BE1004079A6 - Process for forming a coating zinc-aluminum strip steel. - Google Patents
Process for forming a coating zinc-aluminum strip steel. Download PDFInfo
- Publication number
- BE1004079A6 BE1004079A6 BE9000428A BE9000428A BE1004079A6 BE 1004079 A6 BE1004079 A6 BE 1004079A6 BE 9000428 A BE9000428 A BE 9000428A BE 9000428 A BE9000428 A BE 9000428A BE 1004079 A6 BE1004079 A6 BE 1004079A6
- Authority
- BE
- Belgium
- Prior art keywords
- zinc
- aluminum
- strip
- coating
- thin layer
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 17
- 239000010959 steel Substances 0.000 title claims abstract description 17
- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims abstract description 14
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 10
- 238000000576 coating method Methods 0.000 title description 22
- 239000011248 coating agent Substances 0.000 title description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000003618 dip coating Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
-
- 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
Abstract
On dépose par voie électrolytique sur la bande une couche mince d'un métal choisi parmi le nickel, le cobalt et le chrome et on fait passer la bande ainsi revêtue à travers un bain de zinc présentant une teneur en aluminium d'environ 55 % en poids. De préférence, on soumet la bande d'acier à un recuit sous une atmosphère protectrice après le dépôt de la couche mince précitée et avant le passage de la bande à travers le bain de zinc-aluminium.A thin layer of a metal chosen from nickel, cobalt and chromium is deposited on the strip electrolytically and the strip thus coated is passed through a zinc bath having an aluminum content of approximately 55%. weight. Preferably, the steel strip is subjected to annealing under a protective atmosphere after the deposition of the aforementioned thin layer and before the passage of the strip through the zinc-aluminum bath.
Description
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Procédé pour former un revêtement de zinc-aluminium sur une bande d'acier.
La présente invention concerne un procédé pour former un revêtement au trempé de zinc-aluminium sur une bande d'acier.
Le revêtement au trempé d'une bande d'acier en continu est une technique qui est connue et largement appliquée depuis de nombreuses années. Pour l'essentiel, elle consiste à faire défiler une bande d'acier dans un bain de métal ou d'alliage fondu, puis à solidifier le revêtement après avoir réglé son épaisseur. Généralement, l'opération de revêtement au trempé est précédée d'un recuit sous une atmosphère réductrice, afin de débarrasser la surface de la bande de toute trace d'oxyde pouvant compromettre l'adhérence du revêtement.
On utilise couramment dans ce cadre, des alliages de zinc-aluminium, contenant typiquement, en poids, outre le zinc, 55 % d'aluminium ainsi que 1,6 % de silicium. De tels alliages combinent la haute résistance à la corrosion de l'aluminium et la protection cathodique assurée par le zinc. L'addition de silicium a pour but de modérer la réaction entre le fer de la bande d'acier et l'aluminium du revêtement. En l'absence de silicium, cette réaction conduit en effet à une très importante perte en fer et à un revêtement complètement transformé en Fe-Al qui ne présente aucune adhérence.
Il est cependant apparu que ces revêtements de Zn-Al-Si présentent de graves défauts d'adhérence et de ductilité lorsque les articles revêtus sont soumis à des opérations de pliage ou de profilage, par exemple lors de la fabrication de panneaux destinés à la construction. Ces défauts conduisent à la fissuration du revêtement, les fissures formées pouvant quelquefois mener à l'écaillage et même à la pelade du revêtement.
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La fragilité et le manque d'adhérence de ces revêtements semblent provenir de trois causes principales.
En premier lieu, les revêtements présentent une structure, composée essentiellement d'un mélange métastable de deux phases qui ne se solidifient pas simultanément ; il apparaît ainsi des zones riches en aluminium et des zones riches en zinc, qui présentent des propriétés physiques distinctes et sont le siège de contraintes internes. De plus, il se forme à l'interface entre le substrat en acier et le revêtement de zinc-aluminium, une couche de particules intermétalliques fragiles qui dégradent l'adhérence. Enfin, le silicium ajouté pour modérer la réaction entre le fer et l'aluminium ne reste pas entièrement en solution ; au refroidissement, il précipite sous forme d'aiguilles qui sont à l'origine de concentrations de contraintes et entraînent la fragilité du revêtement.
On a déjà cherché à remédier à ces inconvénients au moyen de traitements thermiques spécifiques. On a notamment proposé d'effectuer un réchauffage de la bande revêtue à 300 - 350. C pendant 3 minutes, ou encore un recuit en bobine à 150*C pendant 24 heures. Ces traitements se sont avérés techniquement satisfaisants, mais non viables sur le plan économique en raison des charges qu'ils imposent.
La présente invention propose un procédé pour former un revêtement au trempé de zinc-aluminium sur une bande d'acier qui ne donne pas lieu aux inconvénients précités et qui permet, par des moyens simples et économiquement acceptables en fonctionnement industriel, de conférer à ce revêtement d'excellentes propriétés d'adhérence et de ductilité sans altérer son pouvoir de protection contre la corrosion.
Conformément à la présente invention, un procédé pour former un revêtement au trempé de zinc-aluminium sur une bande d'acier est caractérisé en ce que l'on dépose par voie électrolytique sur ladite bande, une couche mince d'un métal choisi parmi le nickel, le cobalt et le chrome, et en ce que l'on fait passer ladite bande ainsi revêtue à travers un bain de zinc présentant une teneur en
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aluminium d'environ 55 % en poids.
Suivant une mise en oeuvre particulière, on soumet ladite bande d'acier à un recuit sous une atmosphère protectrice après le dépôt de ladite couche mince et avant le passage de la bande à travers ledit bain de zinc-aluminium.
Suivant une caractéristique supplémentaire du procédé de l'invention, on opère le dépôt électrolytique de ladite couche mince avec une densité de courant d'au moins 300 A/dm2, et de préférence comprise entre 350 et 450 A/dm2.
La couche mince de métal a notamment pour effet de freiner ou d'empêcher les échanges entre le substrat en acier d'une part et le revêtement de zinc-aluminium d'autre part. Elle atténue ainsi la réaction entre le fer du substrat et l'aluminium du revêtement et contribue à améliorer l'adhérence de ce dernier. En outre, elle permet d'éviter la présence de silicium dans le bain de zincaluminium ; le revêtement de zinc-aluminium ne comporte donc plus de précipités de silicium fragilisants et sa ductilité s'en trouve nettement améliorée.
A titre d'exemple, on a déposé du nickel en couche mince, correspondant à environ 3 g Ni/m2 en double face, sur des panneaux en acier. On a utilisé à cet effet une solution électrolytique à 260 g/l de NiS04. 6H20 et 35 g/l de H3B03'dont le pH a été ajusté à 2,5 par addition d'acide sulfurique. La densité de courant était de 330 A/dm2. Les panneaux ont ensuite subi un recuit à 720. C sous une atmosphère de N2 - 5 % H2 pendant 3 minutes, puis ils ont été revêtus par immersion dans un bain de zinc contenant 55 % en poids d'aluminium et pas de silicium.
L'analyse des revêtements obtenus montre que le nickel ne joue pas uniquement un rôle de barrière entre l'acier et le revêtement. Les couches les plus intérieures de la zone de réaction, c'est-à-dire du côté de l'acier, sont essentiellement constituées de Fe-Al, avec de très faibles pourcentages de nickel et de zinc. En se déplaçant
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vers l'extérieur, on rencontre alors des couches à base d'aluminium enrichies en nickel et en zinc, avec une teneur en fer très faible.
Le revêtement proprement dit, c'est-à-dire la couche extérieure, est constituée de deux phases principales, respectivement enrichies en aluminium et en zinc, qui contiennent encore des traces de fer.
Par endroits, le revêtement présente en outre des particules très riches en nickel.
Cette structure résiste très bien à la flexion à 180'sur deux fois l'épaisseur du panneau, ainsi qu'au profilage, sans fissuration notable ni écaillage.
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Process for forming a zinc-aluminum coating on a steel strip.
The present invention relates to a method for forming a zinc-aluminum dip coating on a steel strip.
The dip coating of a continuous steel strip is a technique which has been known and widely applied for many years. Essentially, it consists of running a strip of steel through a bath of molten metal or alloy, then solidifying the coating after adjusting its thickness. Generally, the dip coating operation is preceded by annealing in a reducing atmosphere, in order to rid the surface of the strip of any trace of oxide which may compromise the adhesion of the coating.
In this context, zinc-aluminum alloys are commonly used, typically containing, by weight, in addition to zinc, 55% of aluminum as well as 1.6% of silicon. Such alloys combine the high corrosion resistance of aluminum and the cathodic protection provided by zinc. The purpose of the addition of silicon is to moderate the reaction between the iron of the steel strip and the aluminum of the coating. In the absence of silicon, this reaction leads in fact to a very significant loss of iron and to a coating completely transformed into Fe-Al which has no adhesion.
However, it has appeared that these Zn-Al-Si coatings have serious adhesion and ductility defects when the coated articles are subjected to bending or profiling operations, for example during the manufacture of panels intended for construction. . These defects lead to cracking of the coating, the cracks formed can sometimes lead to chipping and even to the coating of the coating.
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The fragility and lack of adhesion of these coatings appear to stem from three main causes.
First, the coatings have a structure, essentially composed of a metastable mixture of two phases which do not solidify simultaneously; zones rich in aluminum and zones rich in zinc appear, which have distinct physical properties and are the seat of internal stresses. In addition, a layer of fragile intermetallic particles is formed at the interface between the steel substrate and the zinc-aluminum coating, which degrades adhesion. Finally, the silicon added to moderate the reaction between iron and aluminum does not remain entirely in solution; on cooling, it precipitates in the form of needles which are the source of stress concentrations and cause the fragility of the coating.
We have already sought to remedy these drawbacks by means of specific heat treatments. In particular, it has been proposed to reheat the coated strip at 300-350 ° C. for 3 minutes, or else coil annealing at 150 ° C. for 24 hours. These treatments have proven to be technically satisfactory, but not economically viable because of the costs they impose.
The present invention provides a process for forming a zinc-aluminum dip coating on a steel strip which does not give rise to the aforementioned drawbacks and which allows, by simple and economically acceptable means in industrial operation, to give this coating excellent adhesion and ductility properties without impairing its corrosion protection power.
According to the present invention, a method for forming a zinc-aluminum dip coating on a steel strip is characterized in that an thin layer of a metal chosen from the nickel, cobalt and chromium, and in that said strip thus coated is passed through a zinc bath having a content of
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aluminum about 55% by weight.
According to a particular implementation, said steel strip is subjected to annealing under a protective atmosphere after the deposition of said thin layer and before the passage of the strip through said zinc-aluminum bath.
According to an additional characteristic of the method of the invention, the electrolytic deposition of said thin layer is carried out with a current density of at least 300 A / dm2, and preferably between 350 and 450 A / dm2.
The thin layer of metal has in particular the effect of slowing down or preventing the exchanges between the steel substrate on the one hand and the zinc-aluminum coating on the other hand. It thus attenuates the reaction between the iron of the substrate and the aluminum of the coating and contributes to improving the adhesion of the latter. In addition, it avoids the presence of silicon in the zincaluminium bath; the zinc-aluminum coating therefore no longer contains embrittling silicon precipitates and its ductility is markedly improved.
For example, nickel was deposited in a thin layer, corresponding to approximately 3 g Ni / m2 in double face, on steel panels. An electrolytic solution containing 260 g / l of NiSO 4 was used for this purpose. 6H20 and 35 g / l of H3B03 ', the pH of which was adjusted to 2.5 by addition of sulfuric acid. The current density was 330 A / dm2. The panels were then annealed at 720 ° C. under an atmosphere of N2 - 5% H2 for 3 minutes, then they were coated by immersion in a zinc bath containing 55% by weight of aluminum and not of silicon.
Analysis of the coatings obtained shows that nickel does not only act as a barrier between the steel and the coating. The innermost layers of the reaction zone, i.e. on the steel side, are essentially made of Fe-Al, with very low percentages of nickel and zinc. By moving
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outwards, we then come across aluminum-based layers enriched in nickel and zinc, with a very low iron content.
The actual coating, that is to say the outer layer, consists of two main phases, respectively enriched with aluminum and zinc, which still contain traces of iron.
In places, the coating also has particles very rich in nickel.
This structure is very resistant to bending at 180 ur twice the thickness of the panel, as well as to profiling, without significant cracking or chipping.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9000428A BE1004079A6 (en) | 1990-04-17 | 1990-04-17 | Process for forming a coating zinc-aluminum strip steel. |
| EP91870059A EP0453432B1 (en) | 1990-04-17 | 1991-04-12 | A method of forming a zinc-aluminium coating on a steel strip |
| DE69105340T DE69105340D1 (en) | 1990-04-17 | 1991-04-12 | Process for forming a zinc-aluminum coating on a steel strip. |
| AT91870059T ATE114739T1 (en) | 1990-04-17 | 1991-04-12 | PROCESS FOR FORMING A ZINC-ALUMINUM COATING ON A STEEL STRIP. |
| JP3176277A JPH0726357A (en) | 1990-04-17 | 1991-04-15 | Formation of zinc-aluminum coating on band steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9000428A BE1004079A6 (en) | 1990-04-17 | 1990-04-17 | Process for forming a coating zinc-aluminum strip steel. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE1004079A6 true BE1004079A6 (en) | 1992-09-22 |
Family
ID=3884763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE9000428A BE1004079A6 (en) | 1990-04-17 | 1990-04-17 | Process for forming a coating zinc-aluminum strip steel. |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0453432B1 (en) |
| JP (1) | JPH0726357A (en) |
| AT (1) | ATE114739T1 (en) |
| BE (1) | BE1004079A6 (en) |
| DE (1) | DE69105340D1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1521824A (en) * | 1966-05-04 | 1968-04-19 | M & T Chemicals Inc | Process for depositing chromium on metal strips |
| SE393403B (en) * | 1972-08-09 | 1977-05-09 | Bethlehem Steel Corp | WAY TO COVER THE SURFACE OF AN IRON STRING WITH AN AL-ZN ALLOY |
| SE378118B (en) * | 1974-03-14 | 1975-08-18 | Nordstjernan Rederi Ab |
-
1990
- 1990-04-17 BE BE9000428A patent/BE1004079A6/en not_active IP Right Cessation
-
1991
- 1991-04-12 AT AT91870059T patent/ATE114739T1/en not_active IP Right Cessation
- 1991-04-12 EP EP91870059A patent/EP0453432B1/en not_active Expired - Lifetime
- 1991-04-12 DE DE69105340T patent/DE69105340D1/en not_active Expired - Lifetime
- 1991-04-15 JP JP3176277A patent/JPH0726357A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0453432A1 (en) | 1991-10-23 |
| ATE114739T1 (en) | 1994-12-15 |
| EP0453432B1 (en) | 1994-11-30 |
| DE69105340D1 (en) | 1995-01-12 |
| JPH0726357A (en) | 1995-01-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RE | Patent lapsed |
Owner name: CENTRE DE RECHERCHES METALLURGIQUES - CENTRUM VOO Effective date: 19950430 |