance and can be applied to various purposes, such as for home electrical appliances and building materials, and a process for production thereof.
  • the known process meets the requirements set by the users, it also comprises certain disadvantages as demonstrated particularly in a relative high power consumption and, as result, in use of relatively aggressive medium.
  • the layer thickness of the anti-corrosive protection on products exceeds 20 ⁇ m and are thus useless in the environment with very demanding and up to extremely demanding climatic load.
  • a process of electrolytic galvanizing with an enhanced anti-corrosive protection comprises a pretreatment, wherein organic impurities, rust, dross and similar is removed from the surface of a product to be protected.
  • Said pretreatment is carried out in alkaline solutions comprising sodium metasilicate, sodium hydroxide, sodium carbonate, and in acidic water solutions comprising sodium hydroxide and sodium carbonate.
  • step of the process of electrolytic galvanizing with an enhanced anti-corrosive protection comprises galvanization being carried out in an alkaline cyanide-free media.
  • the alkalinity of said cyanide-free media is as high as possible.
  • Said alkaline cyanide-free media comprises silicic acid, sodium salt comprising sodium silicate, components of a water polymer solution comprising nitrogen, a solution of trition trisodium salt and triazine, and a polymer solution comprising methanol and formaldehyde.
  • the process of electrolytic galvanizing with an enhanced anti-corrosive protection comprises a step of final treatment, wherein a thick layer passivation based on chromium III compounds and cobalt compounds represents the primary layer on the zinc coating applied by means of galvanization to the product to be protected.
  • Said product to be protected is treated in a working bath at the temperature in the range between about 19 °C and about 30 °C, preferably in the range between about 21 °C and about 28 °C.
  • Said working bath comprises a pH value in the range between about 2,0 and about 3,0, preferably in the range between about 2,3 and about 2,7.
  • said product is flushed by means of a pure water, preferably by means of demineralized and deionized water.
  • the previous step is followed by sinking said product for the first time period into a polymer dispersion of silicate and polyurethane in water.
  • the ratio between the silicate and the polyurethane in said polymer dispersion in water amounts to approximately 10 : 1.
  • Said first time period lies in the range between 40 seconds and 80 seconds, preferably between 50 seconds and 70 seconds.
  • said polymer dispersion in water comprises a pH value in the range between about 8,0 and about 11,0, preferably in the range between about 8,5 and about 10,5.
  • said product to be protected is removed for the second time period from said polymer dispersion of silicate and polyurethane in water. It is provided for according to the invention that said second time period lies in the range of about 10 seconds.
  • the removal of said product from said polymer dispersion of silicate and polyurethane in water is followed by a re-immersion for the third time of period of said product to be protected into said polymer dispersion of silicate and polyurethane in water.
  • Said third time period lies in the range between 15 seconds and 50 seconds, preferably between 20 seconds and 40 seconds.
  • said polymer dispersion of silicate and polyurethane in water must be continuously stirred during the process.
  • the above disclosed process step is followed by draining and/or removing of the surplus of said polymer dispersion in water off the product to be protected being followed by drying.
  • the drying is carried out during the fourth time period by means of a hot air in closed or partially closed drying chambers in the temperature range between about 50 °C and about 90 °C, preferably in the temperature range between about 60 °C and about 80 °C.
  • said forth time period ranges between 6 minutes and 15 minutes, preferably between 8 minutes and 12 minutes.
  • the above disclosed process of electrolytic galvanizing with an enhanced anti-corrosive protection according to the invention is carried out entirely at relatively low temperatures, thus having significant advantages over the present solutions.
  • the process of low-temperature thick layer passivation features substantial energy savings since it is carried out at the room temperature.
  • less aggressive media having smaller content of Zn 2+ and Fe 2+ ions is used during the process, resulting in waste waters comprising no nano particles.
  • the anti-corrosion protection increases on products intended for building hardware and other sectors where high anti-corrosion protection on zinc coating is required.
  • the layer of the anti-corrosion protection is equally distributed over the entire surface of the product to be protected.
  • an outstanding anti-corrosion protection is obtained where the thickness of an average layer of the anti-corrosion protection lies in the thickness range of 10 ⁇ m without reducing the anti-corrosion protection of products being used in extreme climate conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (10)

  1. Verfahren zur elektrolytischen Verzinkung, Dickschichtpassivierung und Nachbehandlung zur Verbesserung des Korrosionsschutzes, wobei das Verfahren jeweils eine Vorbehandlung und Reinigung der Produkte, die vor Korrosion geschützt werden sollen, eine Verzinkung in einem alkalischen Medium und eine Endbehandlung umfasst, dadurch gekennzeichnet, dass die Endbehandlung, bei welcher eine Dickschichtpassivierung basierend auf Chrom-(III)-Verbindungen und Cobalt-Verbindungen die Primärschicht auf der Zinkbeschichtung bildet, die durch Galvanisierung auf dem zu schützenden Produkt aufgebracht worden ist, umfasst:
    a) Behandeln des zu schützenden Produkts in einem Bearbeitungsbad,
    b) Spülen des zu schützenden Produkts mithilfe von Reinwasser, vorzugsweise mittels demineralisiertem und entionisiertem Wasser,
    c) Eintauchen des zu schützenden Produkts für eine erste Zeitspanne in eine Polymerdispersion aus Silikat und Polyurethan in Wasser, wobei die Polymerdispersion aus Silikat und Polyurethan in Wasser kontinuierlich gerührt werden muss,
    d) Entnehmen des zu schützenden Produkts für eine zweite Zeitspanne aus der Polymerdispersion aus Silikat und Polyurethan in Wasser,
    e) Wiedereintauchen des zu schützenden Produkts für eine dritte Zeitspanne in die Polymerdispersion aus Silikat und Polyurethan in Wasser, wobei die Polymerdispersion aus Silikat und Polyurethan in Wasser kontinuierlich gerührt werden muss,
    f) Abgießen und/oder Entfernen des Überschusses der Polymerdispersion aus Silikat und Polyurethan in Wasser von dem zu schützenden Produkt,
    g) Trocknen des zu schützenden Produkts während einer vierten Zeitspanne mittels Heißluft.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Temperatur eines Bearbeitungsbads in einem Bereich zwischen etwa 19 °C und etwa 30 °C, vorzugsweise in einem Bereich zwischen etwa 21 °C und etwa 28 °C, liegt.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein pH - Wert des Bearbeitungsbads in einem Bereich zwischen etwa 2,0 und etwa 3,0, vorzugsweise in einem Bereich zwischen etwa 2,3 und etwa 2,7, liegt.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Verhältnis zwischen Silikat und Polyurethan in der Polymerdispersion in Wasser näherungsweise 10:1 beträgt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerdispersion in Wasser einen pH - Wert aufweist, der in einem Bereich zwischen etwa 8,0 und etwa 11,0, vorzugsweise in einem Bereich zwischen etwa 8,5 und etwa 10,5, liegt.
  6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die erste Zeitspanne in einem Bereich zwischen 40 Sekunden und 80 Sekunden, vorzugsweise zwischen 50 Sekunden und 70 Sekunden, liegt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die zweite Zeitspanne in einem Bereich von etwa 10 Sekunden liegt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die dritte Zeitspanne in einem Bereich zwischen 15 Sekunden und 50 Sekunden, vorzugsweise zwischen 20 Sekunden und 40 Sekunden, liegt.
  9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Temperatur der Heißluft zur Trocknung in einem Bereich zwischen etwa 50 °C und etwa 90 °C, vorzugsweise in einem Bereich zwischen etwa 60 °C und etwa 80 °C, liegt.
  10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die vierte Zeitspanne zwischen 6 Minuten und 15 Minuten, vorzugsweise zwischen 8 Minuten und 12 Minuten, beträgt.
EP12716407.7A 2011-05-19 2012-04-23 Verfahren zur elektrolytischen verzinkung mit verbessertem korrosionsschutz Not-in-force EP2712331B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SI201100179A SI23452A (sl) 2011-05-19 2011-05-19 Postopek elektrolitskega cinkanja s povečano protikorozijsko zaščito
PCT/EP2012/057334 WO2012156176A1 (en) 2011-05-19 2012-04-23 A process of electrolytic galvanizing with an enhanced anti-corrosive protection

Publications (2)

Publication Number Publication Date
EP2712331A1 EP2712331A1 (de) 2014-04-02
EP2712331B1 true EP2712331B1 (de) 2016-11-16

Family

ID=45782028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12716407.7A Not-in-force EP2712331B1 (de) 2011-05-19 2012-04-23 Verfahren zur elektrolytischen verzinkung mit verbessertem korrosionsschutz

Country Status (5)

Country Link
EP (1) EP2712331B1 (de)
CN (1) CN103608125A (de)
EA (1) EA024221B1 (de)
SI (1) SI23452A (de)
WO (1) WO2012156176A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017186931A1 (de) * 2016-04-29 2017-11-02 Chemetall Gmbh Verfahren zur korrosionsschützenden behandlung einer metallischen oberfläche mit vermindertem beizabtrag
IT201700117705A1 (it) 2017-10-18 2019-04-18 Me Ga S R L Telaio a cestelli rotanti per galvanizzazione
CN112410710A (zh) * 2020-11-11 2021-02-26 合肥亿昌兴精密机械有限公司 抗腐蚀高强度的镀锌板和镀锌板制备工艺

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2211762B (en) * 1987-11-13 1991-11-13 Kobe Steel Ltd Zinc alloy-plated corrosion preventive steel sheet having an organic coating layer thereon and a method for making the same
US5108554A (en) * 1990-09-07 1992-04-28 Collis, Inc. Continuous method for preparing steel parts for resin coating
US6465114B1 (en) * 1999-05-24 2002-10-15 Nippon Steel Corporation -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same
CN1740402A (zh) * 2000-03-22 2006-03-01 以利沙控股有限公司 一种用于处理导电表面的增强性工艺方法以及由此形成的产品
US7291402B2 (en) * 2002-07-23 2007-11-06 Jfe Steel Corporation Surface-treated steel sheets of good white rust resistance, and method for producing them
DE10309908B4 (de) * 2003-03-07 2006-12-14 Benteler Stahl/Rohr Gmbh Verfahren zur Herstellung eines verzinkten und mit einem Polymer beschichteten Stahlrohrs

Non-Patent Citations (1)

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Title
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Also Published As

Publication number Publication date
EP2712331A1 (de) 2014-04-02
SI23452A (sl) 2012-02-29
EA024221B1 (ru) 2016-08-31
CN103608125A (zh) 2014-02-26
WO2012156176A1 (en) 2012-11-22
EA201370240A1 (ru) 2014-02-28

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