EP1072689A1 - Procédé de fabrication de bandes minces en acier de type "TRIP" , et bandes minces ainsi obtenues - Google Patents
Procédé de fabrication de bandes minces en acier de type "TRIP" , et bandes minces ainsi obtenues Download PDFInfo
- Publication number
- EP1072689A1 EP1072689A1 EP00402035A EP00402035A EP1072689A1 EP 1072689 A1 EP1072689 A1 EP 1072689A1 EP 00402035 A EP00402035 A EP 00402035A EP 00402035 A EP00402035 A EP 00402035A EP 1072689 A1 EP1072689 A1 EP 1072689A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- strip
- steel
- cooling
- less
- trip
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/021—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular fabrication or treatment of ingot or slab
- C21D8/0215—Rapid solidification; Thin strip casting
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/20—Isothermal quenching, e.g. bainitic hardening
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
Definitions
- the invention relates to the continuous casting of thin steel strips. More in particular, it relates to the manufacture of thin steel strips of the “TRIP” type directly from liquid metal.
- TRIP Transformation Induced Plasticity
- steels which simultaneously have a very high strength and high ductility, which makes them particularly suitable for laying form. These properties are obtained thanks to their particular microscopic structure. They have, in fact, within a ferritic matrix, a hard phase of bainite and / or martensite, as well as residual austenite representing 5 to 20% of the structure.
- the TRIP steel sheets are usually obtained by either continuous casting from slabs - hot rolling (the shortest route, therefore the most economical, but which provides relatively thick products), either by continuous casting slabs - hot rolling - cold rolling - annealing (used for products of low thickness).
- the bainite stabilizes the austenite.
- the object of the invention is to make possible the reliable production of steel strips High quality TRIP through a short manufacturing chain, i.e. not including cold rolling and annealing step.
- the subject of the invention is also a thin steel strip of the “TRIP” type, likely to be obtained by the above process.
- a first essential aspect of the invention is the use of a continuous casting process of steel in thin strips directly to from liquid metal, instead of a conventional slab casting process intended to be hot rolled on a strip train.
- the strip thus produced is subjected to hot rolling online and then cooling which brings it into the temperature range where the bainitic transformation occurs. It’s only after this transformation occurred and the desired microstructure, typical of TRIP steels, was obtained that a second cooling takes place which interrupts the transformation, and brings the strip its winding temperature. This is located at a lower value than that of hot rolled strips produced by the conventional process, since the transformation bainitique has already taken place, and that an extended stay of the wound strip in the range of temperatures where this transformation took place could lead to an evolution undesirable microstructure.
- the continuous casting of thin strips directly from liquid metal is a technique which has been tested for several years for the casting of carbon steels, stainless steels and other ferrous alloys, but has never been used before for the production of TRIP type steels.
- the most commonly used technique in casting thin strips of ferrous alloys which is reaching the stage industrial, is the technique called "casting between cylinders", according to which we introduce liquid metal between two close cylinders with horizontal axes, rotated in direction reverse and internally cooled. The pouring space is closed laterally by refractory plates applied against the flat side faces of the cylinders.
- “Skins” of solidified metal are formed on each of the cylinders, and meet at the level the neck (the area where the gap between the cylindrical side surfaces of the cylinders is greatest low and corresponds substantially to the desired thickness for the strip) to form a solidified strip.
- the strip Before being wound, the strip can then undergo various treatments thermal and / or thermomechanical such as one or more hot rolling, cooling, reheating ... It is a particular set of such treatments which constitutes one of the essential elements of the invention.
- a steel is cast, the composition of which is defined as follows (all percentages are weight percentages).
- Its carbon content is between 0.05 and 0.25%.
- the lower limit is required by the stabilization of the residual austenite, which takes place during cooling of the strip by rejection of carbon from the ferritic phase in the phase austenitic. Above 0.25%, it is considered that the strip will no longer have a weldability sufficient for the usual applications of TRIP steels.
- Manganese content is between 0.5 and 3%.
- Manganese has for functions to stabilize austenite (it is a gamma element) and to harden steel. In below 0.5%, these effects are not sufficiently marked. Above 3%, the effect gammagen becomes too important to guarantee the formation of a ferritic matrix, and more manganese segregates exaggeratedly, which degrades the properties tape mechanics.
- Manganese can be partially substituted by copper and / or nickel which also have gamma effects.
- the copper added specifically allows hardening by precipitation.
- the copper being insoluble in cementite, it allows like silicon and aluminum to obtain a beneficial effect for the residual austenite.
- the conditions of rapid cooling imposed by the casting of thin strips makes it possible to avoid problems of degradation of the surface condition of the product which dissuade from making this addition of copper in TRIP steels produced by conventional processes.
- the total of its silicon and aluminum contents is between 0.1 and 4%. These elements prevent precipitation of cementite in austenite and promote formation high temperature ferrite. Compared to the silicon contents usually encountered on TRIP steels (from 0.2 to 1.5%), it will be noted that the process according to the invention may authorize higher contents, for reasons and under conditions which will be seen later.
- the cumulative content of phosphorus, tin, arsenic, antimony must not exceed 0.3%, to limit the fragility of the products, and preferably the phosphorus content does not not exceed 0.05%.
- titanium, niobium, vanadium, zirconium or rare earths in contents the sum of which does not exceed 0.3%.
- These elements form carbides, nitrides or carbonitrides that block the growth of grains at high temperature and increase the resistance by the precipitation effect.
- the other elements present in the steel are those which one expects usually to be found as impurities resulting from processing, in proportions which do not have a significant influence on the properties sought for steels TRIP.
- Liquid metal whose composition meets the criteria set out above is cast on a casting installation between cylinders, so as to continuously form a solidified strip whose thickness can range from 0.5 to 10 mm and more conventionally range from 1 at 5 mm.
- the strip preferably crosses an inerting zone, such as that a sealed enclosure, inside which is maintained in the vicinity of the strip a non-oxidizing atmosphere for the metal, thanks to an insufflation of a neutral gas (nitrogen or argon) lowering the oxygen content to a very low level.
- a neutral gas nitrogen or argon
- the purpose of this blanketing is to avoid, or at least significantly limit, the scale formation on the surface of the strip, the presence of which during the step of hot rolling which will follow, would lead to the appearance of defects such as scale inlays on the surface of the strip.
- the inerting device can be replaced or supplemented by a device ensuring the removal of the scale formed, by example a set of rotating brushes.
- the strip After it has been poured, and after having passed through any inerting zone, the strip is then hot-rolled in line, in known manner, to give it a thickness generally between 1 and 3 mm.
- This rolling must be carried out in the austenitic domain, therefore at a temperature higher than the temperature Ar 3 of the cast grade. It is carried out with a total reduction rate of between 25 and 70%.
- the role of this inline hot rolling is twofold. It must first close the porosities which may have formed at the heart of the strip during its solidification. Above all, it must "break" the microstructure resulting from solidification, so as to refine it and make it possible to obtain the desired final microstructure.
- This hot rolling can take place in one or more passes, that is to say by passing the strip through a single rolling stand, or by passing the strip through several successive stands, the first ensuring a slight reduction aimed at closing the porosities, and the one or the following ensuring the obtaining of the final thickness.
- the following triplets can be proposed (casting thickness / reduction ratio in hot rolling / final thickness): examples of triplets (casting thickness / reduction rate in hot rolling / final thickness) Initial strip thickness (mm) Hot rolling rate (%) Final strip thickness (mm) 4 25 3 4 50 2 2 40 1.2 1.5 40 0.9 1 60 0.6
- a first forced cooling of the tape for example by means of a sprinkling of water.
- This cooling aims to form the within the band a ferritic structure, while avoiding the appearance of perlite. To this end, it must be carried out at a speed between 5 and 100 ° C / s, preferably between 25 and 80 ° C / s, which is perfectly compatible with conventional technologies of cooling of strips having the thicknesses considered. Cooling speed too low would cause perlite to appear, making transformation impossible bainitique which constitutes one of the essential characteristics of the invention. A speed too high cooling risk of not allowing the ferritic structure to be obtained as sought for the matrix, because one would pass directly in the field bainitic, even in the martensitic domain. The range of cooling speeds preferential allows to better ensure the obtaining of an optimal result.
- This first cooling must be such, in speed and duration, that it brings about the strip in a thermal state which allows the strip to remain in the air in the area of temperatures 550-400 ° C, preferably 530-470 ° C (in order to obtain the austenite rate sought for reasonable retention times, while ensuring that no training will be no perlite) for the time necessary for a transformation to occur bainitique stabilizing the proportion of austenite remaining at more than 5%, while avoiding the perlite formation.
- the band undergoes a second forced cooling, for example by spraying water, so as to bring the strip out from the previous temperature range (therefore less than 400 ° C), preferably until its winding temperature, which must be less than 350 ° C.
- This temperature range of winding is chosen to avoid any major change in the structure of the wound strip, such as a precipitation of carbides which would destabilize the austenite.
- the length of stay of the strip in air without forced cooling necessary for obtaining the bainitic transformation as desired varies according to the casting parameters precise, i.e. the composition of the tape and its speed of movement in the the corresponding installation. This duration must be determined experimentally, in using the classic transformation curves of the steel grades considered, and function of the precise residual austenite level that one wishes to obtain. Austenite level high improves ductility, but conversely, an austenite level of less than 5% at the end of bainitic transformation will provide insufficient martensite formation to obtain the TRIP effect.
- an austenite content of 6% is obtained for maintaining the strip of 10 s at 470 ° C or 20s at 530 ° C.
- the duration of this stay may be generally between 5 and 30 s.
- the running speed of the strip hot rolled in the bainitic transformation zone varies according to the hot rolling rate applied to it.
- Table 2 shows examples of strip running speeds in the bainitic transformation zone as a function of the hot rolling rate, taking into account the previous hypotheses.
- strip running speeds in the bainitic transformation zone as a function of the hot rolling rate (casting thickness 3 mm, casting speed 60 m / min) Hot rolling rate (%)
- Belt speed (m / s) 25 1.3 40 1.7 60 2.5 70 3.3
- the cooling zones are consist of a succession of water spray bars, you can choose to use a variable number of ramps to flexibly adjust the lengths of these zones.
- the essential step of the method according to the invention is the stay of the strip in the bainitic transformation field after its hot rolling, to which the second cooling imposes a short duration, as well as the realization of the winding of the strip in a range of temperatures where the bainitic transformation has already happened.
- the fact of making the strip by casting between cylinders (or, so general, by direct casting of thin strips from 1.5 to 10 mm and in particular from 1 to 5 mm thick) and hot rolling in line is almost a prerequisite for the economic viability of carrying out the bainitic transformation in these conditions.
- the strips obtained by the process according to the invention are ready to be used in the same way as TRIP steel strips as well composition obtained by the conventional continuous casting slab die - rolling to hot.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Metal Rolling (AREA)
- Continuous Casting (AREA)
- Heat Treatment Of Steel (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Abstract
Description
- on coule directement à partir d'acier liquide une bande d'épaisseur comprise entre 1,5 et 10 mm, preférentiellement 1 à 5 mm, ledit acier ayant la composition (en pourcentages pondéraux) C% compris entre 0,05 et 0,25, (Mn + Cu + Ni)% compris entre 0,5 et 3, (Si + Al)% compris entre 0,1 et 4, (P + Sn + As + Sb)% inférieur ou égal à 0,1 , (Ti + Nb + V + Zr + terres rares)% inférieur à 0,3, Cr% inférieur à 1, Mo% inférieur à 1, V% inférieur à 1, le reste étant du fer et des impuretés résultant de l'élaboration ;
- on effectue un laminage à chaud en ligne de ladite bande à une température supérieure à la température Ar3 dudit acier avec un taux de réduction compris entre 25 et 70%, en une ou plusieurs passes ;
- on effectue un premier refroidissement forcé de ladite bande à une vitesse comprise entre 5 et 100°C/s ;
- on laisse séjourner la bande à des températures comprises entre 550 et 400°C pendant le temps nécessaire pour que s'y produise une transformation bainitique avec une proportion d'austénite résiduelle supérieure à 5%, tout en évitant la formation de perlite, puis on interrompt cette transformation par un second refroidissement forcé de ladite bande qui l'amène à une température inférieure à 400°C ;
- on effectue un bobinage de ladite bande à une température inférieure à 350°C.
exemples de triplets (épaisseur coulée/taux de réduction au laminage à chaud/épaisseur finale) | ||
Epaisseur de bande initiale (mm) | Taux de laminage à chaud (%) | Epaisseur de bande finale (mm) |
4 | 25 | 3 |
4 | 50 | 2 |
2 | 40 | 1,2 |
1.5 | 40 | 0.9 |
1 | 60 | 0,6 |
vitesses de défilement de la bande dans la zone de transformation bainitique en fonction du taux de laminage à chaud (épaisseur coulée 3 mm, vitesse de coulée 60 m/min) | |
Taux de laminage à chaud (%) | Vitesse de la bande (m/s) |
25 | 1,3 |
40 | 1,7 |
60 | 2,5 |
70 | 3,3 |
Claims (13)
- Procédé de fabrication de bandes minces en acier de type «TRIP », selon lequel :on coule directement à partir d'acier liquide une bande d'épaisseur comprise entre 1,5 et 10 mm préférentiellement 1 à 5 mm, ledit acier ayant la composition (en pourcentages pondéraux) C% compris entre 0,05 et 0,25, (Mn + Cu + Ni)% compris entre 0,5 et 3, (Si + Al)% compris entre 0,1 et 4, (P + Sn + As + Sb)% inférieur ou égal à 0,1, (Ti + Nb + V + Zr + terres rares)% inférieur à 0,3, Cr% inférieur à 1, Mo% inférieur à 1, V% inférieur à 1, le reste étant du fer et des impuretés résultant de l'élaboration ;on effectue un laminage à chaud en ligne de ladite bande à une température supérieure à la température Ar3 dudit acier avec un taux de réduction compris entre 25 et 70%, en une ou plusieurs passes ;on effectue un premier refroidissement forcé de ladite bande à une vitesse comprise entre 5 et 100°C/s ;on laisse séjourner la bande à des températures comprises entre 550 et 400°C pendant le temps nécessaire pour que s'y produise une transformation bainitique avec une proportion d'austénite résiduelle supérieure à 5%, tout en évitant la formation de perlite, puis on interrompt cette transformation par un second refroidissement forcé de ladite bande qui l'amène à une température inférieure à 400°C ;on effectue un bobinage de ladite bande à une température inférieure à 350°C.
- Procédé selon la revendication 1, caractérisé en ce que la teneur en phosphore de l'acier est inférieure ou égale à 0,05%
- Procédé selon la revendication 1 ou 2, caractérisé en ce que le total des teneurs en chrome, molybdène et vanadium ne dépasse pas 0,3%.
- Procédé selon la revendication 3, caractérisé en ce que le total des teneurs en chrome, molybdène et vanadium ne dépasse pas 0,05%.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la teneur en cuivre est comprise entre 0.5 et 2 %.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la vitesse du premier refroidissement est comprise entre 25 et 80°C/s.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'après le premier refroidissement on laisse séjourner la bande entre 530 et 470°C pendant le temps nécessaire pour que s'y produise une transformation bainitique avec une proportion d'austénite résiduelle supérieure à 5%, tout en évitant la formation de perlite.
- Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la durée du séjour de ladite bande dans le domaine où se produit la transformation bainitique est comprise entre 5 et 30 s.
- Procédé selon l'une des revendications 1 à 8, caractérisé en ce que ledit second refroidissement amène ladite bande à sa température de bobinage.
- Procédé selon l'une des revendications 1 à 9, caractérisé en ce qu'entre sa coulée et son laminage à chaud, ladite bande traverse une zone où on maintient au voisinage de sa surface une atmosphère non oxydante pour le métal.
- Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'avant le laminage à chaud, on effectue une opération de décalaminage de la surface de ladite bande.
- Procédé selon l'une des revendications 1 à 11, caractérisé en ce que ladite bande est coulée entre deux cylindres rapprochés à axes horizontaux mis en rotation en sens inverses et refroidis intérieurement.
- Bande mince en acier de type « TRIP », susceptible d'être obtenue par un procédé selon l'une des revendications 1 à 12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9910060A FR2796966B1 (fr) | 1999-07-30 | 1999-07-30 | Procede de fabrication de bandes minces en acier de type "trip" et bandes minces ainsi obtenues |
FR9910060 | 1999-07-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1072689A1 true EP1072689A1 (fr) | 2001-01-31 |
EP1072689B1 EP1072689B1 (fr) | 2004-04-07 |
Family
ID=9548832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00402035A Expired - Lifetime EP1072689B1 (fr) | 1999-07-30 | 2000-07-17 | Procédé de fabrication de bandes minces en acier de type "TRIP" , et bandes minces ainsi obtenues |
Country Status (9)
Country | Link |
---|---|
US (1) | US6328826B1 (fr) |
EP (1) | EP1072689B1 (fr) |
JP (2) | JP4684397B2 (fr) |
KR (1) | KR100656974B1 (fr) |
AT (1) | ATE263846T1 (fr) |
BR (1) | BR0003612A (fr) |
CA (1) | CA2314830C (fr) |
DE (1) | DE60009611T2 (fr) |
FR (1) | FR2796966B1 (fr) |
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EP1365037A1 (fr) * | 2001-01-31 | 2003-11-26 | Kabushiki Kaisha Kobe Seiko Sho | Feuillard en acier a haute resistance ayant une excellente formabilite, et son procede de production |
FR2847271A1 (fr) * | 2002-11-19 | 2004-05-21 | Usinor | Procede pour fabriquer une tole en acier resistant a l'abrasion et tole obtenue |
FR2847908A1 (fr) * | 2002-12-03 | 2004-06-04 | Ascometal Sa | Piece en acier bainitique, refroidie et revenue, et son procede de fabrication. |
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DE50208550D1 (de) * | 2002-08-28 | 2006-12-07 | Thyssenkrupp Steel Ag | Verfahren zum Herstellen eines perlitfreien warmgewalzten Stahlbands und nach diesem Verfahren hergestelltes Warmband |
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EP1326723A4 (fr) * | 2000-09-29 | 2004-09-08 | Nucor Corp | Procede de production d'acier |
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EP1365037A1 (fr) * | 2001-01-31 | 2003-11-26 | Kabushiki Kaisha Kobe Seiko Sho | Feuillard en acier a haute resistance ayant une excellente formabilite, et son procede de production |
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WO2003057928A1 (fr) * | 2002-01-14 | 2003-07-17 | Usinor | Procede de fabrication d'un produit siderurgique en acier au carbone riche en cuivre, et produit siderurgique ainsi obtenu |
FR2834722A1 (fr) * | 2002-01-14 | 2003-07-18 | Usinor | Procede de fabrication d'un produit siderurgique en acier au carbone riche en cuivre, et produit siderurgique ainsi obtenu |
US7425240B2 (en) | 2002-01-14 | 2008-09-16 | Usinor | Method for the production of a siderurgical product made of carbon steel with a high copper content |
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WO2004048618A1 (fr) * | 2002-11-19 | 2004-06-10 | Industeel Creusot | Procede pour fabriquer une tole en acier resistant a l'abrasion et tôle obtenue |
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Also Published As
Publication number | Publication date |
---|---|
FR2796966A1 (fr) | 2001-02-02 |
US6328826B1 (en) | 2001-12-11 |
JP2001073040A (ja) | 2001-03-21 |
JP2011047054A (ja) | 2011-03-10 |
KR100656974B1 (ko) | 2006-12-15 |
FR2796966B1 (fr) | 2001-09-21 |
DE60009611D1 (de) | 2004-05-13 |
BR0003612A (pt) | 2001-03-13 |
CA2314830C (fr) | 2009-03-17 |
EP1072689B1 (fr) | 2004-04-07 |
JP4684397B2 (ja) | 2011-05-18 |
DE60009611T2 (de) | 2005-03-31 |
KR20010021143A (ko) | 2001-03-15 |
ATE263846T1 (de) | 2004-04-15 |
CA2314830A1 (fr) | 2001-01-30 |
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