EP0848076B1 - Verfahren zur Heisstauch-Beschichtung einer Stahlplatte; galvanisierte oder aluminisierte Stahlplatte so hergestellt - Google Patents

Verfahren zur Heisstauch-Beschichtung einer Stahlplatte; galvanisierte oder aluminisierte Stahlplatte so hergestellt Download PDF

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Publication number
EP0848076B1
EP0848076B1 EP97402985A EP97402985A EP0848076B1 EP 0848076 B1 EP0848076 B1 EP 0848076B1 EP 97402985 A EP97402985 A EP 97402985A EP 97402985 A EP97402985 A EP 97402985A EP 0848076 B1 EP0848076 B1 EP 0848076B1
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EP
European Patent Office
Prior art keywords
coating
iron
layer
sheet
metal
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Expired - Lifetime
Application number
EP97402985A
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English (en)
French (fr)
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EP0848076A1 (de
Inventor
Philippe Guesdon
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Sollac SA
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Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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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
    • 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
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection

Definitions

  • the coating conditions in particular the recrystallization heat treatment atmosphere and the nature of the bath, are therefore best suited to the formation and wetting of a surface of pure iron.
  • the disadvantage of dipping steel sheet coating processes is that the coating conditions must be adapted to the type of steel grade to to coat, in particular according to the nature and the proportion of the elements addition it contains, to obtain a wettable surface and a coating adherent.
  • the addition, in the bath, of an alloying inhibitor such as aluminum, makes it possible to limit the interfacial layer (here: Fe 2 Al 5 ) to a very small thickness, generally less than 0.01 ⁇ m.
  • the object of the invention is, on a dip coating line, to avoid to have to significantly modify the coating conditions according to the nuances steel to be coated.
  • the object of the invention is also, in particular in the case of aluminizing, to make more resistant and / or higher-grade coatings by dipping in aluminium.
  • the function of the first sublayer is essentially a function "Barrier” or “anti-ally” between the elements of the substrate, in particular the iron, and those of the metallic coating, such as generally zinc and / or aluminum; as such, the first underlay plays a role comparable to that of silicon in an aluminum bath, or that of aluminum in a zinc bath, that is to say a role of inhibition of the alliance with the substrate.
  • this first underlay must therefore be sufficient high to form a barrier to the diffusion of the elements of the sheet metal substrate towards its surface, but must remain sufficiently small (less than or equal to 0.1 ⁇ m) to avoid risks of flaking of the coated sheet (for example flaking after folding).
  • the function of the second sublayer is essentially a function "wetting" in the coating bath; the nature of this second underlay must therefore be adapted to that of the bath; if necessary, a second function of this second sublayer is to provide a “Resource” or controlled quantity of elements of addition and of alloying coating applied by dipping.
  • this first undercoat is applied before the annealing heat treatment step, its function is also to limit diffusion towards the surface of the elements of addition of steel, where some of them may oxidize in the annealing atmosphere.
  • the continuous coating installation includes, from upstream to downstream, cleaning means, means for depositing a first undercoat thin oxide, means for depositing a second thin sublayer metal, heat treatment means, quenching means, means for wringing and regulating thickness and means for solidification.
  • the coating installation also includes means for making continuously scroll the sheet metal strip to be coated in the installation.
  • the means for depositing a first sub-layer and the means for deposition of a second sub-layer can be for example means of vacuum deposition, electrodeposition deposition means, or means chemical vapor deposition.
  • the first embodiment of the invention relates to galvanization without alloy: we will therefore use a zinc bath with aluminum additive at more than 0.15% to inhibit the iron-zinc alloy in a conventional manner.
  • Zinc-based coating called non-alloy galvanizing, the average iron content remains below about 1%, while being higher than that of iron in the bath (which is generally 0.03% in weight).
  • the sheet to be coated therefore runs through the coating installation using the scrolling means.
  • the sheet metal surface to be coated is cleaned, for example by passing through an open flame.
  • a oxide underlay of average thickness between 0.01 and 0.1 ⁇ m.
  • this underlay must be high enough to form a barrier to the diffusion of the elements of addition of the steel from the sheet to its surface, but sufficiently small (less than or equal to 0.1 ⁇ m) to avoid risks of flaking of the coated sheet (for example when bending).
  • this first sub-layer is adapted to provide one or more oxides as stable as possible under the conditions of the stages following of the process.
  • the nature of the first sub-layer is oxide of chromium (trivalent) or zirconium oxide.
  • this second sub-layer is, in the present case of non-alloy coating, adapted to provide the iron resources which will be necessary, at the time of quenching, to form a conventional inhibition layer of the Fe 2 Al 5 type. ; as this inhibition layer which forms on soaking is always very thin, a thickness of less than 0.5 ⁇ m of iron for this second sub-layer will always in practice provide a sufficient resource.
  • this second sub-layer must, conversely, remain low enough to prevent the formation of iron-zinc alloy in quantity significant, which would risk dispersing in the thickness of the coating layer and deteriorate its properties.
  • the surface obtained has good wettability thanks to the second underlay, external, of metallic iron.
  • this preliminary surface preparation is that it can be fixed thus a “universal” surface identical for all steel grades to coating in the same installation, and that we can then use the same dip coating conditions (annealing atmosphere, temperature soaking bath etc.) for all these steel grades (for one type of coating given).
  • the procedure is a conventional, known in itself: heat annealing treatment of recrystallization, quenching, spinning to regulate the thickness deposited and finally solidification of the coating.
  • the first and second sublayers have been applied before the annealing heat treatment, the first undercoat prevents the diffusion towards the surface of the elements of addition of steel and their oxidation at vicinity of this surface.
  • the first and second sub-layers after the annealing heat treatment step are advantageous because a deterioration of the "bi-layer is avoided "By heat treatment, the risk is all the greater as this" bi-layer Is thick, as is generally the case with alloy coatings described below.
  • the "barrier" function of the first undercoat makes it possible to avoid, during tempering, the formation of "outburst” (in English) or alloy growths in the substrate-coating interface.
  • the second embodiment of the invention relates to galvanization with ally; for this purpose, a zinc bath will be conventionally used aluminum additive less than 0.15% (or without aluminum); installation then comprises, downstream, conventional heat treatment means of alliance.
  • the thickness of the first sub-layer (oxide) must also be high enough to form a barrier to diffusion iron from the substrate in the coating, at processing temperatures thermal alloy (conventionally around 500 ° C in the case of zinc coatings) which are generally lower than temperatures annealing (conventionally around 800 ° C).
  • the structure of an alloyed galvanized coating is laminated in several superimposed sublayers of different iron-zinc alloy phases, richer in zinc from the surface, richer in iron from the substrate-coating interface.
  • Alloyed galvanized coating taken as a whole generally an average iron content of between 8 and 14% by weight.
  • the invention in particular to the first oxide sublayer, can now adapt in a manner known per se the conditions of the alloy heat treatment to obtain an alloyed galvanized coating whose structure is no longer stratified into several different phases of alloys iron-zinc; a coating is then obtained which no longer contains, essentially, only one alloy phase in its thickness.
  • the thickness of this layer is generally greater than 6 ⁇ m.
  • the structure of the coating layer is therefore homogeneous in its thickness ; the phase which mainly constitutes it may obviously contain impurities or inclusions.
  • alloyed galvanized sheets according to the invention have properties different depending on the nature of this phase; depending on the case, we thus obtain a very good resistance to dusting, or very good resistance to flaking, or very good hardness, or even other known properties attached to the phase considered.
  • the nature of the coating can easily be adapted galvanized alloy depending on the use of the sheet.
  • the third embodiment of the invention relates to galvanization without alloying using a zinc bath with aluminum additive at less than 0.15%, that is to say a zinc bath normally used in the prior art for the coating of zinc alloy coating.
  • the thickness of this second sublayer is less than 0.5 ⁇ m.
  • An advantage of the invention is therefore to be able to use the same types baths for non-alloy coatings and for alloy coatings.
  • the invention therefore makes it possible to facilitate the management of the metal baths of coating.
  • the fourth embodiment of the invention relates to aluminization "Without alliances": a bath will therefore be used in a conventional manner of aluminum containing more than 6% of silicon to limit the alloy at the interface steel-coating.
  • a non-alloyed aluminization is a coating based on aluminum with an average iron content of around 10%, while being higher than that of iron in the bath (which is generally around 3% in weight).
  • the sheet metal surface to be coated is cleaned and then the treatment is carried out thermal annealing, as for a conventional aluminizing operation.
  • an oxide undercoat of medium thickness is deposited between 0.01 and 0.1 ⁇ m and previously adapted to the barrier function described.
  • the nature of the first sub-layer is oxide of chromium (trivalent) or zirconium oxide.
  • the deposition means of the second sub-layer it is deposited then a sub-layer of a phase of an alloy of iron and aluminum which, at solid state, is likely to be in equilibrium with the coating bath to liquid state.
  • the parameters that define this balance and, therefore, said phase and its composition include the bath temperature during the soaking step and the composition of the bath, which in practice is saturated with iron.
  • the silicon content of the bath being greater than 6%, preferably said alloy of iron and aluminum corresponds to the so-called ⁇ 5 phase or to the so-called phase ⁇ 6 which are alloys of aluminum, iron and silicon.
  • the ⁇ 5 phase has a hexagonal structure; it is sometimes called ⁇ H or H; the iron content of this phase is generally between 29 and 36% by weight; the silicon content of this phase is generally between 6 and 12% by weight; the balance consists mainly of aluminum.
  • the ⁇ 6 phase has a monoclinic structure; it is sometimes called ⁇ or M; the iron content of this phase is generally between 26 and 29% in weight ; the silicon content of this phase is generally between 13 and 16% by weight; the balance consists mainly of aluminum.
  • this second sub-layer is, in the present case of non-alloy coating, suitable for providing good adhesion to the layer of aluminum to be applied by dipping.
  • the procedure is a classic, known in itself: soaked in the coating bath, spin to regulate the thickness deposited and finally solidification of the coating.
  • a steel sheet coated with an aluminum-silicon alloy is then obtained. comparable to those of the prior art with, at the process level, the advantages identical to those previously described, in particular those of the first embodiment.
  • the interfacial layer is considered fragile; this drawback results in the appearance of cracks in the coating when the sheet is bent; the addition of more than 6% of silicon in the bath is generally intended to limit the thickness of this interfacial layer to a value of the order of 3 ⁇ m.
  • This surface layer contains for example of the order of 3% by weight of iron, of the order of 9% by weight of silicon, the rest being essentially made of aluminum; this layer therefore generally comprises phase inclusions based on silicon or aluminum alloy, iron and silicon; it seems that the presence of these phases leads to a weakening of this surface layer and a decrease in corrosion protection.
  • the thickness of the second sub-layer according to the invention is weak, in particular less than 0.5 ⁇ m
  • a coating is obtained whose interfacial layer of iron-aluminum-silicon alloy has a thickness less than that encountered in aluminized sheets at quenched from the prior art, in particular less than 1 ⁇ m.
  • the total thickness of the metal layer is more than 6 ⁇ m.
  • the aluminum content of the surface layer depends on the content of aluminum in the coating bath; it is generally greater than 80%; it is commonly of the order of 87% by weight.
  • the average iron content of the coating (which takes into account the iron contained in the interfacial layer) is then much less than 10% in weight; it is then less than or equal to 6% by weight.
  • aluminized sheets according to the invention having the structure previously described using a bath aluminum with a silicon content of less than 6%, i.e. a bath - pondered to lead to alloyed aluminum coatings.
  • the coating bath contains little or no of an alloying inhibitor, such as silicon, a sheet coated with a aluminum-based layer with an interfacial alloy layer yet a small thickness.
  • an alloying inhibitor such as silicon
  • the two sublayers according to the invention therefore serve as an inhibitor to replace the silicon in the bath.
  • the surface layer of the coating then contains much less of inclusions of the phases mentioned above, which improves the resistance to coating cracking and corrosion protection.
  • the following example illustrates the first embodiment of the invention:
  • the first is deposited and the second vacuum sublayers by magnetron sputtering.
  • First sublayer Cr2O3 - thicknesses: a test at 30 nm and a test at 50 nm.
  • Second undercoat pure iron - thicknesses: a test at 30 nm and a test at 50 nm.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)

Claims (17)

  1. Verfahren zur metallischen Beschichtung eines Stahlbleches, bei dem:
    die Oberfläche des zu beschichtenden Bleches gereinigt wird,
    eine thermische Glühbehandlung des gereinigten Bleches durchgeführt wird,
    das behandelte Blech in ein Flüssigbad aus dem Beschichtungsmetall eingetaucht wird,
    das Blech anschliessend aus dem Bad genommen wird und
    eine Erstarrung der vom Blech aus dem Bad mitgenommenen metallischen Beschichtung vorgenommen wird,
    dadurch gekennzeichnet, dass nach dem Reinigungsvorgang und vor dem Tauchvorgang:
    auf der Oberfläche eine erste Unterschicht aufgebracht wird auf Basis wenigstens eines Oxyds, deren mittlere Dicke zwischen 0,01 und 0,1 µm liegt und
    anschliessend auf die erste Unterschicht eine zweite metallische Unterschicht aufgebracht wird, die mindestens 20 Gewichtsprozent Eisen enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass diese erste Unterschicht und diese zweite Unterschicht nach dem Glühvorgang aufgebracht werden.
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass der Stahl ein legierter oder mikrolegierter Stahl ist, der Legierungselemente enthält, die bei den Bedingungen der thermischen Glühbehandlung oxydierbar sind, insbesondere Silizium.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die erste Unterschicht eine Schicht auf Basis eines dreiwertigen Chromoxyds oder eines Zirkonoxyds ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass:
    das Beschichtungsmetall ein Metall auf Basis Zink ist
    die zweite metallische Unterschicht eine Schicht auf Basis Eisen ist.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass:
    das Beschichtungsmetall ein Metall auf Basis Aluminium ist
    die zweite metallische Unterschicht eine Schicht auf Basis einer Legierung aus Eisen und Aluminium ist, die sich im Gleichgewicht mit dem mit Eisen gesättigten Bad befindet.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass:
    der Gehalt an Silizium im Bad geringer als 6% ist,
    die Legierung aus Eisen und Aluminium der Zusammensetzung FeAl3 entspricht.
  8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass
    der Gehalt an Silizium im Bad grösser als 6% ist
    die Legierung aus Eisen und Aluminium ausserdem Silizium enthält und einen Aufbau entsprechend einer sogenannten τ5-Phase oder einer sogenannten τ6-Phase aufweist.
  9. Verfahren nach einem der vorhergehenden Ansprüche zur Herstellung einer nicht mit Eisen legierten Beschichtung, dadurch gekennzeichnet, dass die mittlere Dicke der aufgebrachten zweiten Unterschicht kleiner als 0,5 µm ist.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das Beschichtungsmetall ein Metall auf Basis Zink ist, wobei der Gehalt an Aluminium im Metallbad kleiner als 0,15% ist.
  11. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass, wenn das Beschichtungsmetall ein Metall auf Basis Aluminium ist, der Gehalt an Silizium im Metallbad kleiner als 6% ist.
  12. Verfahren nach einem der Ansprüche 1 bis 8 zur Herstellung einer mit Eisen legierten Beschichtung, die eine vorgegebene Menge an Eisen enthält, dadurch gekennzeichnet, dass :
    die Dicke der zweiten Unterschicht derart gewählt wird, dass diese Menge an Eisen für die Beschichtung zur Verfügung steht
    nach dem Herausnehmen des Bleches aus dem Bad eine thermische Behandlung der Legierungsbildung unter derartigen Bedingungen vorgenommen wird, dass das in der zweiten Unterschicht enthaltene Eisen eine Legierung bildet mit der vom Blech mitgenommenen metallischen Beschichtung.
  13. Stahlblech, das mit einer metallischen Schicht auf Basis einer Legierung aus Eisen und Zink beschichtet ist, die durch ein Tauchverfahren aufgebracht ist und das durch ein Verfahren nach 12 hergestellt worden ist, dadurch gekennzeichnet, dass diese Schicht über ihre Dicke homogen ist und im wesentlichen aus einer einzigen Phase einer Eisen - Zink - Legierung besteht.
  14. Stahlblech, das mit einer metallischen Schicht auf Basis Aluminium beschichtet ist, die durch ein Tauchverfahren aufgebracht ist und das durch ein Verfahren nach einem der Ansprüche 6 bis 8 und 9 bis 11 hergestellt worden ist, die von einem der Ansprüche 6 bis 8 abhängen, wobei diese Schicht geschichtet ist und eine Übergangsflächenschicht aufweist, die im wesentlichen aus einer oder mehreren Legierungen auf Basis Eisen und Aluminium besteht, dadurch gekennzeichnet, dass die Dicke dieser Übergangsflächenschicht kleiner als 1 µm ist.
  15. Blech nach Anspruch 14, dessen geschichtete metallische Schicht ausserdem eine Oberflächenschicht aufweist, dadurch gekennzeichnet, dass der Gehalt an Aluminium in dieser Oberflächenschicht grösser als oder gleich 90% ist.
  16. Blech nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, dass es eine Unterschicht auf Basis wenigstens eines Oxyds aufweist, die zwischen dem Substrat aus Stahl und der Beschichtung angeordnet ist und deren mittlere Dicke zwischen 0,01 und 0,1 µm liegt.
  17. Blech nach einem der Ansprüche 13 bis 16, dadurch gekennzeichnet, dass die Dicker dieser metallischen Schicht grösser als 6 µm ist.
EP97402985A 1996-12-11 1997-12-10 Verfahren zur Heisstauch-Beschichtung einer Stahlplatte; galvanisierte oder aluminisierte Stahlplatte so hergestellt Expired - Lifetime EP0848076B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9615195A FR2756846B1 (fr) 1996-12-11 1996-12-11 Procede de revetement au trempe d'une tole d'acier
FR9615195 1996-12-11

Publications (2)

Publication Number Publication Date
EP0848076A1 EP0848076A1 (de) 1998-06-17
EP0848076B1 true EP0848076B1 (de) 2001-08-22

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EP97402985A Expired - Lifetime EP0848076B1 (de) 1996-12-11 1997-12-10 Verfahren zur Heisstauch-Beschichtung einer Stahlplatte; galvanisierte oder aluminisierte Stahlplatte so hergestellt

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EP (1) EP0848076B1 (de)
AT (1) ATE204614T1 (de)
DE (1) DE69706269T2 (de)
DK (1) DK0848076T3 (de)
ES (1) ES2162220T3 (de)
FR (1) FR2756846B1 (de)
PT (1) PT848076E (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2312011A1 (de) 2009-10-15 2011-04-20 Georg Fischer Automotive AG Verfahren zur metallischen Beschichtung eines Gussformteiles und aluminisiertes Gussformteil hergestellt durch das Verfahren

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU60512A1 (de) * 1970-03-11 1971-11-08
DE3150998C2 (de) * 1981-12-23 1984-06-20 Peri-Werk Artur Schwörer GmbH & Co KG, 7912 Weißenhorn Verfahren zum Feuerverzinken und zum Feuerverzinken bestimmtes Teil
JPS61194186A (ja) * 1985-02-25 1986-08-28 Nippon Steel Corp 複合鋼管の製造方法
JPS61243162A (ja) * 1985-04-19 1986-10-29 Nippon Steel Corp 耐熱性に優れたＡｌ系溶融メツキ鋼板の製造法
JP2769350B2 (ja) * 1989-03-28 1998-06-25 新日本製鐵株式会社 溶融めっき鋼板の製造方法
JPH05132747A (ja) * 1991-11-12 1993-05-28 Kawasaki Steel Corp 溶融Ｚｎめつきクロム含有鋼板の製造方法

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PT848076E (pt) 2002-01-30
ATE204614T1 (de) 2001-09-15
FR2756846B1 (fr) 1999-01-08
FR2756846A1 (fr) 1998-06-12
ES2162220T3 (es) 2001-12-16
EP0848076A1 (de) 1998-06-17
DE69706269D1 (de) 2001-09-27
DE69706269T2 (de) 2002-05-08
DK0848076T3 (da) 2001-11-12

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