EP0496678A1 - Verfahren zum kontinuierlichen Feuerverzinken bei hoher Temperatur - Google Patents

Verfahren zum kontinuierlichen Feuerverzinken bei hoher Temperatur Download PDF

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Publication number
EP0496678A1
EP0496678A1 EP19920400178 EP92400178A EP0496678A1 EP 0496678 A1 EP0496678 A1 EP 0496678A1 EP 19920400178 EP19920400178 EP 19920400178 EP 92400178 A EP92400178 A EP 92400178A EP 0496678 A1 EP0496678 A1 EP 0496678A1
Authority
EP
European Patent Office
Prior art keywords
zinc
phase
layer
products
iron
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.)
Ceased
Application number
EP19920400178
Other languages
English (en)
French (fr)
Inventor
José Delot
Guy Dussous
Gérald Sanchez
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.)
Delot Process SA
Original Assignee
Delot Process SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Delot Process SA filed Critical Delot Process SA
Publication of EP0496678A1 publication Critical patent/EP0496678A1/de
Ceased legal-status Critical Current

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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
    • C23C2/02—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
    • C23C2/02—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

Definitions

  • the present invention relates to a continuous galvanizing process at high temperature, more particularly intended for galvanizing steels from zinc baths or molten zinc alloys.
  • the annealing can be carried out during the galvanization, the rise in temperature necessary for the annealing being exploited to condition the metallurgical product treated in a manner suitable for its subsequent coating with a protective layer of zinc. .
  • a continuous galvanizing process is also known which is particularly suitable for obtaining protective layers of thin zinc on continuous or discontinuous elongated products.
  • the galvanizing operations consist in activating by blasting the reactivity of the surface of the products, which are then rapidly heated by induction before passing into a "bubble" of molten zinc where the metallurgical reaction, all taking place under a slightly reducing inert atmosphere; on leaving this zinc "bubble", the coated products are "wiped” by means capable of eliminating the thickness of excess zinc, before being finally immediately cooled, always in a neutral atmosphere.
  • This process makes it possible to very quickly treat products of the type of concrete reinforcing wire, angles, or even sheets, the other advantage of this process being the economy which it makes it possible to achieve on the consumption of and zinc.
  • the balance diagram of the iron-zinc alloy shows that the coating deposited by galvanization has, after cooling, a complex crystallographic structure formed of several phases, known under the names of "delta phase” and “dzeta phase", the surface layer of zinc being, for its part, in a crystallographic phase called “eta”.
  • the thicknesses of the layers of stable intermetallic compounds formed by these various phases naturally depend on the galvanization kinetics, in particular on the cooling rate, rapid cooling making it possible to avoid or moderate the thermal diffusion of the phases between them which is responsible for the 'grayish or brown appearance of certain galvanized parts.
  • Japanese patent JP-A-63,447 relates to a process for manufacturing hot-dip galvanized steel parts having high plasticity; this process uses a zinc bath enriched with aluminum (of the order of 20 to 24%) which is maintained at a temperature of between 500 ° and 540 ° C, the immersion time of the products being between 1 and 5 seconds .
  • the primary objective of adding aluminum in a percentage as high as that recommended in this last patent is to inhibit the iron-zinc reaction, and therefore the formation of intermetallic layers between the underlying steel and the layer. zinc.
  • t (C2 - C02) / a with C the percentage of aluminum and has a parameter determining the inhibition; under the conditions of the above-mentioned patent, the inhibition period t is equal to 133 hours, with the consequence of a total inhibition of the reactions for the formation of iron-zinc intermetallic alloys.
  • the melting point of the iron-aluminum alloys is higher the higher the percentage of aluminum; under the conditions of the process described in the aforementioned patent, the melting temperature of the iron-aluminum alloy is thus between 480 ° and 500 ° C. Consequently, if one wants to respect the normal conditions of supercooling of the bath, namely from 20 ° to 40 ° C minimum - this in order to avoid the problems linked to the accidental freezing of molten liquid metal in the enclosures and the galvanizing ovens -, the temperature of the previous iron-aluminum alloy bath should be maintained between 500 ° and 540 ° C.
  • pure zinc bath a zinc bath which may contain a certain percentage of wetting agents, such as lead, which the person skilled in the art knows that they do not exert. that little influence on the growth kinetics of intermetallic iron-zinc compounds.
  • the invention thus aims to obtain in a single step metallurgical products galvanized with zinc having, at their iron-zinc interface, a layer of a intermetallic alloy in the delta crystallographic phase, without the presence of any other crystallographic phase, the nature and thickness of this same layer being controlled, mainly, by the galvanization temperature.
  • the time taken for the metallurgical products to pass through the high-temperature galvanizing bath must be very short, for example less than 5 seconds, the coated metallurgical products leaving the enclosure having to be cooled with about 100 ° C as quickly as possible, for example in less than half a second.
  • the intermetallic iron-zinc layer in the "delta” phase has a thickness of less than 10 microns, while the thickness of practically pure surface zinc reaches from a few microns to a few tens of microns depending on the type of "wiping" used at the exit of the galvanizing chamber - "wiping” consists in removing surpluses of non-frozen zinc alloy from the surface of the treated products; this operation, which is done by gravity in the oldest technologies, can be forced by gas blowing means or by electromagnetic means).
  • the ratio between the two previously mentioned thicknesses ie that of the layer of pure zinc over that of the intermetallic layer
  • a limit value of the order of 3, beyond which the structure of the coating, perpendicular to the surface of the coated metallurgical products, is particularly favorable to their cold plastic transformation.
  • the presence of a majority of practically pure zinc on the surface makes it possible to significantly reduce the work required to carry out this operation, since, in fact, the pure zinc is particularly ductile.
  • this ratio reaches a value equal to approximately 6.
  • the tests consisted in passing the concrete wires through, at a speed of 80 m / mm, in an enclosure containing a bath of molten zinc at a temperature of approximately 560 ° C. after having descaled by shot blasting, then heated by induction at around 550 ° C, all under a slightly reducing inert atmosphere, and finally cooled in water or in air in forced convection at 25 ° C. This cooling lowers the temperature of the wires very quickly, since they lose 100 ° C in 0.03 seconds in water and in 0.62 seconds in air.
  • the following table lists the characteristics of cold-treated wires, before and after treatment, as well as those of their coating: with Ag b the uniformly distributed elongation of the raw rolling wire, Ag g the uniformly distributed elongation of the galvanized wire according to the process according to the invention, E total the total thickness of the coating and E inter the thickness of the layer of Fe / Zn intermetallic compounds in the "delta" phase, these two thicknesses being given in micrometers.
  • a cold forged metallurgical product originally uncoated and having a given coefficient of elongation, becomes, due to the structure of the coating and the simultaneous and consequent improvement of its elongation, perfectly suitable for being stamped.

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)
EP19920400178 1991-01-23 1992-01-23 Verfahren zum kontinuierlichen Feuerverzinken bei hoher Temperatur Ceased EP0496678A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9100784 1991-01-23
FR9100784A FR2671809B1 (fr) 1991-01-23 1991-01-23 Procede de galvanisation en continu a haute temperature.

Publications (1)

Publication Number Publication Date
EP0496678A1 true EP0496678A1 (de) 1992-07-29

Family

ID=9408997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920400178 Ceased EP0496678A1 (de) 1991-01-23 1992-01-23 Verfahren zum kontinuierlichen Feuerverzinken bei hoher Temperatur

Country Status (2)

Country Link
EP (1) EP0496678A1 (de)
FR (1) FR2671809B1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1029940A1 (de) * 1999-02-18 2000-08-23 Sollac Verfahren zur Aluminisierung von Stahl zum Erzeugen einer dünnen Grenzflächenschicht
EP2071047A1 (de) 2007-12-10 2009-06-17 Benteler Automobiltechnik GmbH Verfahren zur Herstellung eines verzinkten Formbauteils aus Stahl
EP2419548A1 (de) * 2009-04-15 2012-02-22 Hot Dip Solutions, Llc Verfahren zum beschichten eines substrats

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259148A (en) * 1961-05-01 1966-07-05 Allied Tube & Conduit Corp Galvanized steel tubing
GB1085744A (en) * 1965-03-25 1967-10-04 Ruthner Ind Planungs Ag Hot dip galvanizing process

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3010844A (en) * 1961-01-06 1961-11-28 Nat Steel Corp Galvanizing
JPS6026652A (ja) * 1983-07-23 1985-02-09 Nippon Steel Corp プレス加工用溶融亜鉛メツキ鋼板
JPS6289856A (ja) * 1985-06-19 1987-04-24 Nippon Steel Corp 耐経時めつき剥離性に優れた溶融亜鉛・アルミニウム合金めつき鋼板及びその製造方法
JPS624858A (ja) * 1985-06-29 1987-01-10 Nippon Steel Corp 接着性，加工性に優れた溶融亜鉛メツキ鋼板及びその製造方法
JPS63447A (ja) * 1986-06-18 1988-01-05 Seiko Instr & Electronics Ltd 高減衰能を有する溶融めつき鋼材とその製造方法
JPS63157847A (ja) * 1986-12-19 1988-06-30 Nippon Steel Corp 合金化亜鉛メツキ鋼板の製造方法
JPS63317658A (ja) * 1988-05-17 1988-12-26 Nikko Aen Kk 溶融メッキ用亜鉛合金およびその使用方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259148A (en) * 1961-05-01 1966-07-05 Allied Tube & Conduit Corp Galvanized steel tubing
GB1085744A (en) * 1965-03-25 1967-10-04 Ruthner Ind Planungs Ag Hot dip galvanizing process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1029940A1 (de) * 1999-02-18 2000-08-23 Sollac Verfahren zur Aluminisierung von Stahl zum Erzeugen einer dünnen Grenzflächenschicht
FR2790010A1 (fr) * 1999-02-18 2000-08-25 Lorraine Laminage Procede d'aluminiage d'acier permettant d'obtenir une couche d'alliage interfaciale de faible epaisseur
US6309761B1 (en) 1999-02-18 2001-10-30 Sollac Process of aluminizing steel to obtain and interfacial alloy layer and product therefrom
EP2071047A1 (de) 2007-12-10 2009-06-17 Benteler Automobiltechnik GmbH Verfahren zur Herstellung eines verzinkten Formbauteils aus Stahl
EP2419548A1 (de) * 2009-04-15 2012-02-22 Hot Dip Solutions, Llc Verfahren zum beschichten eines substrats

Also Published As

Publication number Publication date
FR2671809B1 (fr) 1994-03-11
FR2671809A1 (fr) 1992-07-24

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