EP1358360B1 - Verfahren zum verzinken von stahl - Google Patents

Verfahren zum verzinken von stahl Download PDF

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Publication number
EP1358360B1
EP1358360B1 EP01273287A EP01273287A EP1358360B1 EP 1358360 B1 EP1358360 B1 EP 1358360B1 EP 01273287 A EP01273287 A EP 01273287A EP 01273287 A EP01273287 A EP 01273287A EP 1358360 B1 EP1358360 B1 EP 1358360B1
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EP
European Patent Office
Prior art keywords
zone
oxidising
sheet
atmosphere
oxidizing
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.)
Expired - Lifetime
Application number
EP01273287A
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English (en)
French (fr)
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EP1358360A1 (de
Inventor
Michel Dubois
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.)
ArcelorMittal France SA
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Arcelor France SA
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Publication date
Application filed by Arcelor France SA filed Critical Arcelor France SA
Priority to EP01273287A priority Critical patent/EP1358360B1/de
Publication of EP1358360A1 publication Critical patent/EP1358360A1/de
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Publication of EP1358360B1 publication Critical patent/EP1358360B1/de
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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor

Definitions

  • the present invention relates to a novel method of hot-coating a steel sheet by dipping in a bath of liquid metal, in particular containing molten zinc.
  • the invention relates to the control of the oxidation-reduction of the atmosphere of the input horn in the liquid zinc bath, with respect to iron and liquid zinc, more specifically in the vicinity of the wetting line.
  • US Pat. No. 4,557,953 (corresponding to EP-A-0 172 681) proposes a method in which an atmosphere of inert gases containing 1-8% hydrogen by volume in combination with 300 to 4500 ppm of water vapor.
  • the ratio H 2 / H 2 O must be at least 4.
  • the oxidation-reduction potential recommended in the state of the art for oxidizing the surface of the liquid zinc does not prevent the oxidation of the alloying elements contained in the steel such as the manganese, chromium, silicon, etc. These are commonly used in the production of so-called hard steels high yield strength (HLE).
  • the recommended oxidation-reduction potential also causes excessive oxidation of the surface at the level of the wetting line inside the horn. This results in the formation of large clusters of zinc oxide (ZnO) which always end up detaching, usually unpredictably. This occurs when the viscous driving forces of the surface liquid zinc become greater than those of adhesion and surface tension with respect to the horn.
  • the present invention aims to provide a solution to the problems posed in the state of the art and in particular related to the zinc oxidation process which is recommended.
  • the present invention has the particular object of reducing to a minimum the zone in which the oxidation of liquid zinc and alloying elements of the sheet, with the exception of iron, is achieved, therefore the time corresponding oxidation, before the entry of the strip into the zinc bath.
  • an injection of oxidizing gas for the liquid and non-oxidizing metal for iron is carried out in said second zone of said horn.
  • This gas contains for example a mixture of H 2 O and H 2 , and / or of H 2 O and N 2 , and / or of CO 2 , CO, H 2 O, H 2 and / or O 2 .
  • the difference in oxidizing power, expressed in equivalent P (H 2 ) / P (H 2 O), between said first zone, non-oxidizing, and said second zone, oxidizing is at least a factor 8 , that is to say [P (H 2 ) / P (H 2 O)] oxidant x 8 ⁇ [P (H 2 ) / P (H 2 O)] non-oxidizing .
  • said first zone is reducing vis-à-vis the iron.
  • Figure 1 shows schematically a sectional view of an installation type trompe galvanizing steel, according to the state of the art.
  • Figure 2 schematically shows a sectional view of an installation type steel tubing horn, according to the present invention.
  • the steel strip 1 enters the molten zinc bath 5 at a horn 2 and changes direction, in order to exit the bath again, at the level
  • the atmosphere 7 in the horn 2 above the molten zinc bath 5 is oxidizing at least with respect to zinc, but not iron.
  • Clusters of zinc oxide 4 are formed at the level of the wetting line 6 on the inner surface of the horn 2.
  • Figure 2 shows the schematic galvanizing installation adapted to the features of the present invention.
  • the present invention relates to a device for producing a bell or horn 2 in two distinct sections by means of a separation zone 8, the atmospheres 9,10 respectively corresponding to the two sections, said zone 1 and zone 2, being of nature different.
  • Zone 1 corresponds to a non-oxidizing atmosphere 9
  • zone 2 corresponds to an oxidizing atmosphere 10 vis-a-vis liquid zinc.
  • the zone 2 has an injector 12 of oxidizing gas with typically a ratio H 2 / H 2 O, or equivalent (H 2 + CO) / (CO 2 + H 2 O), from 1 to 70, with an H 2 content ⁇ 1% by volume and a flow rate of between 5 and 50 Nm 3 / h.
  • injector 12 of oxidizing gas typically a ratio H 2 / H 2 O, or equivalent (H 2 + CO) / (CO 2 + H 2 O), from 1 to 70, with an H 2 content ⁇ 1% by volume and a flow rate of between 5 and 50 Nm 3 / h.
  • zone 2 is as short as possible.
  • Zone 2 has a length typically between 10 and 2000 mm and advantageously between 100 and 300 mm, in order to optimize the distribution of oxidizing gas over the width of the zone and to simultaneously minimize the oxidation time of the sheet.
  • the oxidation time of the substrate is typically 0.1 to 0.2 seconds.
  • the present invention thus makes it possible to obtain the oxidation of liquid zinc in zone 2 and at the same time to limit the oxidation time available for the sheet before entering the zinc bath, by the presence of a zone 1 non-oxidizing.
  • the invention consists in reducing to a minimum the zone in which the intentional oxidation of zinc is carried out in order to reduce the undesired available oxidation time for the alloying elements contained in the sheet metal. steel.
  • this reducing material makes it possible to limit as much as possible the adhesion of the boundary layer of the liquid metal to the tube, at the level of the wetting zone, by locally preventing the oxidation of zinc therein.

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  • 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)

Claims (6)

  1. Verfahren zum Feuerbeschichten eines Stahlblechs (1) durch Eintauchen in ein flüssiges Metallbad (5), das vorzugsweise mehr als 10% Zink enthält, unter Verwendung eines Einlaufs (2), der mindestens teilweise eine geregelte oxidierende Atmosphäre aufweist, dadurch gekennzeichnet, dass es die untenstehenden, aufeinander folgenden Schritte umfasst:
    - das Blech (1) durchläuft den Einlauf (2) bei einer ersten Zone (9), deren Atmosphäre, die wenigstens Wasserstoff und Wasserdampf enthält, für Eisen überhaupt nicht oxidierend ist, wobei die erste Zone (9) einen Wasserdampf-Teildruck P(H2O) < 264 ppm und ein Verhältnis der Teildrücke P(H2)/P(H2O) > 70 aufweist;
    - das Blech (1) durchläuft den Einlauf (2) bei einer zweiten Zone (10), deren Atmosphäre, die wenigstens Wasserstoff und Wasserdampf enthält, und eventuell auch CO2 und CO, für die Metallschmelze und die Legierungselemente des Stahls, der das besagte Blech bildet, oxidierend ist, wobei die zweite Zone (10) einen H2-Gehalt unter 1 Vol.-% aufweist und das Oxidationsvermögen des Gases in der zweiten Zone (10) dem Sauerstoff-Teildruck entspricht, der 1 < P(H2)/P(H2O) oder P(H2+CO)/P(H2O+CO2) < 70 entspricht.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der zweiten Zone (10) des besagten Einlaufs (2) das Einspritzen (12) eines für das flüssige Metall oxidierenden und für das Eisen nicht oxidierenden Gases durchgeführt wird.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das besagte oxidierende Gas eine Mischung aus H2O und H2 und/oder von H2O und N2 und/oder von CO2, CO, H2O, H2 und/oder O2 enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Differenz zwischen dem Oxidationsvermögen, ausgedrückt als Äquivalent P(H2)/P(H2O), zwischen der besagten ersten, nicht oxidierenden Zone (9) und der besagten zweiten, oxidierenden Zone (10) mindestens dem Faktor 8 entspricht, das heißt

            [P(H2)/P(H2O)]oxidierend x 8 < [P(H2)/P(H2O)]nicht oxidierend

  5. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass folgende Beziehung zwischen den Teildrücken der besagten ersten, nicht oxidierenden Zone (9) und der besagten zweiten, oxidierenden Zone (10) besteht:

            [P(H2+CO)/P(H2O+CO2)]oxidierend x 8 < [ P (H2+CO)/P(H2O+CO2)]nicht oxidierend

  6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die besagte erste Zone (9) für Eisen reduzierend wirkt.
EP01273287A 2001-01-17 2001-11-16 Verfahren zum verzinken von stahl Expired - Lifetime EP1358360B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01273287A EP1358360B1 (de) 2001-01-17 2001-11-16 Verfahren zum verzinken von stahl

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP01870009 2001-01-17
EP01870009A EP1225244A1 (de) 2001-01-17 2001-01-17 Verfahren zum Galvanisieren von Stahl
PCT/BE2001/000199 WO2002057504A1 (fr) 2001-01-17 2001-11-16 Procede de galvanisation de l'acier
EP01273287A EP1358360B1 (de) 2001-01-17 2001-11-16 Verfahren zum verzinken von stahl

Publications (2)

Publication Number Publication Date
EP1358360A1 EP1358360A1 (de) 2003-11-05
EP1358360B1 true EP1358360B1 (de) 2007-03-21

Family

ID=8184913

Family Applications (2)

Application Number Title Priority Date Filing Date
EP01870009A Withdrawn EP1225244A1 (de) 2001-01-17 2001-01-17 Verfahren zum Galvanisieren von Stahl
EP01273287A Expired - Lifetime EP1358360B1 (de) 2001-01-17 2001-11-16 Verfahren zum verzinken von stahl

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP01870009A Withdrawn EP1225244A1 (de) 2001-01-17 2001-01-17 Verfahren zum Galvanisieren von Stahl

Country Status (5)

Country Link
EP (2) EP1225244A1 (de)
AT (1) ATE357541T1 (de)
DE (1) DE60127456T2 (de)
ES (1) ES2283377T3 (de)
WO (1) WO2002057504A1 (de)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557953A (en) * 1984-07-30 1985-12-10 Armco Inc. Process for controlling snout zinc vapor in a hot dip zinc based coating on a ferrous base metal strip
DE3933244C1 (en) * 1989-10-05 1990-06-13 Hoesch Stahl Ag, 4600 Dortmund, De Continuous zinc coating appts. for coating metal strip - comprises melt alloy bath covered with hood having hydrogen, steam and inert gas atmos. and control system
JPH0649610A (ja) * 1992-07-29 1994-02-22 Kawasaki Steel Corp 溶融金属の連続めっき方法および装置
JPH06330271A (ja) * 1993-05-26 1994-11-29 Nippon Steel Corp 溶融亜鉛めっき鋼板の製造方法
JPH07145465A (ja) * 1993-11-24 1995-06-06 Nippon Steel Corp 溶融金属めっき方法及び装置
JP3437731B2 (ja) * 1996-11-27 2003-08-18 新日本製鐵株式会社 溶融めっきにおけるスナウト内生成異物の鋼板付着防止装置
FR2782326B1 (fr) * 1998-08-13 2000-09-15 Air Liquide Procede de galvanisation d'une bande metallique
JP2000290761A (ja) * 1999-04-06 2000-10-17 Nkk Corp 連続溶融金属めっき設備及びその使用方法

Also Published As

Publication number Publication date
EP1358360A1 (de) 2003-11-05
ATE357541T1 (de) 2007-04-15
EP1225244A1 (de) 2002-07-24
DE60127456D1 (de) 2007-05-03
WO2002057504A1 (fr) 2002-07-25
DE60127456T2 (de) 2007-12-06
ES2283377T3 (es) 2007-11-01

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