EP0252828B1 - Composite steel roll for a hot rolling mill - Google Patents
Composite steel roll for a hot rolling mill Download PDFInfo
- Publication number
- EP0252828B1 EP0252828B1 EP87401571A EP87401571A EP0252828B1 EP 0252828 B1 EP0252828 B1 EP 0252828B1 EP 87401571 A EP87401571 A EP 87401571A EP 87401571 A EP87401571 A EP 87401571A EP 0252828 B1 EP0252828 B1 EP 0252828B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- molybdenum
- chromium
- steel
- rolling mill
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
Definitions
- the present invention relates to bimetallic or composite working rolls for rolling mills intended in particular to equip the finishing cages of a hot strip train, as well as the heavy-duty quarto cages.
- the wear modes of hot working cylinders are multiple, in addition to the well-known banding mechanism, which originates from the breaking and loosening of carbides from the working surface.
- the variable metal-cylinder sliding friction along the contact arc and the rolling conditions can lead to superficial plastic shear which is characterized by a continuous seizing working regime.
- French patent FR-A 21 469 221 already gives interesting solutions which translate into significant industrial development on most hot rolling mills in the world, considerably improving the resistance to breakage of carbides on the work surface and to fatigue. thermal, by adjusting the morphology of eutectic carbides M7 C3 by a judicious choice of the content of chromium and carbon elements and their ratio.
- the carbide M7 C3 built on the chromium element gives a matrix rich in chromium which leads to a low kinetics of oxidation, in particular when the contact temperature between cylinder and strip decreases, which is the case in the last finishing cages.
- the scale of the laminated material has insufficient plastic deformation capacity, especially when the temperature decreases to ensure uniform coverage of the sheet in the grip and the metal-cylinder contacts can occur where the metal is exposed. If the cylinder is not in turn covered with an oxide layer, bonding becomes inevitable.
- the problem to be solved by the invention is, therefore, to provide rolling rolls intended to equip the finishing stands of a hot strip train having longer service lives by giving a better quality rolled product.
- the morphology of the carbide phase must be satisfactory, that is to say have a sufficient degree of dissociation
- the present invention thus relates to a composite working cylinder cast by centrifugation, in particular for a finisher cage of a hot strip train or for a quarto cage with heavy plates, comprising a core of nodular cast iron and an external working zone in one chromium-molybdenum steel, characterized in that the chromium-molybdenum steel of the external working zone contains from 1.0 to 1.8% by weight of carbon, from 5 to 8% by weight of chromium, from 3 at 8% by weight of molybdenum, the sum of the chromium and molydene content being between 8 and 15% by weight.
- the molybdenum content is between 5 and 8% by weight.
- the external working area additionally contains from 1 to 2% by weight of vanadium.
- the invention also relates to the use of such a cylinder in a hot train rolling mill stand.
- the recommended solution is based on an original approach which consists of combining chromium and molybdenum as alloying elements capable of forming a eutectic with a high degree of dissociation, while adjusting the quantity of this eutectic phase by a defined carbon content.
- the chromium content in this case, is limited to 8%, so that the chromium content of the matrix is relatively low and leads to good oxidation kinetics. It is also limited to avoid ferrite ⁇ . It is, however, at least 5%, chromium having to intervene in the formation of carbides M7 C3 and M2 C and in order to maintain resistance minimum oxidation essential for heat treatment.
- Molybdenum can vary between 3% and 8%. Its maximum content being limited by economic and metallurgical considerations, in order to avoid in particular the formation of M6 C relatively fragile. The sum Mo + Cr must be between 8 and 15%.
- the carbon content must vary between 1 and 1.8%.
- a content of less than 1% the quantity of eutectic carbides is insufficient and the resistance to abrasion wear is affected.
- a carbon of less than 1% leads to a large amount of phase ⁇ which cannot be hardened.
- the carbon must, moreover, be less than 1.8%, in order to avoid the formation of solid carbides and insufficiently dissociated, which would have the consequence of reducing the resistance to incrustations and to thermal fatigue.
- the hot hardness already greatly improved by the presence of molybdenum in the matrix can be further improved by the addition of 1 to 2% of V. This is not, however, of an indispensable nature and does not in any case constitute that an improvement.
- a cylinder produced according to these composition rules has a very favorable structure with a content of dissociated eutectic carbides of the order of 10%, that is to say close to the structure of high-grade steels chrome used for hot cylinders, for which the percentage of carbides varies between 4 and 9%. Its hardness is still 540 HV after tempering at 580 ° C, while the best materials known until now for the rolls of finishing mills, in this case chromium cast iron has a hardness of 450 HV, after tempering at 580 ° C.
- V 0.3.
- This composition is obviously that of the work table or external zone of the cylinder, the core of which can be made of nodular cast iron, by centrifugal casting.
- the heat treatment can be carried out by subcritical treatment or by re-austenitization treatment.
- the hardness of such a cylinder exceeds 80 Shore C.
Abstract
Description
La présente invention concerne les cylindres bimétalliques ou composites de travail de laminoirs destinés à équiper notamment les cages finisseuses d'un train à bandes à chaud, ainsi que les cages quarto à tô-les fortes.The present invention relates to bimetallic or composite working rolls for rolling mills intended in particular to equip the finishing cages of a hot strip train, as well as the heavy-duty quarto cages.
Les modes d'usure des cylindres de travail à chaud sont multiples, outre le mécanisme de banding bien connu, et qui a pour origine le bris et le déchaussement des carbures de la surface de travail. Le frottement de glissement métal-cylindre variable le long de l'arc de contact et les conditions de laminage peuvent conduire au cisaillement plastique superficiel qui se caractérise par un régime de travail en grippage continu.The wear modes of hot working cylinders are multiple, in addition to the well-known banding mechanism, which originates from the breaking and loosening of carbides from the working surface. The variable metal-cylinder sliding friction along the contact arc and the rolling conditions can lead to superficial plastic shear which is characterized by a continuous seizing working regime.
Les manifestations négatives de ce régime de grippage continu sont la formation à la surface du cylindre d'un relief en forme de chevrons et au delà, l'apparition d'un phénomène d'usure adhésive catastrophique : le collage. L'un et l'autre au même titre que le banding sont dommageables pour le rendement d'un cylindre exprimé en tonnes par millimètre usé et pour le produit laminé caractérisé par des rebuts ou des déclassements.The negative manifestations of this continuous seizure regime are the formation on the surface of the cylinder of a relief in the form of chevrons and beyond, the appearance of a phenomenon of catastrophic adhesive wear: bonding. Both in the same way as the banding are damaging for the performance of a cylinder expressed in tonnes per millimeter spent and for the rolled product characterized by scrap or downgrading.
Le brevet français FR-A 21 469 221 donne déjà des solutions intéressantes qui se traduisent par un développement industriel important sur la plupart des laminoirs à chaud du monde, en améliorant considérablement la résistance au bris des carbures de la surface de travail et à la fatigue thermique, en ajustant la morphologie des carbures eutectiques M7 C3 par un choix judicieux de la teneur des éléments chrome et carbone et de leur rapport.French patent FR-A 21 469 221 already gives interesting solutions which translate into significant industrial development on most hot rolling mills in the world, considerably improving the resistance to breakage of carbides on the work surface and to fatigue. thermal, by adjusting the morphology of eutectic carbides M7 C3 by a judicious choice of the content of chromium and carbon elements and their ratio.
Cependant, le carbure M7 C3 construit sur l'élément chrome donne une matrice riche en chrome qui conduit à une faible cinétique d'oxydation, notamment quand la température de contact cylindre-bande diminue, ce qui est le cas dans les dernières cages finisseuses.However, the carbide M7 C3 built on the chromium element gives a matrix rich in chromium which leads to a low kinetics of oxidation, in particular when the contact temperature between cylinder and strip decreases, which is the case in the last finishing cages.
Or, la calamine du matériau laminé a une capacité de déformation plastique insuffisante, notamment lorsque la température diminue pour assurer une couverture uniforme de la tôle dans l'emprise et les contacts métal-cylindre peuvent se produire là où le métal est à nu. Si de son côté, le cylindre n'est pas à son tour recouvert d'une couche d'oxyde, le collage devient inévitable.However, the scale of the laminated material has insufficient plastic deformation capacity, especially when the temperature decreases to ensure uniform coverage of the sheet in the grip and the metal-cylinder contacts can occur where the metal is exposed. If the cylinder is not in turn covered with an oxide layer, bonding becomes inevitable.
On a également proposé dans le document EP-A-0178022 de réaliser la couche externe des cylindres de travail pour train à chaud en acier à haut chrome additionné de molybdène. Cependant ces cylindres comme les précédents tout en améliorant certaines propriétés de surface ne permettent pas de résoudre les problèmes liés à la présence d'une couche d'oxyde insuffisante, qui sont dus aux teneurs relativement élevées en chrome.It has also been proposed in document EP-A-0178022 to produce the outer layer of the working rolls for hot train in high chromium steel added with molybdenum. However, these cylinders like the previous ones while improving certain surface properties do not make it possible to solve the problems linked to the presence of an insufficient oxide layer, which are due to the relatively high contents of chromium.
Ainsi, lorsque la couche d'oxyde du cylindre est insuffisante, la conduction thermique devient importante et la température superficielle du cylindre croît, ce qui a pour conséquence de diminuer sa limite élastique et d'accélérer le mécanisme de formation des chevrons par le cisaillement plastique superficiel.Thus, when the oxide layer of the cylinder is insufficient, the thermal conduction becomes significant and the surface temperature of the cylinder increases, which has the consequence of reducing its elastic limit and of accelerating the mechanism of formation of the rafters by plastic shear superficial.
Le problème que vise à résoudre l'invention est, par conséquent, de fournir des cylindres de laminage destinés à équiper les cages finisseuses d'un train à bandes à chaud ayant des durées d'utilisation accrues en donnant un produit laminé de meilleure qualité.The problem to be solved by the invention is, therefore, to provide rolling rolls intended to equip the finishing stands of a hot strip train having longer service lives by giving a better quality rolled product.
Les critères que devront remplir ces nouveaux cylindres sont les suivants :The criteria to be met by these new cylinders are as follows:
- la morphologie de la phase carbure doit être satisfaisante, c'est-à-dire présenter un degré de dissociation suffisant;- the morphology of the carbide phase must be satisfactory, that is to say have a sufficient degree of dissociation;
- sa cinétique d'oxydation, notamment dans les conditions de laminage de la dernière cage, c'est-à-dire aux environs de 500°C doit être suffisante ;- Its oxidation kinetics, especially under the rolling conditions of the last stand, that is to say around 500 ° C must be sufficient;
- sa limite élastique à chaud doit être la plus élevée possible pour résister au fluage superficiel.- its hot elastic limit must be the most high possible to resist surface creep.
La présente invention a ainsi pour objet un cylindre de travail composite coulé par centrifugation, notamment pour cage finisseuse d'un train à bandes à chaud ou pour cage quarto à tôles fortes, comportant un coeur en fonte nodulaire et une zone externe de travail en un acier au chrome-molybdène, caractérisé en ce que l'acier au chrome-molybdène de la zone externe de travail contient de 1,0 à 1,8% en poids de carbone, de 5 à 8% en poids de chrome, de 3 à 8% en poids de molybdène, la somme de la teneur en chrome et en molydène étant comprise entre 8 et 15% en poids.The present invention thus relates to a composite working cylinder cast by centrifugation, in particular for a finisher cage of a hot strip train or for a quarto cage with heavy plates, comprising a core of nodular cast iron and an external working zone in one chromium-molybdenum steel, characterized in that the chromium-molybdenum steel of the external working zone contains from 1.0 to 1.8% by weight of carbon, from 5 to 8% by weight of chromium, from 3 at 8% by weight of molybdenum, the sum of the chromium and molydene content being between 8 and 15% by weight.
Selon un mode de réalisation préféré, la te-neur en molybdène est comprise entre 5 et 8% en poids.According to a preferred embodiment, the molybdenum content is between 5 and 8% by weight.
En variante, la zone externe de travail contient en outre de 1 à 2% en poids de vanadium.Alternatively, the external working area additionally contains from 1 to 2% by weight of vanadium.
L'invention a également pour objet l'utilisation d'un tel cylindre dans une cage de laminoir de train à chaud.The invention also relates to the use of such a cylinder in a hot train rolling mill stand.
La solution préconisée repose sur une approche originale qui consiste à associer le chrome et le molybdène comme éléments d'alliage susceptibles de former un eutectique à haut degré de dissociation, tout en ajustant la quantité de cette phase eutectique par une teneur définie en carbone. La teneur en chrome, dans ce cas de figure, est limitée à 8%, de façon à ce que la teneur en chrome de la matrice soit relativement faible et conduise à une bonne cinétique d'oxydation. Elle est aussi limitée pour éviter la ferrite δ. Elle est, cependant, au minimum de 5%, le chrome devant intervenir dans la formation des carbures M7 C3 et M2 C et afin de conserver une résistance à l'oxydation minimum indispensable au traitement thermique.The recommended solution is based on an original approach which consists of combining chromium and molybdenum as alloying elements capable of forming a eutectic with a high degree of dissociation, while adjusting the quantity of this eutectic phase by a defined carbon content. The chromium content, in this case, is limited to 8%, so that the chromium content of the matrix is relatively low and leads to good oxidation kinetics. It is also limited to avoid ferrite δ. It is, however, at least 5%, chromium having to intervene in the formation of carbides M7 C3 and M2 C and in order to maintain resistance minimum oxidation essential for heat treatment.
Le molybdène peut varier entre 3% et 8%. Sa teneur maximum étant limitée par des considérations économiques et métallurgiques, afin d'éviter notamment la formation de M6 C relativement fragile. La somme Mo + Cr doit être comprise entre 8 et 15 %.Molybdenum can vary between 3% and 8%. Its maximum content being limited by economic and metallurgical considerations, in order to avoid in particular the formation of M6 C relatively fragile. The sum Mo + Cr must be between 8 and 15%.
Enfin, la teneur en carbone doit varier entre 1 et 1,8 %. Pour une teneur inférieure à 1 %, la quantité de carbures eutectiques est insuffisante et la résistance à l'usure par abrasion s'en ressent. En outre, un carbone de moins de 1 % conduit à une quantité importante de phase δ impossible à durcir.Finally, the carbon content must vary between 1 and 1.8%. For a content of less than 1%, the quantity of eutectic carbides is insufficient and the resistance to abrasion wear is affected. In addition, a carbon of less than 1% leads to a large amount of phase δ which cannot be hardened.
Le carbone doit, en outre, être inférieur à 1,8%, afin d'éviter la formation de carbures massifs et insuffisamment dissociés, ce qui aurait pour conséquence de diminuer la résistance aux incrustations et à la fatigue thermique.The carbon must, moreover, be less than 1.8%, in order to avoid the formation of solid carbides and insufficiently dissociated, which would have the consequence of reducing the resistance to incrustations and to thermal fatigue.
Enfin, la dureté à chaud déjà très améliorée par la présence de molybdène dans la matrice peut encore être améliorée par l'addition de 1 à 2 % de V. Ceci n'a pas néanmoins de caractère indispensable et ne constitue en tout état de cause qu'une amélioration.Finally, the hot hardness already greatly improved by the presence of molybdenum in the matrix can be further improved by the addition of 1 to 2% of V. This is not, however, of an indispensable nature and does not in any case constitute that an improvement.
On a pu aussi constater qu'un cylindre réalisé suivant ces règles de composition présente une structure très favorable avec une teneur en carbures eutectiques dissociés de l'ordre de 10 %, c'est-à-dire proche de la structure des aciers à haut chrome utilisé pour les cylindres à chaud, pour lesquels le pourcentage de carbures varie entre 4 et 9 %. Sa dureté est encore de 540 HV après revenu à 580°C, alors que les meilleurs matériaux connus jusqu'à présent pour les cylindres de laminoirs finisseurs, en l'occurence la fonte au chrome a une dureté de 450 HV, après revenu à 580°C.It has also been observed that a cylinder produced according to these composition rules has a very favorable structure with a content of dissociated eutectic carbides of the order of 10%, that is to say close to the structure of high-grade steels chrome used for hot cylinders, for which the percentage of carbides varies between 4 and 9%. Its hardness is still 540 HV after tempering at 580 ° C, while the best materials known until now for the rolls of finishing mills, in this case chromium cast iron has a hardness of 450 HV, after tempering at 580 ° C.
Enfin, la cinétique d'oxydabilité mesurée par simulation à 600°C en atmosphère saturée humide est deux fois plus rapide que celle de l'acier à haut chrome.Finally, the kinetics of oxidizability measured by simulation at 600 ° C in a humid saturated atmosphere is twice as fast as that of high chromium steel.
A titre d'exemple, un cylindre de ce type ayant la composition suivante a été réalisé :By way of example, a cylinder of this type having the following composition has been produced:
C = 1,20 ;C = 1.20;
Si = 1,25 ;If = 1.25;
Mn = 0,47 ;Mn = 0.47;
Ni = 0,54 ;Ni = 0.54;
Cr = 7,4 ;Cr = 7.4;
Mo = 6,9 ;Mo = 6.9;
V = 0,3.V = 0.3.
Cette composition est évidemment celle de la table de travail ou zone externe du cylindre, dont le coeur peut être réalisé en fonte nodulaire, par coulée centrifuge. Le traitement thermique peut être réalisé par traitement subcritique ou par traitement de réausténitisation.This composition is obviously that of the work table or external zone of the cylinder, the core of which can be made of nodular cast iron, by centrifugal casting. The heat treatment can be carried out by subcritical treatment or by re-austenitization treatment.
La dureté d'un tel cylindre dépasse 80 Shore C.The hardness of such a cylinder exceeds 80 Shore C.
Claims (4)
- A centrifugally cast composite working roll, particularly for a finishing frame of a hot strip rolling mill or for a four-high stand for heavy plate, comprising a nodular cast-iron core and an outer working zone of a chrome-molybdenum steel, characterised in that the chrome-molybdenum steel of the outer working zone contains from 1.0 to 1.8% by weight carbon, 5 to 8% by weight chrome, 3 to 8% by weight molybdenum, the sum of the chrome and molybdenum content being comprised between 8 and 15% by weight.
- A roll according to Claim 1, characterised in that the molybdenum content is preferably 5 to 8% by weight.
- A roll according to Claim 1 or 2, characterised in that the steel of the outer working zone furthermore contains from 1 to 2% by weight vanadium.
- The use of a roll according to any one of Claims 1 to 3 in a frame of a hot rolling mill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87401571T ATE61949T1 (en) | 1986-07-11 | 1987-07-03 | COMPOUND STEEL ROLLER FOR A HOT ROLLING MILL. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8610216A FR2601268B1 (en) | 1986-07-11 | 1986-07-11 | COMPOSITE STEEL WORKING CYLINDER FOR HOT TRAIN. |
| FR8610216 | 1986-07-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0252828A1 EP0252828A1 (en) | 1988-01-13 |
| EP0252828B1 true EP0252828B1 (en) | 1991-03-27 |
Family
ID=9337399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87401571A Expired - Lifetime EP0252828B1 (en) | 1986-07-11 | 1987-07-03 | Composite steel roll for a hot rolling mill |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0252828B1 (en) |
| AT (1) | ATE61949T1 (en) |
| DE (1) | DE3768871D1 (en) |
| ES (1) | ES2021734B3 (en) |
| FR (1) | FR2601268B1 (en) |
| GR (1) | GR3002077T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT399673B (en) * | 1992-09-11 | 1995-06-26 | Boehler Edelstahl | COMPOSITE ROLLER AND METHOD FOR THEIR PRODUCTION |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536230A (en) * | 1987-12-23 | 1996-07-16 | Chavanne-Ketin | Composite working roll for hot rolling flat products |
| BE1006356A3 (en) * | 1991-12-19 | 1994-08-02 | Fond Marichal Ketin & Cie Sa D | Bimetal working cylinder for hot rolling of steel strips |
| EP2455180A1 (en) * | 2010-11-17 | 2012-05-23 | Cetto Maschinenbau Gmbh & Co. Kg. | Iron-chromium molybdenum manganese alloy, use of same, method for producing this alloy, a roller for a roller assembly with a surface composed of this alloy and a roller for a roller assembly with a surface produced according to the method used to produce this alloy |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1214413B (en) * | 1959-04-10 | 1966-04-14 | Clevite Corp | Use of a steel alloy as a material for sliding arrangements |
| US3342058A (en) * | 1962-03-26 | 1967-09-19 | Hitachi Ltd | Roll for cold-rolling metallic sheet materials |
| DE1215940B (en) * | 1963-04-03 | 1966-05-05 | Vanadium Alloys Steel Company | Use of a corrosion-, rust-resistant and malleable steel alloy for roller and slide bearings as well as sliding guides at working temperatures above 260 ° C |
| US3855015A (en) * | 1969-11-04 | 1974-12-17 | Hitachi Ltd | Work roll for hot rolling |
| DE2122439A1 (en) * | 1971-05-06 | 1972-11-30 | Crucible Inc | Tool steel - free of grain coarsening during austenitising |
| US3768378A (en) * | 1971-11-10 | 1973-10-30 | Abex Corp | Machines |
| DE2263576B2 (en) * | 1972-12-27 | 1978-06-01 | Thyssen Edelstahlwerke Ag, 4000 Duesseldorf | Process for producing an M2 C-free structure in high-speed steel |
| JPS52111411A (en) * | 1976-03-17 | 1977-09-19 | Hitachi Metals Ltd | High speed tool steel |
| SE8106207L (en) * | 1980-11-10 | 1982-05-11 | Teledyne Ind | SPEEDS AND OTHER TOOLS |
| FR2509640A1 (en) * | 1981-07-17 | 1983-01-21 | Creusot Loire | PROCESS FOR PRODUCING A COMPOSITE METAL PART AND PRODUCTS OBTAINED |
| LU85579A1 (en) * | 1984-10-08 | 1986-06-11 | Marichal Ketin & Cie | TWO-METAL ROLLER CYLINDER FOR DEGREASER OR FINISHER CAGE OF A HOT BAD TRAIN |
-
1986
- 1986-07-11 FR FR8610216A patent/FR2601268B1/en not_active Expired - Lifetime
-
1987
- 1987-07-03 ES ES87401571T patent/ES2021734B3/en not_active Expired - Lifetime
- 1987-07-03 DE DE8787401571T patent/DE3768871D1/en not_active Expired - Lifetime
- 1987-07-03 AT AT87401571T patent/ATE61949T1/en not_active IP Right Cessation
- 1987-07-03 EP EP87401571A patent/EP0252828B1/en not_active Expired - Lifetime
-
1991
- 1991-06-06 GR GR91400747T patent/GR3002077T3/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT399673B (en) * | 1992-09-11 | 1995-06-26 | Boehler Edelstahl | COMPOSITE ROLLER AND METHOD FOR THEIR PRODUCTION |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2601268B1 (en) | 1992-07-24 |
| EP0252828A1 (en) | 1988-01-13 |
| DE3768871D1 (en) | 1991-05-02 |
| ATE61949T1 (en) | 1991-04-15 |
| FR2601268A1 (en) | 1988-01-15 |
| GR3002077T3 (en) | 1992-12-30 |
| ES2021734B3 (en) | 1991-11-16 |
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