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EP1448330B1 - Procede de coulee continue - Google Patents

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Publication number
EP1448330B1
EP1448330B1 EP02791589A EP02791589A EP1448330B1 EP 1448330 B1 EP1448330 B1 EP 1448330B1 EP 02791589 A EP02791589 A EP 02791589A EP 02791589 A EP02791589 A EP 02791589A EP 1448330 B1 EP1448330 B1 EP 1448330B1
Authority
EP
European Patent Office
Prior art keywords
casting
metal strip
several
model
metal
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
Application number
EP02791589A
Other languages
German (de)
English (en)
Other versions
EP1448330A2 (fr
Inventor
Kurt Etzelsdorfer
Gerald Hohenbichler
Christian Chimani
Gerhard F. Hubmer
Dietmar Auzinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Primetals Technologies Austria GmbH
Original Assignee
Voest Alpine Industrienlagenbau GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Voest Alpine Industrienlagenbau GmbH filed Critical Voest Alpine Industrienlagenbau GmbH
Publication of EP1448330A2 publication Critical patent/EP1448330A2/fr
Application granted granted Critical
Publication of EP1448330B1 publication Critical patent/EP1448330B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/16Controlling or regulating processes or operations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels

Definitions

  • the invention relates to a method for casting casting a thin metal strip in the two-roll process, in particular a steel strip, preferably having a thickness less than 10 mm, wherein molten metal is poured into one of two casting rolls in the thickness of the metal strip to be cast casting gap to form a molten bath.
  • JP-A-60 027 458 it is known to control the geometry of the tape by measuring the thickness at the center as well as at the edges during operation. In order to influence the geometry, the crowning of the rolls is changed.
  • EP-A-0 813 700 A relates to the use of a computer model for controlling and adjusting a strip caster.
  • the calculation model taught here demonstrates learning ability, knowledge gained through integration into the ongoing process. Solidification and Seigerwags are not addressed directly here.
  • the invention according to which online data are taken and processed, largely off-line calculations are carried out according to EP-A-0 813 700 A.
  • the invention aims to avoid these disadvantages and difficulties and has as its object to provide a continuous casting of the type described above, which makes it possible for the metal strip compliance with predetermined quality characteristics such as in particular the formation of a desired microstructure of the metal or the assurance of a particular To allow geometry, u.zw. for metals of different chemical composition, i. for a large number of steel grades or steel grades to be cast.
  • the invention has the task of avoiding deviations in the quality of the metal strip from the outset, u.zw. by making it possible to intervene in production stages in which an actual value of the metal strip which determines the quality is not yet readily recognizable or can not be ascertained directly.
  • This object is achieved in that the formation of a certain microstructure in the cast metal strip, the continuous casting is carried out under on-line calculation under Switzerlandnmdelegung a the formation of the particular microstructure of the metal descriptive computing model, the microstructure influencing variables influencing the continuous casting on-line dynamically, ie during ongoing casting, are set.
  • the structuring of the surface of the casting rolls is detected, preferably detected on-line, and integrated into the calculation model, taking into account the consequent solidification and segregation conditions, in particular in the primary solidification.
  • the structure of the casting roll surfaces forms an important factor in solidification. This structure is only replicated to a certain extent by the liquid metal, i. Depending on the structure of the surface of the casting rolls in certain surface areas to a stronger and in other surface areas to a delayed solidification.
  • the structuring of the surface of the casting rolls is preferably detected, preferably detected on-line, and integrated into the calculation model, taking into account the consequent solidification and segregation conditions, in particular in primary solidification.
  • the solidification of the metal on the surfaces of the casting rolls it is essential to condition these surfaces, such as by cleaning, spraying, coating, in particular by purging with gas or with gas mixtures.
  • This gas or these gas mixtures determine the heat transfer from the melt or already solidified metal to the casting rolls, and there are therefore according to a preferred embodiment, the chemical composition of the gas or the gas mixture and the amount and optionally the distribution over the length of G manwalzen detected, preferably detected on-line, and in the calculation model, taking into account the resulting solidification and Seigerungs discipline, especially in the primary solidification integiert.
  • thermodynamic changes in state of the entire metal strip such as changes in Temperature
  • thermodynamic changes in state of the entire metal strip such as changes in Temperature
  • the thickness of the metal strip by dissolving a heat equation and solving a phase conversion kinetics describing equation or equation systems constantly counted and the temperature setting of the metal strip and optionally the casting rolls is set depending on the calculated value of at least one of the thermodynamic state variables, wherein for the simulation, the thickness of the metal strip , the chemical analysis of the metal and the casting speed are taken into account, the values of which are preferably measured repeatedly during casting, in particular the thickness concerning constantly measured.
  • a continuous phase transformation model of the metal is integrated into the calculation model, in particular according to Avrami.
  • the Avrami equation describes in its general form all diffusion-controlled transformation processes for the respective temperature under isothermal conditions. By taking this equation into account in the calculation model, ferrite, pearlite and bainite fractions can be set in a very targeted manner during steel casting, u.zw. also taking into account a holding time at a certain temperature.
  • the method is characterized in that with the calculation model thermodynamically changes in state of the entire metal strip, such as changes in temperature, by solving a heat equation and solving a the Ausscheidungskinetik during and / or after solidification, in particular non-metallic and intermetallic precipitations, describing equation or equation systems
  • the temperature setting of the metal strip and, if appropriate, of the casting rolls is set as a function of the calculated value of at least one of the thermodynamic state variables, whereby the thickness of the metal strip, the chemical analysis of the metal and the casting speed are taken into account for the simulation, preferably their values during the G manens be repeatedly measured, in particular the thickness concerning constantly measured.
  • microstructure ratios according to multi-component system diagrams, such as, for example, according to the Fe-C diagram, into the calculation model.
  • grain growth properties and / or grain formation properties are integrated into the calculation model.
  • dynamic and / or delayed and / or post-recrystallization i. a recrystallization, which takes place later in an oven, are taken into account in the calculation model.
  • thermomechanical rolling for example, high-temperature thermomechanical rolling
  • a line temperature greater than A C3 can be taken into account for a line temperature greater than A C3 .
  • the mechanical state such as the deformation behavior
  • further model equations in particular by solving the continuum technical basic equations for the visco-elasto-plastic material behavior, is also always included in the calculation model.
  • a preferred embodiment is characterized in that a quantitatively defined structure is adjusted by applying an on-line calculated strand deformation, which causes a recrystallization of the microstructure.
  • a thermal influence of the molten metal and already solidified metal is expediently integrated into the computer model by the casting rolls with on-line detection of the casting roll cooling.
  • An advantageous variant of the method according to the invention is characterized in that a rolling process model, preferably a hot rolling process model, is integrated into the calculation model, wherein the rolling process model expediently comprises a rolling force calculation and / or a roll bending force calculation and / or for specially profiled rolls a rolling displacement calculation and / or a rolling deformation calculation and / or for thermally induced rolling geometry changes has integrated a deformation calculation.
  • a rolling process model preferably a hot rolling process model
  • mechanical properties of the metal strip such as yield strength, tensile strength, elongation, etc.
  • yield strength tensile strength
  • elongation elongation
  • mechanical properties of the metal strip can be calculated in advance with the mathematical model, so that a corrective action can be taken in good time when a deviation of these predicted values from predetermined target values is ascertained.
  • the most suitable generation stages i. during solidification and subsequent thermal influences or during subsequent rolling, recrystallization, etc.
  • a thin strip for casting a thin strip 1, in particular a steel strip with a thickness between 1 and 10 mm, is one of two parallel to each other and juxtaposed casting rolls 2 formed casting mold.
  • the casting rolls 2 form a casting gap 3, the so-called "kissing point", at which the strip 1 emerges from the continuous casting mold.
  • Above the G fauxspaltes 3 is a space 4, which is shielded by a cover forming a cover plate 5 upwards, formed and which serves to receive a molten bath 6.
  • the molten metal 7 is supplied via an opening 8 of the cover, through which a dip tube projects into the molten bath 6 below the bath level 9.
  • the casting rolls 2 are provided with an internal cooling, not shown. Side of the casting rolls 2 side plates are provided for sealing the space 6 receiving the molten bath 4.
  • brush systems can be provided, the brushes of which can be set against the surfaces 10 of the casting rolls 2.
  • For quality assurance of the cast steel strip 1 is a computer 11, in the machine data, the desired format of the metal strip, material data, such as the chemical analysis of molten steel, the casting state, the casting speed, the liquid steel temperature at which the molten steel enters between the casting rolls, and the desired structure and optionally a deformation of the steel strip, which can take place on-line or outside the continuous casting, are entered.
  • the calculator calculates various parameters influencing the quality of the hot strip, such as influencing the temperature of the molten steel and / or the steel strip, using a thermal calculation model that enables the temperature analysis based on the solution of a heat transfer equation using a metallurgical calculation model that includes the phase transformation kinetics and nucleation kinetics Furthermore, the internal cooling of the casting rolls, the gas loading of the casting rolls, the degree of deformation of the on-line in the example shown roll stand 12, and optionally reel conditions for the reel 13, etc.
  • the calculation model used according to the invention is essentially based on a strip casting model and a rolling model.
  • the former includes a cast roll, solidification, segregation, primary microstructure, phase transformation and precipitation model.
  • the rolling model includes a thermophysical model, a phase transformation, hot rolling, precipitation, recrystallization and grain size model, and a model for predicting mechanical characteristics.
  • the structuring of the casting roll surfaces 10 is decisive.
  • the surface profile of the casting rolls 2 is simulated by the steel 7, but only to a certain extent. Due to the surface tension of the liquid steel 7, "valleys" are often straddled, in which media (for example gases) are stored. Since the gases reduce the heat dissipation from the liquid steel 7 to the casting rolls 2, the solidification is delayed.
  • media for example gases
  • heat transitions are determined off-line by flow simulations and experiments, thus assigning each surface class a specific distribution of heat fluxes. These heat flow / temperature distributions are transferred to the downstream program parts.
  • a presetting of the (integral) heat flows can be made possible by the setting of the casting roll temperature. This in turn is determined by the G cleverwalzenwerkstoffe, the cooling water temperature and the amount of cooling water.
  • the first step of this calculation model is thus to describe the condition of the casting surface and to calculate and classify the relevant heat transfers (surface "mountains”, gas-filled “valleys”, transition areas) into classes (fuzzyfication) as well as to transmit the respective temperatures.
  • the primary solidification to the different classes is calculated.
  • the primary solidification dendrite growth, alignments, lengths, arm distances
  • the aim of this step is the calculation of the size distribution and growth direction of the dendrites.
  • Segregation and excretion models are used to determine segregation and excretion. The latter, in combination with the temperature model for the particular tape position, determines the degree of exudates that are fuzzified.
  • All parameters are passed to a rolling model whose goal it is to predict structure, mechanical parameters and cooling conditions in the outlet part and geometric parameters, such as. Flatness, predict.
  • All fuzzyfied parameters are passed on an on-line calculation model, which determines the current conditions for the steel strip 1 on the basis of the constantly running temperature model and optionally influences the control parameters by means of control circuits.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Metal Rolling (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)

Claims (22)

  1. Procédé pour la coulée continue d'une bande de métal (1) mince dans le procédé à deux cylindres, en particulier d'une bande d'acier, de préférence avec une épaisseur inférieure à 10 mm, une masse fondue de métal (7) étant coulée dans une fente de coulée (3) formée par deux cylindres de coulée (2) dans l'épaisseur de la bande de métal (1) à couler en formant un bain de fusion (6), caractérisé en ce que, pour réaliser une structure définie dans la bande de métal fondue, la coulée continue est effectuée par un calcul en ligne en se basant sur un modèle de calcul décrivant la conception de la structure définie du métal, des variables, influençant la formation de structure, du procédé de coulée continue étant réglées de façon dynamique en ligne, c'est-à-dire pendant la coulée en cours.
  2. Procédé selon la revendication 1, caractérisé en ce que, pour influencer la géométrie de la bande de métal, la coulée continue est effectuée avec un calcul en ligne en se basant sur un modèle de calcul décrivant la réalisation de la géométrie de la bande de métal, des variables, influençant la géométrie, du procédé de coulée continue étant réglées de façon dynamique en ligne, c'est-à-dire pendant la coulée en cours.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la structuration de la surface des cylindres de coulée est enregistrée, de préférence enregistrée en ligne, et est intégrée dans le modèle de calcul compte tenu des conditions de solidification et de ségrégation qui en résultent, en particulier lors de la solidification primaire.
  4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce que les surfaces de (11) des cylindres de coulée (2) sont arrosées au-dessus du bain de fusion (6) avec un gaz ou un mélange de gaz et la composition chimique du gaz ou du mélange de gaz ainsi que la quantité et éventuellement la répartition sur la longueur des cylindres de coulée sont enregistrées, de préférence en ligne, et sont intégrées, en particulier lors de la solidification primaire, dans le modèle de calcul en tenant compte des conditions de solidification et ségrégation qui en résultent.
  5. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 4, caractérisé en ce que des changements d'état thermodynamiques de l'ensemble de la bande de métal, comme des variations de la température, sont également pris en compte constamment avec le modèle de calcul par la résolution d'une équation de conduction de chaleur et la résolution d'une équation ou de systèmes d'équation décrivant la cinétique de transformation de phase et le réglage de température de la bande métallique et éventuellement des cylindres de coulée est ajusté en fonction de la valeur calculée d'au moins l'une des grandeurs d'état thermodynamiques, l'épaisseur de la bande de métal, l'analyse chimique du métal ainsi que la vitesse de coulée étant prises en compte pour la simulation, vitesse d'écoulement dont les valeurs sont mesurées de façon répétée de préférence pendant la coulée, en particulier en ce qui concerne l'épaisseur.
  6. Procédé selon la revendication 5, caractérisé en ce qu'un modèle continu de transformation de phase du métal est intégré dans le modèle de calcul, en particulier selon Avrami.
  7. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 6, caractérisé en ce que des changements d'état thermodynamiques de l'ensemble de la bande de métal, comme les variations de la température, sont prises en compte constamment avec le modèle de calcul par la résolution d'une équation de conduction thermique et la résolution d'une équation ou de systèmes d'équation décrivant la cinétique de précipitation pendant et/ou après la solidification, en particulier de précipitations non métalliques et intermétalliques et le réglage de la température de la bande de métal éventuellement des cylindres de coulée est ajusté en fonction de la valeur calculée d'au moins l'une des grandeurs d'état thermodynamiques, l'épaisseur de la bande métallique, l'analyse chimique du métal ainsi que la vitesse de coulée étant prises en compte pour la simulation, vitesse dont les valeurs sont mesurées de préférence de façon répétée pendant la coulée, en particulier sont mesurées constamment en ce qui concerne l'épaisseur.
  8. Procédé selon l'une quelconque ou plusieurs revendications 1 à 7, caractérisé en ce que la cinétique de précipitation due à une énergie de phase libre et à la formation de germes et à l'utilisation de grandeurs de base thermodynamiques, en particulier de l'énergie de Gibb, et la croissance des germes selon Zener sont intégrées dans le modèle de calcul.
  9. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 8, caractérisé en ce qu'également des conditions de quantité de structure sont intégrées dans le modèle de calcul selon des diagrammes de système à plusieurs composants, comme par exemple selon le diagramme Fe-C.
  10. Procédé selon l'une quelconque ou plusieurs revendications 1 à 9, caractérisé en ce que les propriétés de croissance de grains et/ou les propriétés de formation de grains sont intégrées dans le modèle de calcul, éventuellement en tenant compte de la recristallisation du métal.
  11. Procédé selon l'une quelconque ou plusieurs revendications 1 à 10, caractérisé en ce que, comme variable de la coulée continue qui influence une formation de structure, un laminage à chaud et/ou un laminage à froid en une ou plusieurs étapes, qui ont lieu pendant l'extraction de la bande de métal, est intégré dans le modèle de calcul.
  12. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 11, caractérisé en ce que, avec le modèle de calcul, également l'état mécanique, comme le comportement à la déformation, est constamment pris en compte, par la résolution d'autres équations de modèle, en particulier par la résolution des équations de base de la mécanique du continuum pour le comportement du matériau visco-élasto-plastique.
  13. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 12, caractérisé en ce qu'une structure définie au niveau de la quantité est ajustée par l'application d'une déformation de la coulée continue calculée en ligne, qui entraîne une recristallisation de la structure.
  14. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 13, caractérisé en ce qu'une influence thermique du bain de métal et du métal déjà solidifié par les cylindres de coulée est intégrée dans le modèle de calcul par un enregistrement en ligne du refroidissement des cylindres de coulée.
  15. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 14, caractérisé en ce qu'une influence thermique de la bande de métal, comme le refroidissement et/ou le réchauffement, est intégrée dans le modèle de calcul.
  16. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 15, caractérisé en ce qu'un modèle de procédé de laminage, de préférence un modèle de procédé de laminage à chaud, est intégré dans le modèle de calcul.
  17. Procédé selon la revendication 16, caractérisé en ce que le modèle de procédé de laminage a intégré un calcul de force de laminage.
  18. Procédé selon la revendication 16 ou 17, caractérisé en ce que le modèle de procédé de laminage a intégré à un calcul de force de pliage de laminage.
  19. Procédé selon l'une quelconque ou plusieurs des revendications 16 à 18, caractérisé en ce que le modèle de procédé de laminage a intégré un calcul de déplacement de laminage pour des cylindres profilés.
  20. Procédé selon l'une quelconque ou plusieurs des revendications 16 à 19, caractérisé en ce que le modèle de procédé de laminage a intégré un calcul de déformation de cylindre.
  21. Procédé selon l'une quelconque ou plusieurs des revendications 16 à 20, caractérisé en ce que le modèle de procédé de laminage a intégré un calcul de déformation pour des variations de la géométrie de laminage qui sont provoquées thermiquement.
  22. Procédé selon l'une quelconque ou plusieurs des revendications 1 à 21, caractérisé en ce qu'au moyen du modèle de calcul, des propriétés de la bande de métal, comme la limite d'élasticité, la résistance à la traction, la dilatation, etc., sont calculées en même temps constamment ou sont calculées au moins pour la fin du procédé de coulée en bande.
EP02791589A 2001-11-30 2002-11-28 Procede de coulee continue Expired - Lifetime EP1448330B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0187701A AT411026B (de) 2001-11-30 2001-11-30 Verfahren zum stranggiessen
AT18772001 2001-11-30
PCT/AT2002/000333 WO2003045607A2 (fr) 2001-11-30 2002-11-28 Procede de coulee continue

Publications (2)

Publication Number Publication Date
EP1448330A2 EP1448330A2 (fr) 2004-08-25
EP1448330B1 true EP1448330B1 (fr) 2006-06-28

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EP02791589A Expired - Lifetime EP1448330B1 (fr) 2001-11-30 2002-11-28 Procede de coulee continue

Country Status (18)

Country Link
US (1) US7044193B2 (fr)
EP (1) EP1448330B1 (fr)
JP (1) JP2005509530A (fr)
KR (1) KR100945607B1 (fr)
CN (2) CN1974064A (fr)
AT (2) AT411026B (fr)
AU (1) AU2002357956B2 (fr)
BR (1) BR0214608A (fr)
CA (1) CA2468319C (fr)
DE (1) DE50207404D1 (fr)
ES (1) ES2268138T3 (fr)
MX (1) MXPA04005028A (fr)
PL (1) PL204970B1 (fr)
RU (1) RU2301129C2 (fr)
TW (1) TWI289485B (fr)
UA (1) UA77725C2 (fr)
WO (1) WO2003045607A2 (fr)
ZA (1) ZA200404193B (fr)

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EP2633929A1 (fr) 2012-03-01 2013-09-04 Siemens Aktiengesellschaft Modélisation d'une installation de laminoirs par coulée
DE102012216514B4 (de) * 2012-06-28 2014-10-30 Siemens Aktiengesellschaft Verfahren zur statistischen Qualitätssicherung bei einer Untersuchung von Stahlprodukten innerhalb einer Stahlklasse
CN107107401B (zh) * 2014-10-24 2019-10-01 百德福钢带有限公司 用于带铸造设备的过程优化
CN106311997A (zh) * 2016-09-30 2017-01-11 江苏非晶电气有限公司 一种增加非晶合金带材厚度的工艺方法
JP7200982B2 (ja) 2020-09-14 2023-01-10 Jfeスチール株式会社 材料特性値予測システム及び金属板の製造方法
CN120079820B (zh) * 2025-04-30 2025-08-01 东北大学 薄带连铸铸机工艺参数的确定方法及装置、介质、终端

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IT1294228B1 (it) * 1997-08-01 1999-03-24 Acciai Speciali Terni Spa Procedimento per la produzione di nastri di acciaio inossidabile austenitico, nastri di acciaio inossidabile austenitico cosi'
AT408198B (de) * 1998-03-25 2001-09-25 Voest Alpine Ind Anlagen Verfahren zum stranggiessen eines dünnen bandes sowie vorrichtung zur durchführung des verfahrens
FR2783444B1 (fr) * 1998-09-21 2000-12-15 Kvaerner Metals Clecim Procede de laminage d'un produit metallique
JP2000210759A (ja) * 1999-01-26 2000-08-02 Nippon Steel Corp 双ドラム式連続鋳造機による鋳造方法
AT409352B (de) * 2000-06-02 2002-07-25 Voest Alpine Ind Anlagen Verfahren zum stranggiessen eines metallstranges
US6314776B1 (en) * 2000-10-03 2001-11-13 Alcoa Inc. Sixth order actuator and mill set-up system for rolling mill profile and flatness control

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US20040216861A1 (en) 2004-11-04
BR0214608A (pt) 2004-09-14
UA77725C2 (en) 2007-01-15
RU2301129C2 (ru) 2007-06-20
AU2002357956A1 (en) 2003-06-10
KR100945607B1 (ko) 2010-03-04
ES2268138T3 (es) 2007-03-16
DE50207404D1 (de) 2006-08-10
MXPA04005028A (es) 2004-08-11
CA2468319C (fr) 2010-06-22
ZA200404193B (en) 2005-01-24
TWI289485B (en) 2007-11-11
CN1974064A (zh) 2007-06-06
WO2003045607A3 (fr) 2003-11-27
KR20040063162A (ko) 2004-07-12
PL204970B1 (pl) 2010-02-26
CA2468319A1 (fr) 2003-06-05
WO2003045607A2 (fr) 2003-06-05
AU2002357956B2 (en) 2008-07-31
EP1448330A2 (fr) 2004-08-25
TW200300371A (en) 2003-06-01
CN1596163A (zh) 2005-03-16
ATA18772001A (de) 2003-02-15
JP2005509530A (ja) 2005-04-14
US7044193B2 (en) 2006-05-16
RU2004119834A (ru) 2005-06-10
ATE331577T1 (de) 2006-07-15
PL370797A1 (en) 2005-05-30
AT411026B (de) 2003-09-25

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