EP2430206B1 - Modification of the composition of the flux solution for hot-dip batch galvanizing of steel parts - Google Patents

Modification of the composition of the flux solution for hot-dip batch galvanizing of steel parts Download PDF

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Publication number
EP2430206B1
EP2430206B1 EP10711936.4A EP10711936A EP2430206B1 EP 2430206 B1 EP2430206 B1 EP 2430206B1 EP 10711936 A EP10711936 A EP 10711936A EP 2430206 B1 EP2430206 B1 EP 2430206B1
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EP
European Patent Office
Prior art keywords
flux solution
process according
steel parts
hot
minutes
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.)
Active
Application number
EP10711936.4A
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German (de)
English (en)
French (fr)
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EP2430206A1 (en
Inventor
Ugo Bottanelli
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SETRA Srl
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SETRA Srl
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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30—Fluxes or coverings on molten baths

Definitions

  • the present invention has as object the improvement of the surface preparation of pre-fabricated steel parts to be hot-dip galvanized and more specifically it refers to the influence of the flux solution composition or the coating quality obtained in batch galvanizing processes where molten Zinc baths containing up to 0,1 wt% A1 are used.
  • Batch hot-dip galvanizing is one of the most important technologies for steels coating against corrosion especially atmospheric.
  • steel parts are immersed into molten Zinc at 440-450°C.
  • the sequence of these operations are still the same since many years: a) degreasing followed by water rinsing, b) 10wt% HCl pickling followed by water rinsing, c) fluxing into a water-based saline solution which contains ZnC12+NH4Cl, followed by drying without rinsing, d) immersion into a molten Zn-based alloy at ⁇ 440-450°C.
  • Steels that my be galvanized include those so-called: reactive. Steels reactivity depends on a critical concentration of Si and P in the steel (Sandelin effect) which may vary not only among the steels but also in the same steel where they may be unevenly distributed. Coatings obtained with reactive steels are gray and dull, the interface with the steel is fragile, the thickness of the coating is high causing excessive Zinc consumption and therefore an economical damage.
  • the fragile interface contains Zn-Fe phases that may reach the outer surface of the coating which due to its fragility may flake after a mechanical deformation.
  • Examples of these modification of the galvanizing baths composition are the so-called Polygalva based on 0.06wt% A1 addition, other methods based on less A1 additions, or the so-called Technigalva based on 0.05wt% ofNi addition.
  • the flux solution which traditionally contains a mixture of salts among which ZnCl2 is, according to its concentration, a potential source of danger for the environment and thus must be carefully monitored.
  • US 2007/0137731 and WO 2007/146161 disclose a flux for using in a hot dip galvanisation process containing e.g. 15-40 wt.% ZnCl2, 1-10 wt.% NH3CI, 1-6 wt.% KCI and more than 0.05 wt.% Bi2O3 and including an acidic component so that the flux has a pH of about 1.5 or less.
  • the present invention aims at contributing to the solution of potential problems arising from the presence of ZnCl2 in the galvanizing shop, by means of a procedure for the preparation of surface of pre-fabricated steel pieces to be hot-dip galvanized in a Zn-Al-alloy, according to which the concentration of ZnCl2 into the flux solution is maintained below the limit prescribed by the law and preferably down to zero.
  • the steel pieces, after pickling are immersed into an aqueous solution containing: 0-50 g/L of ZnCl 2 , preferably 0-25, and more preferably 0-10, 20-300 g/L of NH 4 Cl, 0.1-1 g/L of Bi 2 O 3 , at a pH ranging from 0.1 e 1.5, preferably between 0.5 e 1, maintained in the optimum interval by means of HCl 0.1N or KOH 0.1N additions; pieces are immersed in the flux solution at a temperature between 4 and 50°C, preferably between 10 and 30°C and more preferably between 15 and 25°C, for an immersion time between 10s and 10 minutes, preferably between20s and 2 min. and more preferably between 30s and 1 min. After extraction from the flux solution, the steel pieces are dried at 60-120°C for a maximum time of 60 min.
  • the salts from the flux solution remain adherent to the steel pieces and have a fusion temperature well below the temperature of the molten galvanizing bath and are therefore easily eliminated upon immersion forming ashes and dross.
  • the flux solution according to the present invention it is possible to coat in a batch galvanizing bath containing a Zn-Al-afloy, both carbon and high strength steels.
  • steels with high Si content, and/or Mn, and/or P i.e. steels commercially known as Sandelin or Iper-sandelin steels
  • the flux solution according to the present invention may be easily coated using the flux solution according to the present invention obtaining coating with uniform thickness, with no surface defects and with a smooth surface without non-homogeneous areas.
  • Table 1 contains the symbols with which the surface quality of coatings was assessed according its coating homogeneity & continuity, uniformity of the colour.
  • Table 1. Symbol Merit ⁇ Very bad Bad ⁇ Sufficient ⁇ Good ⁇ Excellent Table 2 FLUX GALVANIZING ZnCl 2 NH 4 Cl KOH KCl Bi 3+ Fe 2+ (pH) Al in the molten bath Immersion time Merit g/L g/L g/L g/L g/L % (s) Control 138.00 144.00 95.35 63.00 0.52 3.49 1.2 0.02 180 ⁇ 1 - - - - 0.50 - 1 5.00 60 ⁇ 2 0 50 75.68 50 0.50 - 1 5.00 60 3 0 100 75.68 50 0.50 - 1 5.00 60 ⁇ 4 25 100 75.68 50 0.50 - 1 5.00 60 ⁇ 5 - - - - - 8 (**) 0.03 60 ⁇ 6 - - - - - -

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP10711936.4A 2009-02-19 2010-02-17 Modification of the composition of the flux solution for hot-dip batch galvanizing of steel parts Active EP2430206B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITAL2009A000002A IT1392855B1 (it) 2009-02-19 2009-02-19 Nuova formulazione della soluzione di flussaggio nei processi di zincatura generale a caldo dell'acciaio
PCT/IT2010/000052 WO2010095154A1 (en) 2009-02-19 2010-02-17 Modification of the composition of the flux solution for hot-dip batch galvanizing of steel parts

Publications (2)

Publication Number Publication Date
EP2430206A1 EP2430206A1 (en) 2012-03-21
EP2430206B1 true EP2430206B1 (en) 2013-07-03

Family

ID=41055106

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10711936.4A Active EP2430206B1 (en) 2009-02-19 2010-02-17 Modification of the composition of the flux solution for hot-dip batch galvanizing of steel parts

Country Status (3)

Country Link
EP (1) EP2430206B1 (it)
IT (1) IT1392855B1 (it)
WO (1) WO2010095154A1 (it)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2646303C2 (ru) * 2016-07-12 2018-03-02 Акционерное общество "Уралэлектромедь" Флюс для горячего цинкования стальных изделий
DE102021111089A1 (de) 2021-04-29 2022-11-03 Seppeler Holding Und Verwaltungs Gmbh & Co. Kg Verfahren, Anlage und Verwendung dieser in der diskontinuierlichen Stückverzinkung
CN115323304B (zh) * 2022-08-30 2024-02-09 重庆广仁能源装备股份有限公司 一种低硅活性钢的热镀锌方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060228482A1 (en) * 2005-04-07 2006-10-12 International Lead Zinc Research Organization, Inc. Zinc-aluminum alloy coating of metal objects
CA2628470C (en) * 2005-12-20 2011-10-18 Teck Cominco Metals Ltd. Flux and process for hot dip galvanization
CA2669074A1 (en) * 2006-06-09 2007-12-21 Teck Cominco Metals Ltd. High-aluminum alloy for general galvanizing

Also Published As

Publication number Publication date
IT1392855B1 (it) 2012-04-02
WO2010095154A1 (en) 2010-08-26
EP2430206A1 (en) 2012-03-21
ITAL20090002A1 (it) 2010-08-20

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