EP0366646A1 - Process for producing a clad moulded body - Google Patents
Process for producing a clad moulded body Download PDFInfo
- Publication number
- EP0366646A1 EP0366646A1 EP89890278A EP89890278A EP0366646A1 EP 0366646 A1 EP0366646 A1 EP 0366646A1 EP 89890278 A EP89890278 A EP 89890278A EP 89890278 A EP89890278 A EP 89890278A EP 0366646 A1 EP0366646 A1 EP 0366646A1
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- EP
- European Patent Office
- Prior art keywords
- weight
- temperature
- cooling rate
- clad
- materials
- 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.)
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
Definitions
- the invention relates to a method for producing a plated, in particular roll-clad, molded body consisting of a base material and at least one high-alloy, corrosion-resistant support material.
- Clad molded articles are required for certain areas of use, the base material of which combines high strength with high toughness even at low temperatures and whose support material is particularly corrosion-resistant. These requirements exist for certain components in the offshore industry, in the chemical industry and flue gas desulphurization plants.
- a method of the type mentioned at the outset has already become known from AT-PS 384 245, in which a coating material having 3 to 7% by weight Mo is applied by plating to a base material.
- the composite material obtained in this way has sufficient ductility for apparatus construction and a relatively good corrosion resistance.
- the support material is severely attacked by the highly corrosive stress, which makes the devices unusable for further use under corrosive conditions.
- the invention aims to further improve the corrosion resistance to organic and inorganic acids, in particular H2S, H2SO4, HCl and oxidizing acids or acid mixtures, such as aqua regia, and to achieve higher resistance even at high acid temperatures and higher pressure.
- organic and inorganic acids in particular H2S, H2SO4, HCl and oxidizing acids or acid mixtures, such as aqua regia
- the method according to the invention consists in a method for producing a plated, in particular roll-clad, molded body consisting of a base material and at least one high-alloy, rust-free support material, whereby - the base material up to 0.25% by weight of C, 0.10 to 1.5% by weight of Si, 0.50 to 1.70% by weight of Mn, up to 1.00% by weight of Cr, to 0.30% by weight Cu, up to 0.50% by weight Mo, up to 3.00% by weight Ni, up to 0.05% by weight Nb, up to 0.10% by weight V, to 0.02% by weight of N, up to 0.04% by weight of P, up to 0.025% by weight of S, remainder iron and melting-related impurities,% Nb +% Ti +% V less than or equal to 0.20% -% and (% Al +% Ti +% Zr).
- % N is greater than or equal to 0.005% by weight, - the coating material made of 0.001 to 0.1% by weight of C, 0.001 to 2.0% by weight of Si, 0.01 to 5.0% by weight of Mn, 0.5 to 40.0% by weight Cr, 35.0 to 80.0 wt.% Ni, 7.0 to 30.0 wt.% Mo, to 5.0 wt.% Cu, to 1.0 wt.% Ti, to 1 .0% by weight of Nb, up to 0.04% by weight of P, up to 5.0% by weight of W, up to 0.025% by weight of 5, balance iron and melting-related impurities, and - After plating, the materials are brought to a temperature between 1000 and 1150 ° C, then to a temperature between 700 and 450 ° C, preferably between 620 and 550 ° C, with a cooling rate between 10 ° C / s and 1 ° C / s quenched and then cooled in still air at a cooling rate between 15 ° C / min
- Essential for the invention is further the controlled rapid cooling from austenitizing temperature to 700 ° C to 450 ° C and the subsequent slow cooling.
- austenitizing temperature to 700 ° C to 450 ° C
- subsequent slow cooling With this method, the corrosion resistance deteriorating precipitates in the support material are surely suppressed, whereas the base material is converted into a fine ferrite and pearlite structure or acicular ferrite.
- the process is advantageously carried out in such a way that the materials are roll-plated in such a way that a temperature between 1000 and 1060 ° C. is reached at the end of the rolling process, and the austenitizing temperature is then rapidly cooled.
- the fact that the support materials are still in the precipitation-free state before the rapid cooling ensures that the roll-clad molded articles produced in this way have the highest possible corrosion properties.
- the materials are quenched to a temperature between 620 and 550 ° C with a cooling rate between 7 ° C / s and 3 ° C / s will.
- Such a quenching treatment of the composite material can further increase the strength values of the base material and at the same time ensure excellent corrosion properties of the support material.
- the composite material is advantageously cooled further in still air at a cooling rate of approximately 10 ° C./min.
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Herstellen eines plattierten, insbesondere walzplattierten, aus einem Grundwerkstoff und mindestens einem hochlegierten, korrosionsbeständigen Auflagewerkstoff bestehenden Formkörpers.The invention relates to a method for producing a plated, in particular roll-clad, molded body consisting of a base material and at least one high-alloy, corrosion-resistant support material.
Für bestimmte Verwendungsgebiete werden plattierte Formkörper verlangt, deren Grundwerkstoff eine hohe Festigkeit mit einer hohen Zähigkeit auch bei tiefen Temperaturen verbindet und dessen Auflagewerkstoff in besonderem Maß korrosionsbeständig ist. Diese Forderungen bestehen für bestimmte Komponenten in der Offshore-Industrie, in der chemischen Industrie sowie Rauchgasentschwefelungsanlagen.Clad molded articles are required for certain areas of use, the base material of which combines high strength with high toughness even at low temperatures and whose support material is particularly corrosion-resistant. These requirements exist for certain components in the offshore industry, in the chemical industry and flue gas desulphurization plants.
Ein Verfahren der eingangs genannten Art ist bereits aus der AT-PS 384 245 bekanntgeworden, bei welchem durch Plattieren auf einen Grundwerkstoff ein 3 bis 7 Gew.-% Mo aufweisender Auflagewerkstoff aufgebracht wird. Der auf diese Weise erhaltene Verbundwerkstoff weist eine für den Apparatebau ausreichende Verformbarkeit sowie eine relativ gute Korrosionsbeständigkeit auf. Wenn jedoch aus derartigen Materialien gefertigte Apparaturen längere Zeit extrem starken organischen oder anorganischen Säuren, insbesondere bei höheren Temperaturen, ausgesetzt werden, wird der Auflagewerkstoff durch die hoch-korrosive Beanspruchung stark angegriffen, wodurch die Apparaturen für den weiteren Einsatz unter korrosiven Bedingungen unbrauchbar werden.A method of the type mentioned at the outset has already become known from AT-PS 384 245, in which a coating material having 3 to 7% by weight Mo is applied by plating to a base material. The composite material obtained in this way has sufficient ductility for apparatus construction and a relatively good corrosion resistance. However, if devices made from such materials are exposed to extremely strong organic or inorganic acids, especially at higher temperatures, for a long time, the support material is severely attacked by the highly corrosive stress, which makes the devices unusable for further use under corrosive conditions.
Die Erfindung zielt darauf ab, die Korrosionsbeständigkeit gegenüber organischen und anorganischen Säuren, insbesondere H₂S, H₂SO₄, HCl und oxidierenden Säuren bzw. Säuregemischen, wie Königswasser, weiter zu verbessern und auch bei hohen Säuretemperaturen und höherem Druck höhere Beständigkeit zu erzielen.The invention aims to further improve the corrosion resistance to organic and inorganic acids, in particular H₂S, H₂SO₄, HCl and oxidizing acids or acid mixtures, such as aqua regia, and to achieve higher resistance even at high acid temperatures and higher pressure.
Zur Lösung dieser Aufgabe besteht das erfindungsgemäße Verfahren in einem Verfahren zum Herstellen eines plattierten, insbesondere walzplattierten, aus einem Grundwerkstoff und mindestens einem hochlegierten, nicht rostenden Auflagewerkstoff bestehenden Formkörpers, wobei
- der Grundwerkstoff bis 0,25 Gew.-% C, 0,10 bis 1,5 Gew.-% Si, 0,50 bis 1,70 Gew.-% Mn, bis 1,00 Gew.-% Cr, bis 0,30 Gew.-% Cu, bis 0,50 Gew.-% Mo, bis 3,00 Gew.-% Ni, bis 0,05 Gew.-% Nb, bis 0,10 Gew.-% V, bis 0,02 Gew.-% N, bis 0,04 Gew.-% P, bis 0,025 Gew.-% S, Rest Eisen und erschmelzungsbedingte Verunreinigungen enthält, wobei % Nb + % Ti + % V kleiner gleich 0,20 Gew.-% und
(% Al + % Ti + % Zr) . % N größer gleich 0,005 Gew.-% ist,
- der Auflagewerkstoff aus 0,001 bis 0,1 Gew.-% C, 0,001 bis 2,0 Gew.-% Si, 0,01 bis 5,0 Gew.-% Mn, 0,5 bis 40,0 Gew.-% Cr, 35,0 bis 80,0 Gew.-% Ni, 7,0 bis 30,0 Gew.-% Mo, bis 5,0 Gew.-% Cu, bis 1,0 Gew.-% Ti, bis 1,0 Gew.-% Nb, bis 0,04 Gew.-% P, bis 5,0 Gew.-% W, bis 0,025 Gew.-% 5, Rest Eisen und erschmelzungsbedingte Verunreinigungen besteht, und
- die Werkstoffe nach dem Plattieren auf eine Temperatur zwischen 1000 und 1150°C gebracht, anschließend auf eine Temperatur zwischen 700 und 450°C, vorzugsweise zwischen 620 und 550°C, mit einer Abkühlgeschwindigkeit zwischen 10°C/s und 1°C/s abgeschreckt und danach an ruhender Luft mit einer Abkühlgeschwindigkeit zwischen 15°C/min und 5°C/min abgekühlt werden.To achieve this object, the method according to the invention consists in a method for producing a plated, in particular roll-clad, molded body consisting of a base material and at least one high-alloy, rust-free support material, whereby
- the base material up to 0.25% by weight of C, 0.10 to 1.5% by weight of Si, 0.50 to 1.70% by weight of Mn, up to 1.00% by weight of Cr, to 0.30% by weight Cu, up to 0.50% by weight Mo, up to 3.00% by weight Ni, up to 0.05% by weight Nb, up to 0.10% by weight V, to 0.02% by weight of N, up to 0.04% by weight of P, up to 0.025% by weight of S, remainder iron and melting-related impurities,% Nb +% Ti +% V less than or equal to 0.20% -% and
(% Al +% Ti +% Zr). % N is greater than or equal to 0.005% by weight,
- the coating material made of 0.001 to 0.1% by weight of C, 0.001 to 2.0% by weight of Si, 0.01 to 5.0% by weight of Mn, 0.5 to 40.0% by weight Cr, 35.0 to 80.0 wt.% Ni, 7.0 to 30.0 wt.% Mo, to 5.0 wt.% Cu, to 1.0 wt.% Ti, to 1 .0% by weight of Nb, up to 0.04% by weight of P, up to 5.0% by weight of W, up to 0.025% by weight of 5, balance iron and melting-related impurities, and
- After plating, the materials are brought to a temperature between 1000 and 1150 ° C, then to a temperature between 700 and 450 ° C, preferably between 620 and 550 ° C, with a cooling rate between 10 ° C / s and 1 ° C / s quenched and then cooled in still air at a cooling rate between 15 ° C / min and 5 ° C / min.
Entgegen den Vorurteilen der Fachwelt, die bei Erhöhung des Mo-Gehaltes bei walzplattierten Auflagewerkstoffen keine Verbesserungen in den Korrosionseigenschaften erwarten ließen, hat es sich überraschenderweise herausgestellt, daß die gleichzeitige Anhebung des Ni-Gehaltes im Rahmen des erfindungsgemäßen Verfahrens und die erfindungsgemäße Plattierung eine gute Verformbarkeit bei gleichzeitig wesentlicher Erhöhung der Korrosionsbeständigkeit bei hohen Temperaturen und hohen Drücken zur Folge hat. Die gleichzeitige Erhöhung des Ni-Gehaltes führt hiebei zu den verbesserten Materialeigenschaften, wobei bei hohen Ni-Gehalten eine Anhebung des Cr-Gehaltes gleichfalls zur Austenitstabilisierung bzw. zur Verbesserung der Korrosionsbeständigkeit führt.Contrary to the prejudices of the experts, which could not be expected to improve the corrosion properties when increasing the Mo content in roll-clad support materials, it has surprisingly been found that the simultaneous increase in the Ni content in the context of the process according to the invention and the plating according to the invention have good ductility with a significant increase in corrosion resistance at high Temperatures and high pressures. The simultaneous increase in the Ni content leads to the improved material properties, with an increase in the Cr content likewise leading to stabilization of the austenite or improvement of the corrosion resistance at high Ni contents.
Wesentlich für die Erfindung ist hiebei weiters die gesteuerte rasche Abkühlung von Austenitisierungstemperatur auf 700°C bis 450°C und das daran anschließende langsame Abkühlen. Mit dieser Methode werden die Korrosionsbeständigkeit verschlechternde Ausscheidungen im Auflagewerkstoff mit Sicherheit unterdrückt, wogegen der Grundwerkstoff in ein feines Ferrit- und Perlitgefüge oder azikularen Ferrit umgewandelt wird.Essential for the invention is further the controlled rapid cooling from austenitizing temperature to 700 ° C to 450 ° C and the subsequent slow cooling. With this method, the corrosion resistance deteriorating precipitates in the support material are surely suppressed, whereas the base material is converted into a fine ferrite and pearlite structure or acicular ferrite.
In vorteilhafter Weise wird das Verfahren so geführt, daß die Werkstoffe so walzplattiert werden, daß am Ende des Walzvorganges eine Temperatur zwischen 1000 und 1060°C erreicht wird und anschließend die rasche Abkühlung von Austenitisierungstemperatur erfolgt. Dadurch, daß die Auflagewerkstoffe sich vor der raschen Abkühlung noch im ausscheidungsfreien Zustand befinden, wird sichergestellt, daß die so hergestellten walzplattierten Formkörper höchstmögliche Korrosionseigenschaften aufweisen.The process is advantageously carried out in such a way that the materials are roll-plated in such a way that a temperature between 1000 and 1060 ° C. is reached at the end of the rolling process, and the austenitizing temperature is then rapidly cooled. The fact that the support materials are still in the precipitation-free state before the rapid cooling ensures that the roll-clad molded articles produced in this way have the highest possible corrosion properties.
Um neben einer hohen Korrosionsbeständigkeit auch eine hohe Festigkeit und hohe Kerbschlagzähigkeit des Verbundwerkstoffes sicherzustellen, wird mit Vorteil so vorgegangen, daß die Werkstoffe auf eine Temperatur zwischen 620 und 550°C mit einer Abkühlgeschwindigkeit zwischen 7°C/s und 3°C/s abgeschreckt werden. Durch eine derartige Abschreckbehandlung des Verbundwerkstoffes können die Festigkeitswerte des Grundwerkstoffes weiter erhöht werden und gleichzeitig exzellente Korrosionseigenschaften des Auflagewerkstoffes sichergestellt werden.In order to ensure not only high corrosion resistance but also high strength and high impact strength of the composite material, it is advantageously carried out in such a way that the materials are quenched to a temperature between 620 and 550 ° C with a cooling rate between 7 ° C / s and 3 ° C / s will. Such a quenching treatment of the composite material can further increase the strength values of the base material and at the same time ensure excellent corrosion properties of the support material.
In vorteilhafter Weise wird der Verbundwerkstoff an ruhender Luft mit einer Abkühlgeschwindigkeit von etwa 10°C/min weiter abgekühlt.The composite material is advantageously cooled further in still air at a cooling rate of approximately 10 ° C./min.
Claims (4)
- der Grundwerkstoff bis 0,25 Gew.-% C, 0,10 bis 1,5 Gew.-% Si, 0,50 bis 1,70 Gew.-% Mn, bis 1,00 Gew.-% Cr, bis 0,30 Gew.-% Cu, bis 0,50 Gew.-% Mo, bis 3,00 Gew.-% Ni, bis 0,05 Gew.-% Nb, bis 0,10 Gew.-% V, bis 0,02 Gew.-% N, bis 0,04 Gew.-% P, bis 0,025 Gew.-% S, Rest Eisen und erschmelzungsbedingte Verunreinigungen enthält, wobei % Nb + % Ti + % V kleiner gleich 0,20 Gew.-% und
(% Al + % Ti + % Zr) . % N größer gleich 0,005 Gew.-% ist,
- der Auflagewerkstoff aus 0,001 bis 0,1 Gew.-% C, 0,001 bis 2,0 Gew.-% Si, 0,01 bis 5,0 Gew.-% Mn, 0,5 bis 40,0 Gew.-% Cr, 35,0 bis 80,0 Gew.-% Ni, 7,0 bis 30,0 Gew.-% Mo, bis 5,0 Gew.-% Cu, bis 1,0 Gew.-% Ti, bis 1,0 Gew.-% Nb, bis 0,04 Gew.-% P, bis 5,0 Gew.-% W, bis 0,025 Gew.-% S, Rest Eisen und erschmelzungsbedingte Verunreinigungen besteht, und
- die Werkstoffe nach dem Plattieren auf eine Temperatur zwischen 1000 und 1150°C gebracht, anschließend auf eine Temperatur zwischen 700 und 450°C, vorzugsweise zwischen 620 und 550°C, mit einer Abkühlgeschwindigkeit zwischen 10°C/s und 1°C/s abgeschreckt und danach an ruhender Luft mit einer Abkühlgeschwindigkeit zwischen 15°C/min und 5°C/min abgekühlt werden.1. A method for producing a plated, in particular roll-clad, molded body consisting of a base material and at least one high-alloy, rustproof support material, wherein
- the base material up to 0.25% by weight of C, 0.10 to 1.5% by weight of Si, 0.50 to 1.70% by weight of Mn, up to 1.00% by weight of Cr, to 0.30% by weight Cu, up to 0.50% by weight Mo, up to 3.00% by weight Ni, up to 0.05% by weight Nb, up to 0.10% by weight V, to 0.02% by weight of N, up to 0.04% by weight of P, up to 0.025% by weight of S, remainder iron and melting-related impurities,% Nb +% Ti +% V less than or equal to 0.20% -% and
(% Al +% Ti +% Zr). % N is greater than or equal to 0.005% by weight,
- the coating material made of 0.001 to 0.1% by weight of C, 0.001 to 2.0% by weight of Si, 0.01 to 5.0% by weight of Mn, 0.5 to 40.0% by weight Cr, 35.0 to 80.0% by weight of Ni, 7.0 to 30.0% by weight of Mo, up to 5.0% by weight of Cu, up to 1.0% by weight of Ti, up to 1 , 0% by weight of Nb, up to 0.04% by weight of P, up to 5.0% by weight of W, up to 0.025% by weight of S, balance iron and melting-related impurities, and
- After plating, the materials are brought to a temperature between 1000 and 1150 ° C, then to a temperature between 700 and 450 ° C, preferably between 620 and 550 ° C, with a cooling rate between 10 ° C / s and 1 ° C / s quenched and then cooled in still air at a cooling rate between 15 ° C / min and 5 ° C / min.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0266688A AT397819B (en) | 1988-10-28 | 1988-10-28 | METHOD FOR PRODUCING A PLATED MOLDED BODY |
| AT2666/88 | 1988-10-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0366646A1 true EP0366646A1 (en) | 1990-05-02 |
| EP0366646B1 EP0366646B1 (en) | 1993-11-24 |
Family
ID=3538358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89890278A Expired - Lifetime EP0366646B1 (en) | 1988-10-28 | 1989-10-23 | Process for producing a clad moulded body |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0366646B1 (en) |
| AT (2) | AT397819B (en) |
| DE (1) | DE58906253D1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521774A1 (en) * | 1991-07-03 | 1993-01-07 | Creusot-Loire Industrie | Method for producing a clad steel sheet with a layer of stainless metal |
| US6280540B1 (en) * | 1994-07-22 | 2001-08-28 | Haynes International, Inc. | Copper-containing Ni-Cr-Mo alloys |
| WO2017186112A1 (en) * | 2016-04-26 | 2017-11-02 | 宝山钢铁股份有限公司 | Protective steel plate with excellent cold-bend processing performance and method for manufacturing same |
| WO2017186113A1 (en) * | 2016-04-26 | 2017-11-02 | 宝山钢铁股份有限公司 | Protective composite steel plate and method for manufacturing same |
| US10112254B2 (en) | 2014-08-21 | 2018-10-30 | Huntington Alloys Corporation | Method for making clad metal pipe |
| US11400542B2 (en) | 2016-11-18 | 2022-08-02 | Sms Group Gmbh | Method and device for producing a continuous strip-shaped composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT210235B (en) * | 1955-03-15 | 1960-07-25 | Phoenix Rheinrohr Ag | Process for the production of weld clad steels, preferably sheet metal |
| AT384245B (en) * | 1986-02-21 | 1987-10-12 | Voest Alpine Ag | METHOD FOR PRODUCING A PLATED MOLDED BODY |
-
1988
- 1988-10-28 AT AT0266688A patent/AT397819B/en not_active IP Right Cessation
-
1989
- 1989-10-23 EP EP89890278A patent/EP0366646B1/en not_active Expired - Lifetime
- 1989-10-23 AT AT89890278T patent/ATE97697T1/en not_active IP Right Cessation
- 1989-10-23 DE DE89890278T patent/DE58906253D1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT210235B (en) * | 1955-03-15 | 1960-07-25 | Phoenix Rheinrohr Ag | Process for the production of weld clad steels, preferably sheet metal |
| AT384245B (en) * | 1986-02-21 | 1987-10-12 | Voest Alpine Ag | METHOD FOR PRODUCING A PLATED MOLDED BODY |
Non-Patent Citations (1)
| Title |
|---|
| VOLK: NICKEL UND NICKELLEGIERUNGEN * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521774A1 (en) * | 1991-07-03 | 1993-01-07 | Creusot-Loire Industrie | Method for producing a clad steel sheet with a layer of stainless metal |
| FR2678642A1 (en) * | 1991-07-03 | 1993-01-08 | Creusot Loire | METHOD FOR MANUFACTURING A PLATED PLATE COMPRISING A STAINLESS LAYER AND PLATED PLATE OBTAINED |
| US6280540B1 (en) * | 1994-07-22 | 2001-08-28 | Haynes International, Inc. | Copper-containing Ni-Cr-Mo alloys |
| US10112254B2 (en) | 2014-08-21 | 2018-10-30 | Huntington Alloys Corporation | Method for making clad metal pipe |
| WO2017186112A1 (en) * | 2016-04-26 | 2017-11-02 | 宝山钢铁股份有限公司 | Protective steel plate with excellent cold-bend processing performance and method for manufacturing same |
| WO2017186113A1 (en) * | 2016-04-26 | 2017-11-02 | 宝山钢铁股份有限公司 | Protective composite steel plate and method for manufacturing same |
| US10882277B2 (en) | 2016-04-26 | 2021-01-05 | Baoshan Iron & Steel Co., Ltd.d | Protective composite steel plate and method for manufacturing same |
| US10894388B2 (en) | 2016-04-26 | 2021-01-19 | Baoshan Iron & Steel Co., Ltd. | Protective steel plate with excellent cold-bend processing performance and method for manufacturing same |
| US11400542B2 (en) | 2016-11-18 | 2022-08-02 | Sms Group Gmbh | Method and device for producing a continuous strip-shaped composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0366646B1 (en) | 1993-11-24 |
| DE58906253D1 (en) | 1994-01-05 |
| ATA266688A (en) | 1993-11-15 |
| AT397819B (en) | 1994-07-25 |
| ATE97697T1 (en) | 1993-12-15 |
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