EP2268431A1 - Brassage électromagnétique modulé de métaux à un stade avancé de solidification - Google Patents

Brassage électromagnétique modulé de métaux à un stade avancé de solidification

Info

Publication number
EP2268431A1
EP2268431A1 EP08783247A EP08783247A EP2268431A1 EP 2268431 A1 EP2268431 A1 EP 2268431A1 EP 08783247 A EP08783247 A EP 08783247A EP 08783247 A EP08783247 A EP 08783247A EP 2268431 A1 EP2268431 A1 EP 2268431A1
Authority
EP
European Patent Office
Prior art keywords
stirrers
metallic material
rotating magnetic
magnetic fields
stirrer
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.)
Withdrawn
Application number
EP08783247A
Other languages
German (de)
English (en)
Other versions
EP2268431A4 (fr
Inventor
Leonid S. Beitelman
J. Douglas Lavers
Christopher P. Curran
Gote Tallback
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.)
ABB Inc Canada
ABB Inc USA
Original Assignee
ABB Inc Canada
ABB Inc USA
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 ABB Inc Canada, ABB Inc USA filed Critical ABB Inc Canada
Publication of EP2268431A1 publication Critical patent/EP2268431A1/fr
Publication of EP2268431A4 publication Critical patent/EP2268431A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B22D11/10Supplying or treating molten metal
    • B22D11/11Treating the molten metal
    • B22D11/114Treating the molten metal by using agitating or vibrating means
    • B22D11/115Treating the molten metal by using agitating or vibrating means by using magnetic fields
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/45Magnetic mixers; Mixers with magnetically driven stirrers
    • B01F33/451Magnetic mixers; Mixers with magnetically driven stirrers wherein the mixture is directly exposed to an electromagnetic field without use of a stirrer, e.g. for material comprising ferromagnetic particles or for molten metal
    • 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
    • B22D11/12Accessories for subsequent treating or working cast stock in situ
    • B22D11/122Accessories for subsequent treating or working cast stock in situ using magnetic fields

Definitions

  • the present invention relates to electromagnetic stirring and more particularly to electromagnetic stirring of liquid metals as they solidify.
  • the invention may be used in continuous casting of steel, alloys, or other metallic melts, and in other solidification processes of these materials.
  • Electromagnetic stirring is commonly used in the production of continuously cast steel billets, blooms, and the like; the casting of different alloys; and other liquid metal casting and processing.
  • A.C. electric current is applied to induction coils that surround the melt.
  • the A.C. current excites a continuous rotating A.C. electromagnetic field that stirs a metal, such as in the production in continuous cast steel billets and blooms.
  • the A.C. field may stir the melt in the continuous casting mold, at an early stage of solidification.
  • EMS may also be used for stirring the unsolidified portion of the continuously cast strand below the casting mold, at a later, or an advanced solidification stage.
  • Conventional rotational stirring is not effective at an advanced stage of solidification of the melt, because any turbulence produced by rotational stirring is essentially limited to the solid-liquid interface.
  • the total stirring time available for stirring of continuously cast billets and blooms is limited by the 10 to 40 second period, depending on the cast product cross- section size and the related casting speed. This relatively short time period will restrict both the duration and the number of intermittent or alternating stirring cycles.
  • the alternating stirring can also be performed without dormant periods.
  • an EMS method and apparatus generating greater turbulence in the solidifying melt volume.
  • an applied magnetic field is formed by juxtaposing and thereby modulating at least two independent fields of different frequency to produce turbulent EMS.
  • the method and apparatus are particularly suited for stirring at advanced stages of solidification.
  • a method of electromagnetic stirring a molten metallic material comprises: providing at least two stirrers for generating independent rotating magnetic fields about an axis extending through the molten material. At least first and second ones of the at least two stirrers produce independent first and second rotating magnetic fields have differing angular frequencies.
  • the stirrers are located about the molten metallic material in sufficiently close proximity to each other so that the independent rotating magnetic fields superpose to produce a modulated magnetic field that creates a turbulent flow of the molten metallic material in a transition region of the molten metallic material having a temperature below the liquidus along a central axis of the molten metallic material, and in which the molten metallic material is mixed with at least about 10% of substantially solidified molten metallic material.
  • a casting apparatus comprising a mold for casting a molten metal; a first stirrer for generating a first rotating magnetic field about an axis extending through the molten metal, located downstream of the mold; a second stirrer for generating a second rotating magnetic field, located downstream of the first stirrer; at least one power source for generating the first and second magnetic field, at frequencies of rotation differing from each other; wherein the first and second stirrers are arranged in proximity to each other so that the first and second rotating magnetic fields produce a modulated magnetic field that creates a turbulent flow in a molten metallic material in a region between the first and second stirrers.
  • a method of electromagnetic stirring a metallic melt comprises: providing a first stirrer for generating a first rotating magnetic field that rotates about an axis extending through the melt, at an angular frequency of ⁇ i; providing a second stirrer for generating a second rotating magnetic field that rotates at an angular frequency of ⁇ 2 .
  • the first and second stirrers are located in sufficiently close proximity to each other so that the first and second rotating magnetic field produce a magnetic force having a frequency component with frequency ( ⁇ r ⁇ 2 ) in the metallic melt in a region between the first and second stirrer, wherein ( ⁇ r ⁇ 2 ) is sufficiently small to allow the magnetic force to overcome the inertia of the melt.
  • a method of electromagnetic stirring a molten metallic material comprises: providing a first stirrer for generating a first rotating magnetic field about an axis extending through the molten material; providing a second stirrer for generating a second rotating magnetic field having a frequency of rotation differing from the first rotating magnetic field; wherein the first and second stirrers are located about the molten metallic material in sufficiently close proximity to each other so that the first and second rotating magnetic fields superpose between the first and second stirrers to produce a modulated magnetic field that creates a turbulent flow of the molten metallic material in a transition region of the molten metallic material having a temperature below the liquidus along the axis, and in which the molten metallic material is mixed with at least about 10% of substantially solidified molten metallic material.
  • FIG. 1 is a schematic cross-sectional view of an EMS apparatus on a continuous casting machine, exemplary of an embodiment of the present invention
  • FIG. 2 is a schematic cross-section view of an example stirrers of the EMS apparatus of FIG. 1 ;
  • FIG. 3 is a simplified perspective view of a stirrer of FIG. 1 ;
  • FIG. 4 is a schematic solidification profile, illustrating isolines of solid fraction, of a portion of a cast strand formed by the casting machine of FIG. 1 , in a liquid-to-solid transitional region (the "mushy zone");
  • FIG. 5 is a graph of example axial profiles of magnetic flux density produced by two adjacent stirrers of the EMS apparatus of FIG. 1 ;
  • FIG. 6 is a graph of modulated magnetic force resulting from the superposition of two example magnetic fields of the same rotating direction
  • FIG. 7 is a graph of a low frequency component of magnetic force resulting from filtering the force of FIG. 6 by the melt inertia;
  • FIG. 8 is a graph of angular velocity produced by modulated stirring resulted from superposition of two magnetic fields of the same rotating direction in an example (e.g. mercury) melt.
  • an example e.g. mercury
  • FIG. 9. is a graph of axial profiles of angular stirring velocities produced by different modes of stirring, in the example melt;
  • FIG. 10 is a graph of example angular velocities produced by modulated counter-rotating stirring in the example melt
  • FIG. 11 is graph of stirring velocity profiles at the locales along a central axis of an exemplary melt of steel
  • FIG. 12 is a schematic representation of the melt locales at which axial stirring velocity and turbulent viscosity of FIG. 11 were determined by a 3- dimensional numerical simulation;
  • FIG. 13 is a graph of example of turbulent viscosity at different locales of the stirring pool central axis produced by modulated counter-rotating stirring.
  • FIG. 14 is a graph of example of turbulent viscosity at different locales of the stirring pool central axis produced by conventional, unidirectional stirring.
  • FIG. 1 is a schematic cross-sectional view of a continuous casting machine 10, including an EMS system 12, exemplary of an embodiment of the present invention.
  • Casting machine 10 includes a tundish 14, from which a molten metal, such as liquid steel, or the like is transferred into a casting mold 18 through a submerged entry nozzle 20.
  • a cast strand 22 having an outer shell surrounding a melt 41 takes form.
  • Cast strand 22 exits from the bottom of mold 18.
  • Example EMS system 12 typically includes at least one electro- magnetic stirrer 24 arranged about mold 18.
  • Stirrer 24 could be arranged within the mold housing, or may be enclosed in a housing (not shown) surrounding the mold. As will become apparent, stirrer 24 is arranged to induce stirring motion within the melt inside mold 18 at an early stage of solidification. In the depicted embodiment only one stirrer 24 is arranged about mold 18 to induce rotational stirring of the melt in mold 18. Stirrer 24 could be replaced with a plurality (e.g.2) of electro-magnetic stirrers arranged about mold 18.
  • stirrers 26, 28 are positioned downstream of mold 18 about cast strand 22, at chosen positions detailed below. Again, stirrers 26, 28 are typically enclosed in a housing (not shown), and co- located in this housing.
  • cast strand 22 progresses in its solidification, resulting in a shell of increasing thickness, while the central core of cast strand 22, remains substantially unsolidified as illustrated in FIGS. 1 and 4.
  • the temperature of melt 41 within cast strand 22 declines progressively with time and distance away from mold 18, and, at a certain point, the temperature at the centerline of cast strand 22 crosses under the liquidus temperature for the particular molten material being cast. This point on the centerline of cast strand 22 is illustrated by numeral 48 in FIG. 1.
  • melt 41 As the temperature in melt 41 declines below the liquidus temperature, the solid phase in the form of both free suspended crystals and crystalline cohesive network starts to form throughout the volume of melt 41.
  • the mixture of the liquid and solid phases is commonly termed the "mushy zone" of melt 41 , and is identified as zone 30.
  • the region of cast strand 22, including a solidified shell and mushy zone of melt 41 is referred to as a transitional region of cast strand 22. Formation of a crystalline network in zone 30 typically results in shrinkage porosity, fissures, elemental macrosegregation, and the like, in cast product and may thus affect the quality of the cast product.
  • FIG. 4 An example distribution of liquid and solid along the length of cast strand 22 is depicted in FIG. 4.
  • the graph illustrates the solid fraction of melt 41 , graphed against the thickness of the outer shell. Mushy zone 30 occupies the region between liquid and solid. As illustrated, the solid fraction increases radially away from the centre axis of cast strand 41 , and along the length of cast strand 22, away from the meniscus of melt 41.
  • stirrers 26, 28 are positioned along cast strand 22 at a position corresponding to mushy zone 30.
  • stirrers 26, 28 may be positioned to disrupt the crystals and crystalline structure in mushy zone 30.
  • stirrers 26, 28 may be positioned at a location along the length of cast strand 22, where the temperature along the central axis of melt 41 is below the liquidus temperature and where 10 to 20 volumetric percent of melt 41 has substantially solidified, while the remaining 80 to 90 volumetric percent remains in a substantially liquid state in which the substantially solidified material is mixed.
  • the volumetric percent of mushy zone 30 and its spatial distribution within a particular solidifying melt 41 along strand 22 may be determined by numerical computer simulation using solidification models. Such simulation may be combined in some instances with real-time measurements of major casting variables including casting speed, intensity of the primary and secondary cooling, and the like, which may provide data to improve modelling accuracy.
  • stirrers 26, 28 are illustrated downstream of mold 14.
  • a person of ordinary skill will however appreciated that more than two stirrers could be located downstream of mold 14, in order to disrupt the crystals and crystalline structure in mushy zone 30.
  • FIG. 2 shows an enlarged schematic of cast strand 22 of FIG. 1 , proximate first and second stirrer 26, 28.
  • stirrers 26 and 28 may be arranged in proximity to each other at a predetermined distance L along the lengthwise extent of cast strand 22 about zone 30.
  • L may for example, be in the decimetre to meter range. For instance L may be about 0.2 m.
  • Each of stirrers 24, 26, 28 may, for example, be formed as an inductor, including a stator 32 made of ferromagnetic or similar material, excited by a plurality of winding coils 36, wound about poles 34, as depicted in FIG. 3.
  • One or more controlled A.C. electric power sources may be interconnected with windings 36 to apply an electric current to each winding 36.
  • Currents applied to windings 36 are poly-phase, with currents applied to opposite poles 34 being in phase with each other. The applied currents result in a rotating magnetic field in the volume encompassed by stator 32.
  • stirrers 24, 26, and 28 may be identical or may differ, with each stirrer 24, 26, 28 having its own number of pole pairs, windings, size, and power source.
  • stirrers 26, 28 may each have three pole pairs; alternatively one could have two pole pairs, and the other three. Other combinations will be apparent to those of oridinary skill.
  • the longitudinal extent along cast strand 22, of each stirrer 26, 28 may differ from the longitudinal extent of the others.
  • stirrer 24 is energized to stir molten material in mold 18 (FIG.1 ).
  • Stirrers 26, 28 are also energized to each generate a rotating magnetic field having a common axis of magnetic field rotation. This axis of magnetic field rotation may be parallel, but need not necessarily coincide with, the central axis of cast strand 22.
  • each of windings 36 (FIG. 3) of stirrers 26, 28 is energized by an A.C. polyphase, single frequency electric current supplied from one or more independent power sources (not shown), also controlled by a controller.
  • This electrical arrangement provides independent control of the magnetic fields (and thus independent rotating magnetic fields) produced by each respective stirrer 26, 28.
  • the magnetic flux density produced by first and second stirrers 26, 28 may be the same or different.
  • the difference in magnetic flux densities may be constant or vary in time.
  • Rotational directions of magnetic fields of stirrers 26 and 28 may coincide, as denoted by the arrows B and C in FIG. 2, or oppose each other, as indicated by the arrows of A and C.
  • Direction and angular velocity of rotation may be selected by an operator.
  • the alternating electric currents supplied to windings 36 of stirrers 26, 28 generate a rotational electromagnetic field, having a frequency within the range of about 1 to about 60 Hz, depending on stirring application. For many common applications, such as continuous casting of steel billets and blooms, frequencies within 5 to 30 Hz may be used.
  • the frequency of the field of one stirrer 26 differs from the frequency of the other stirrer 28 by a certain predetermined value in order to produce a modulated magnetic field.
  • the frequency difference may vary in time or be time independent and remain constant.
  • the range of frequency variation may be between about 0.1 and 3.0 Hz (i.e. less that 3.0 Hz).
  • a modulated magnetic fields resulting from superposition of the original magnetic fields produced by the respective adjacent stirrers is predominant, but not limited, in the region between the adjacent stirrers 26, 28 denoted by L in FIG. 2.
  • the magnetic force produced by these superposed magnetic fields is the result of interaction between the magnetic fields of each stirrer 26, 28 and the currents induced by these magnetic fields in melt 41.
  • the magnetic force will have multiple terms, and may create turbulence within melt 41 in mushy zone 30.
  • the magnetic flux density and the current induced in melt 41 are mostly confined between the adjacent inductors will be the vector sums of the respective contributions of each inductor, as a result of superposition of their respective magnetic fields, as shown in FIG. 5.
  • the magnetic force produced within melt 41 will be the vector product of the total magnetic flux density and total current density: Since the magnetic flux and current densities are composed of two contributions from two adjacent stirrers 26, 28 the magnetic force will have multiple terms.
  • this force will have two constant, or DC, terms and two double frequency terms.
  • time varying terms involving the sum of original magnetic field angular frequencies ( ⁇ - ⁇ + ⁇ 2 ) and two time varying terms involving the angular frequency difference, i.e. ( ⁇ r ⁇ 2 ).
  • the double frequency and the frequency sum components of magnetic force or torque typically have little impact on flow in the melt 41 due to the inertial effects of melt 41.
  • the magnetic force or torque of the component having frequency ( O) 1 - ⁇ 2 ) varies sufficiently slowly in time, to overcome inertia of melt 41.
  • FIGS. 6 and 7 illustrate magnetic force resulting from the superposition of two magnetic fields of the same rotating direction.
  • the amplitude of the modulated magnetic force per unit oscillates between 0 and 4, where 1 is the amplitude of non-modulated, steady state force associated with either one of the original magnetic fields.
  • the low frequency force variation oscillates, for example, in the range of +/- 20 percent of the average force amplitude, as shown in an example in FIG. 7.
  • the stirring produced by this force may also be characterized by large oscillations of primary and secondary flows. An example of angular velocity oscillations of the stirring is shown in FIG. 8.
  • FIG. 9 is a graph of depicting angular stirring velocity produced by different modes of stirring.
  • the velocity profile denoted by A produced by stirring with two identical magnetic fields of the same rotating direction.
  • the velocity profile denoted by C is produced by two magnetic fields with opposite rotating directions.
  • the arrows under velocity profile C indicate a counter-rotating stirring motion in the stirring pool.
  • the angular velocity of the counter-rotating stirring denoted by C may be substantially reduced when compared to the velocity of unidirectional stirring flow produced by magnetic fields of the same frequency (marked by A) or different frequencies, as in the case denoted by B.
  • the reduced stirring velocity does not have a negative impact on stirring because the flow kinetic energy is transformed into turbulence.
  • FIG. 10 further shows an example of angular velocity oscillations measured in a column of mercury with induced counter-rotating stirring. The large changes in oscillation result from a combined action of the modulated magnetic field and stirring flows of the opposing directions which are produced by the counter-rotating magnetic fields of the adjacent stirrers 26, 28.
  • FIG. 11 depicts oscillating velocity in the central axial direction obtained by 3-dimensional numerical simulation in an example melt of steel.
  • the velocity profiles shown correspond to the locales in melt 41 identified in FIG. 12. Large velocity oscillations are known to be indicative of highly turbulent flow induced by EMS in melt 41.
  • Turbulence intensity may be qualitatively characterized by turbulent viscosity.
  • FIGS. 13 and 14 further show example turbulent viscosities at different locations of the stirring pool.
  • FIG. 13 shows turbulent viscosity at the stirring pool center, at the locales in FIG. 12. As illustrated in FIG. 13, the highest intensity turbulence occurs at the mid-distance between the adjacent inductors (the locale III in FIG. 12).
  • turbulence intensity at the same locale of the stirring pool produced by conventional unidirectional rotating stirring is shown in FIG. 14.
  • the turbulence created by the counter-rotating stirring in the example melt is up to 5 times greater, having peaks characterized in turbulent viscosity in excess of 2 Ns/m 2 ' and often in excess of 2.5 Ns/m 2 .
  • counter-rotating magnetic fields may be generated at stirrers 26, 28.
  • Counter-rotating magnetic fields produced by adjacent stirrers 26, 28 will excite the counter-rotating flows within melt 41 in zone 30 which collide in the space between adjacent stirrers 26, 28.
  • a steep gradient of declining angular velocity in one rotating direction will be followed by a similar gradient due to increasing velocity in the opposite rotating direction.
  • the angular velocity also exhibits large oscillations. Both these primary flow characteristics, i.e. velocity gradients and oscillations, contribute to generating strong oscillatory recirculating flows in the axial-radial plane.
  • Additional turbulence in the region between stirrers 26, 28 may result from the electromagnetic forces originated from the superposition of counter- rotating magnetic fields of different frequency.
  • low frequency oscillating magnetic forces from magnetic field modulation will generate perturbations in melt 41 , which might become especially significant if those frequencies are within the range of the melt natural frequency due, for example, to the effect of parametric resonance of the melt.
  • other modulation parameters such as electric current amplitude and phase angle variations, can further enhance the modulated forces when compared to non-modulated, time averaged magnetic forces, and consequently, increase turbulence intensity and its effect on improvements in the solidification structure.
  • Proximate stirrers 26, 28 provide for strong modulated magnetic forces resulting from superposed magnetic fields of either common or opposing rotating directions produced by the conventional design equipment, i.e. inductors and power sources.
  • EMS system 12 has been depicted as including two EMS stirrers 26 and 28 arranged to generated a modulated magnetic field, such a field could be generated with three or more stirrers, generating superposing rotating magnetic fields.
  • modulated electromagnetic stirring exemplary of embodiments of the present invention, may be used in most casting and foundry process, where the cast product dimensions and geometry allow for producing rotating flow within a solidifying melt.
  • a modulated electromagnetic stirring system may initially produce unidirectional magnetic fields and therefore unidirectional rotating swirl flow at an early solidification stage.
  • the stirring system may be switched into counter-rotating stirring mode of operation, to generate turbulence at an advanced stage of solidification.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Continuous Casting (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé et un appareil de brassage électromagnétique de métaux fondus à un stade avancé de solidification, qui peut être utilisé dans la coulée continue de billettes et de brames d'acier. Au moins un premier et un deuxième agitateur sont prévus pour produire un premier et un deuxième champ magnétique rotatif de fréquences différentes autour d'un axe de solidification du métal fondu. Les agitateurs sont agencés autour du métal fondu à proximité suffisamment étroite l'un de l'autre pour que leurs champs magnétiques respectifs se superposent en vue de produire un champ magnétique modulé. Les champs magnétiques des différents agitateurs peuvent avoir un sens de rotation commun ou des sens de rotation opposés. Le brassage modulé exercé par les champs magnétiques entraîne la formation d'un écoulement primaire et d'un écoulement secondaire oscillants et ainsi des turbulences dans la masse fondue dans la zone dans laquelle la température du métal fondu le long de son axe central est inférieure au niveau du liquidus et où au moins 10 % de matériau essentiellement solidifié se sont formés. L'écoulement turbulent formé par cette opération de brassage rompt la formation des structures cristallines dans la masse en fusion et mélange le métal fondu enrichi en soluté de la région centrale avec le volume restant, ce qui entraîne une amélioration de la structure de solidification et de la qualité interne globale des produits coulés.
EP08783247.3A 2008-03-25 2008-07-22 Brassage électromagnétique modulé de métaux à un stade avancé de solidification Withdrawn EP2268431A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/076,954 US20090242165A1 (en) 2008-03-25 2008-03-25 Modulated electromagnetic stirring of metals at advanced stage of solidification
PCT/CA2008/001333 WO2009117803A1 (fr) 2008-03-25 2008-07-22 Brassage électromagnétique modulé de métaux à un stade avancé de solidification

Publications (2)

Publication Number Publication Date
EP2268431A1 true EP2268431A1 (fr) 2011-01-05
EP2268431A4 EP2268431A4 (fr) 2017-07-12

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EP08783247.3A Withdrawn EP2268431A4 (fr) 2008-03-25 2008-07-22 Brassage électromagnétique modulé de métaux à un stade avancé de solidification

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Country Link
US (1) US20090242165A1 (fr)
EP (1) EP2268431A4 (fr)
JP (1) JP2011515225A (fr)
KR (1) KR20100139059A (fr)
CN (1) CN101980808A (fr)
AR (1) AR071042A1 (fr)
BR (1) BRPI0822471A2 (fr)
CA (1) CA2719299A1 (fr)
MX (1) MX2010010410A (fr)
RU (1) RU2453395C1 (fr)
UA (1) UA102094C2 (fr)
WO (1) WO2009117803A1 (fr)

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KR20100139059A (ko) 2010-12-31
US20090242165A1 (en) 2009-10-01
EP2268431A4 (fr) 2017-07-12
RU2453395C1 (ru) 2012-06-20
JP2011515225A (ja) 2011-05-19
CA2719299A1 (fr) 2009-10-01
AR071042A1 (es) 2010-05-19
BRPI0822471A2 (pt) 2015-06-16
WO2009117803A1 (fr) 2009-10-01
RU2010143386A (ru) 2012-04-27
CN101980808A (zh) 2011-02-23
MX2010010410A (es) 2010-12-06

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