WO2011069249A1 - Structure de confinement de métal fondu comprenant une ventilation de circulation traversante - Google Patents

Structure de confinement de métal fondu comprenant une ventilation de circulation traversante Download PDF

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Publication number
WO2011069249A1
WO2011069249A1 PCT/CA2010/001936 CA2010001936W WO2011069249A1 WO 2011069249 A1 WO2011069249 A1 WO 2011069249A1 CA 2010001936 W CA2010001936 W CA 2010001936W WO 2011069249 A1 WO2011069249 A1 WO 2011069249A1
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WO
WIPO (PCT)
Prior art keywords
casing
vessel
structure according
metal
gap
Prior art date
Application number
PCT/CA2010/001936
Other languages
English (en)
Inventor
Eric W. Reeves
Jason D. Hymas
John Steven Tingey
Original Assignee
Novelis Inc.
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 Novelis Inc. filed Critical Novelis Inc.
Priority to BR112012013775-1A priority Critical patent/BR112012013775B1/pt
Priority to RU2012127007/02A priority patent/RU2549232C2/ru
Priority to CA2778433A priority patent/CA2778433C/fr
Priority to CN2010800559256A priority patent/CN102812319A/zh
Priority to EP10835334.3A priority patent/EP2510297B1/fr
Priority to JP2012542321A priority patent/JP5613258B2/ja
Publication of WO2011069249A1 publication Critical patent/WO2011069249A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/14—Discharging devices, e.g. for slag
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/12—Casings; Linings; Walls; Roofs incorporating cooling arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/103—Distributing the molten metal, e.g. using runners, floats, distributors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D35/00—Equipment for conveying molten metal into beds or moulds
    • B22D35/04—Equipment for conveying molten metal into beds or moulds into moulds, e.g. base plates, runners
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/5294—General arrangement or layout of the electric melt shop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/14—Supports for linings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/14—Charging or discharging liquid or molten material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to molten metal containment systems and structures used, for example, for conveying molten metal from one location to another, e.g. from a metal melting furnace to a metal casting mold or casting table. More particularly, the invention relates to such structures containing a refractory (usually ceramic) vessel, e.g. a metal distribution trough, crucible, or the like, contained within an outer metal casing used to support, protect and locate the refractory vessel.
  • a refractory (usually ceramic) vessel e.g. a metal distribution trough, crucible, or the like
  • Metal containment structures of this kind suffer from the disadvantage that the refractory vessel may become extremely hot during use due to contact with the molten metal (e.g. 680°C to 750°C when conveying molten aluminum or aluminum alloys). If this heat is transferred to the outer metal casing of the structure, the metal casing may be subjected to expansion, warping or distortion which, in turn, may cause cracks to form in the vessel or, if the refractory vessel is made in sections, may cause gaps to form between the sections, thereby allowing molten metal to leak from the vessel into the casing. Additionally, the outer surfaces of the casing may assume an operating temperature that is unsafe for operators of the equipment.
  • the molten metal e.g. 680°C to 750°C when conveying molten aluminum or aluminum alloys.
  • i s containment (e.g. holding or distribution) structure including a refractory molten metal containment vessel having an external surface, and a metal casing for the vessel having an internal surface at least partially surrounding the external surface of the vessel at a distance therefrom forming a spacing between the vessel and the casing.
  • the spacing includes an unobstructed upwardly extending gap that is
  • a layer of insulating material is positioned in the spacing between the internal surface of the casing and the external surface of the vessel, the layer of insulating material being narrower than the spacing at least at upwardly extending sides of the casing, thereby forming the unobstructed gap.
  • the unobstructed gap is preferably formed between the layer of insulating material and the internal surface of the metal casing, but may alternatively, or additionally, be formed between the layer of insulating material and the external surface of the refractory vessel. Additionally, a second gap (vented or unvented) may be formed on a side of the layer of insulation material opposite to the
  • the unobstructed gap may, if desired, be made to extend across the bottom of the metal casing as well as at the upwardly extending sides.
  • the casing preferably has a bottom wall, side walls and a top, with the upper and lower openings being positioned in or adjacent to the top and the bottom wall of the casing.
  • the lower openings are channels formed between plates used for the bottom wall and side walls of the casing, and the upper openings are holes or slots in the upper wall of the casing.
  • the unobstructed gap and the openings are dimensioned to cause laminar flow of air through the gap.
  • the vessel may be, for example, an elongated molten metal conveying trough having an elongated channel extending from one longitudinal end of the trough to an opposite longitudinal end, a vessel with a channel for conveying molten metal, the channel being provided with a metal filter, a vessel having an interior volume for containing molten metal with at least one metal degassing impeller extending into the interior volume, or a crucible having an interior volume adapted for containing molten metal.
  • a preferred embodiment provides a molten metal distribution structure having a ceramic trough having sides and a bottom, and an external surface, and a metal casing for the ceramic trough having an internal surface at least partially surrounding the external surface of the ceramic trough at a distance therefrom forming a spacing between the trough and the casing.
  • a layer of thermal insulation material is positioned in the spacing between the ceramic trough and the casing.
  • the layer of insulation material adjacent to the sides of the ceramic trough is made narrower than the spacing at these points to form an upwardly- extending continuous unfilled gap within the structure at the sides thereof.
  • the gap communicates with lower and upper openings in the casing positioned to permit external air to enter and flow upwardly through the gap. The gap creates and air flow through the casing that reduces the temperature of the casing.
  • the vessel of all exemplary embodiments is primarily intended for containing or conveying molten aluminium or aluminium alloys, but may be applied for containing or conveying other molten metals and alloys, particularly those having melting points similar to molten aluminium, e.g. magnesium, lead, tin and zinc (which have melting points lower melting points than aluminium) and copper and gold (which have higher melting points). Iron and steel have much higher melting points, but the structures of the invention may also be designed for such metals, if desired.
  • Molten aluminum held in an unheated vessel is typically kept at a temperature in the range of 680 to 720°C. Under such conditions, the
  • temperature of the outer surface of an insulating layer would normally be around 250 to 300°C, and the exemplary embodiments may reduce the temperature of the external metal casing to 100°C or less.
  • the vessel is preferably made of a refractory material.
  • refractory material as used herein to refer to metal containment vessels is intended to include all materials that are relatively resistant to attack by molten metals and that are capable of retaining their strength at the high temperatures contemplated for the vessels. Such materials include, but are not limited to, ceramic materials (inorganic non-metallic solids and heat-resistant glasses) and non-metals.
  • a non- limiting list of suitable materials includes the following: the oxides of aluminum (alumina), silicon (silica, particularly fused silica), magnesium (magnesia), calcium (lime), zirconium (zirconia), boron (boron oxide); metal carbides, borides, nitrides, silicides, such as silicon carbide, nitride-bonded silicon carbide (SiC/Si3N4), boron carbide, boron nitride; aluminosilicates, e.g. calcium aluminum silicate; composite materials (e.g. composites of oxides and non-oxides); glasses, including machinable glasses; mineral wools of fibers or mixtures thereof; carbon or graphite; and the like.
  • metal carbides such as silicon carbide, nitride-bonded silicon carbide (SiC/Si3N4), boron carbide, boron nitride; aluminosilicates, e.g.
  • metal containment vessel includes, without limitation, vessels that are intended and designed to hold molten metal for a period of time and vessels that are intended and designed to convey molten metal from one location to another either continuously or intermittently.
  • Fig. 1 of the accompanying drawings is a perspective view of a molten metal containment structure or launder according to one exemplary embodiment of the present invention
  • Fig. 2 is a transverse cross-section of the structure of Fig. 1
  • Fig. 3 is a side view of part of the structure of Figs. 1 and 2.
  • Figs. 1 to 3 illustrate a molten metal distribution structure 10 (e.g. a launder) according to one exemplary embodiment of the present invention.
  • the structure has a refractory trough 12 acting as a metal containment vessel.
  • the trough which is made up of two trough sections 12A and 12B, may be made of any suitable ceramics material that is resistant to high temperature and to attack by the molten metal conveyed through the trough. Suitable examples include alumina and metal carbides, such as silicon carbide.
  • the trough has a U-shaped channel 13 for conveying molten metal from one end of the structure to the other. In use, the structure would be connected at each end to other equipment, e.g. a launder from a metal melting furnace and a launder leading to a casting mould or casting table (not shown).
  • the trough has longitudinal sides 14, a bottom 15 and narrow top edges 16 running along each side of the channel 13.
  • the trough 2 is positioned within, and partially surrounded by, a metal casing 17 which serves to position the trough, to keep the trough sections mutually aligned and in contact, and to protect the trough.
  • the casing 17 has sides 18, a bottom 19 (see Fig. 2) and top plates 20 extending on each side of the U-shaped channel 13 of the trough.
  • the casing 17 may be made from steel or other metal that exhibits good strength at elevated temperatures.
  • the casing of this exemplary embodiment is made of several parts.
  • the sides and bottom of the casing are made from elongated metal plates 22 and 23, respectively. These plates are held together by means of numerous U- shaped metal ribs 25 spaced along the structure between the longitudinal ends thereof. In turn, the ribs 25 are held by metal side braces 27 and bottom
  • braces 28 extending between the ribs and connected to the outer edges thereof.
  • the casing also has end compression flanges 30 at each longitudinal end that keep the trough under longitudinal compression to minimize cracks.
  • the trough 12 is rigidly supported within the casing by means of vertical compression supports 32 and horizontal compression supports 34.
  • These supports are in the form of metal rods 35, made for example of stainless steel, extending through the bottom braces 28 and the side braces 27 through holes in the plates 23 and 22, and the thermal insulation material 46 and 47 to contact the trough at the bottom 15 and lower ends of the sides 14.
  • the inner ends of the rods 35 are provided with enlarged metal contact pads 36 that spread the load applied by the rods to the trough 12 to avoid damage to the trough.
  • the vertical compression supports 32 not only support the trough but apply compressive force, which is possible because the top edges 16 of the trough are trapped beneath the top plates 20 of the casing that are held down firmly by bolts 37.
  • the horizontal compression supports 34 also apply compressive force adjacent to the bottom of the trough, with supports being positioned opposite to each other to
  • the compression supports suspend the trough within the casing while leaving spaces 40 and 42 separating the outer surfaces of the trough from the casing at the sides and bottom of the trough, respectively.
  • the compressive supports accommodate any expansion and contraction of the trough, and of the casing, caused by thermal cycling, by virtue of compression washers 44 located below heads 45 of bolts passing through compression supports 32 and 34..
  • layers 46 and 47 of thermal insulating material Positioned within the spaces 40 and 42 are layers 46 and 47 of thermal insulating material. These layers may be made of any suitable heat-resistant thermal insulation, e.g. boards made of refractory ceramics such as alumina.
  • the layers 46 and 47 are narrower than the spaces 40 and 42, at least at the sides of the trough, and thus create unfilled continuous gaps 49 and 50 between the insulating layers and inner surfaces of the casing. These gaps are maintained by spacing bolts 48 which hold the layers of insulation away from the internal surface of the side plates 22. Gaps 51 and 52 are also formed between the insulating layers 46 and 47 and the external surface of the trough 12. However, the outer gaps 49 at the side of the casing are fully vented to the external atmosphere since they communicate with upper openings 54 and lower
  • the lower openings 55 are in fact open channels running the length of the structure formed between side plates 22 and bottom plate 23 of the casing since these plates are held in such a manner that their edges do not meet.
  • the upper openings 54 are slots formed in the top plates 20, as best seen from Fig. 1. There are several such slots on each side of the trough arranged longitudinally along the top plates 20. As indicated by the arrows shown in Fig. 2, the upper and lower openings 54 and 55 allow external air to enter the gaps 49, to pass upwardly through the gaps due to convection caused by heating of the air, and to pass out of the gaps and the casing through the upper openings 54.
  • the gaps and openings thus provide a passive form of cooling that removes heat from the interior of the structure adjacent to the internal surface of the casing, and thus help to lower the temperature of the casing walls, thereby reducing the likelihood of warping, distortion and damage, and reducing the risk of burns to the operators.
  • the gap 50 at the bottom of the casing is also vented to the exterior by virtue of the communication of this gap with the side gaps 49, as shown.
  • the bottom of the casing is thus also reduced in temperature due to this venting.
  • the width of the side gaps 49 and the size of openings 54 and 55 are preferably such that a relatively slow laminar flow of air passes through the gaps 49 without causing turbulence because turbulence may increase heat transfer across the gap.
  • the optimum width of the gap is a function of the height of the trough, the surface characteristics of the insulating layers 46 and 47, and the design of the top plate 20, as well as the pressure, moisture content and temperature of the air, so the optimum width may vary according to such parameters.
  • a gap of less than 0.06 inch (2mm) is difficult to maintain over the length of the structure due to cutting and welding tolerances.
  • the width of the top plate 20 must increase, and this requires the plate to be made of a thicker gauge steel or the provision of supporting ribs to withstand the bending moment caused by the vertical compression of the refractory trough.
  • a gap having a width greater than about 2 inches (5.1cm), or even 1 inch (2.5cm) may be problematic, and gaps wider than about 0.375 inch (1cm), or even 0.25 inch (6mm), may require extra structural support for the top plates.
  • the openings 54 and 55 are made suitable in size and possibly shape to promote the smooth laminar flow of the air through the gaps, and indeed the upper openings 54 may be the most important for controlling the air flow.
  • a suitable ratio of the opening size to that of the gap may be chosen by trial and experimentation or by computer modelling techniques.
  • the gaps 51 and 52 formed on the trough side of the insulation layers 46 and 47 are not vented to the exterior in the illustrated exemplary embodiment so they act as unvented thermal breaks or air gaps, but they may alternatively be vented through the provision of appropriate openings, e.g. small upper and lower openings in the insulating layers 46 and 47 providing communication with gaps 49 and 50, in order to produce further vented cooling of the structure. However, even if such additional venting is not provided, the gaps 51 and 52 provide additional thermal isolation of the trough from the casing.
  • Fig. 3 illustrates how the end compression flanges 30 may be placed under compression to act on the ends of trough 12.
  • the flanges 30 are movable relative to the remainder of the casing and are attached to bolts 60 which pass through an adjacent rib 25.
  • Rotation of bolt heads 61 draw the flange 20 axially inwardly and the flange in turn presses on the longitudinal end of the trough 12 (Fig. 2).
  • Compression washers 62 positioned between the bolt head 61 and the rib 25 allow for slight movements of the trough due to contraction and expansion caused by thermal cycling.
  • insulating layers 46 and 47 may be entirely absent from the structure so that just the passive air ventilation is relied upon to protect the outer metal casing from exposure to high temperatures.
  • the vented gap may be provided on the vessel side of the insulating layers rather than on the casing side as shown, although this may have the effect of withdrawing large amounts of heat from the trough.
  • the gap on the trough side of the insulation may be passively vented by providing holes or slots in the bottom layer 47 of insulation and in the side layers 46 of insulation near the top.
  • Figs. 1 to 3 does not include heating means for the trough within the casing, but the use of such heating means is possible.
  • electrical heating elements may be provided in the gaps 51 at each side of the trough 12.
  • Other examples of trough structures having heating means are disclosed in U.S. patent No. 6,973,955 which issued to Tingey et al. on December 13, 2005 (the disclosure of which is specifically incorporated herein by this reference).
  • the rods 35 of the vertical and horizontal compression supports are desirable to make the rods 35 of the vertical and horizontal compression supports partially or fully out of a refractory ceramic material, e.g. alumina, rather than out of metal. This is because the rods are subjected to higher temperatures when heating means are provided within the casing, and such temperatures may cause metal rods to deform or lose compressive strength.
  • a refractory ceramic material e.g. alumina
  • the trough 12 is an elongated molten metal trough of the kind used in molten metal distribution systems used for conveying molten metal from one location (e.g. a metal melting furnace) to another location (e.g. a casting mold).
  • a metal melting furnace e.g. a metal melting furnace
  • a casting mold e.g. a casting mold
  • other kinds of metal containment and distribution vessels may employed, e.g. as an in-line ceramic filter (e.g. a ceramic foam filter) used for filtering particulates out of a molten metal stream as it passes, for example, from a metal melting furnace to a casting table.
  • the vessel includes a channel for conveying molten metal with a filter positioned in the channel. Examples of such vessels and molten metal containment systems are disclosed in U.S. patent No. 5,673,902 which issued to Aubrey et al. on October 7, 1997, and PCT publication no. WO
  • the vessel acts as a container in which molten metal is degassed, e.g. as in a so-called "Alcan compact metal degasser” as disclosed in PCT patent publication WO 95/21273 published on August 10, 1995.
  • the degassing operation removes hydrogen and other impurities from a molten metal stream as it travels from a furnace to a casting table.
  • Such a vessel includes an internal volume for molten metal containment into which rotatable degasser impellers project from above.
  • the vessel may be used for batch processing, or it may be part of a metal distribution system attached to metal conveying vessels.
  • the vessel may be any refractory metal
  • the vessel may also be designed as a refractory ceramic crucible for containing large bodies of molten metal for transport from one location to another. All such alternative embodiments have a refractory vessel positioned within an outer metal casing and may thus be modified to incorporate the inventive features disclosed herein.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Vertical, Hearth, Or Arc Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Furnace Charging Or Discharging (AREA)
  • Crucibles And Fluidized-Bed Furnaces (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)

Abstract

Dans des modes de réalisation donnés comme exemples, la présente invention concerne une structure de confinement de métal fondu comprenant un récipient de confinement de métal fondu réfractaire possédant une surface externe, et une enceinte métallique pour le récipient comprenant une surface interne qui entoure au moins partiellement la surface externe du récipient à distance de celle-ci de manière à former un espace entre le récipient et l'enceinte. L'espace comprend un jour qui s'étend sans obstruction vers le haut et qui donne à l'extérieur de la structure par le biais d'ouvertures supérieures et inférieures dans l'enceinte. Une couche de matériau isolant est de préférence disposée dans l'espace entre la surface interne de l'enceinte et la surface externe du récipient, la couche de matériau isolant étant plus étroite que l'espace au moins au niveau des côtés de l'enceinte s'étendant vers le haut, formant ainsi le jour sans obstruction. Le récipient peut consister en une goulotte de transport de métal, un boîtier pour filtre métallique, un conteneur pour unité de dégazage métallique, un creuset ou analogue.
PCT/CA2010/001936 2009-12-10 2010-12-08 Structure de confinement de métal fondu comprenant une ventilation de circulation traversante WO2011069249A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR112012013775-1A BR112012013775B1 (pt) 2009-12-10 2010-12-08 Estrutura de contenção de metal em fusão
RU2012127007/02A RU2549232C2 (ru) 2009-12-10 2010-12-08 Сосуд для содержания расплавленного металла, имеющий сквозную вентиляцию
CA2778433A CA2778433C (fr) 2009-12-10 2010-12-08 Structure de confinement de metal fondu comprenant une ventilation de circulation traversante
CN2010800559256A CN102812319A (zh) 2009-12-10 2010-12-08 具有流通通风的熔融金属容纳结构
EP10835334.3A EP2510297B1 (fr) 2009-12-10 2010-12-08 Structure de confinement de métal fondu comprenant une ventilation de circulation traversante
JP2012542321A JP5613258B2 (ja) 2009-12-10 2010-12-08 貫流換気口を有する溶融金属収容構造体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28388709P 2009-12-10 2009-12-10
US61/283,887 2009-12-10

Publications (1)

Publication Number Publication Date
WO2011069249A1 true WO2011069249A1 (fr) 2011-06-16

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ID=44142013

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2010/001936 WO2011069249A1 (fr) 2009-12-10 2010-12-08 Structure de confinement de métal fondu comprenant une ventilation de circulation traversante

Country Status (9)

Country Link
US (1) US8883070B2 (fr)
EP (1) EP2510297B1 (fr)
JP (1) JP5613258B2 (fr)
KR (1) KR101542649B1 (fr)
CN (1) CN102812319A (fr)
BR (1) BR112012013775B1 (fr)
CA (1) CA2778433C (fr)
RU (1) RU2549232C2 (fr)
WO (1) WO2011069249A1 (fr)

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BR112012013775A2 (pt) 2016-04-26
CN102812319A (zh) 2012-12-05
EP2510297B1 (fr) 2015-08-26
JP5613258B2 (ja) 2014-10-22
RU2012127007A (ru) 2014-01-20
RU2549232C2 (ru) 2015-04-20
CA2778433C (fr) 2014-07-08
KR101542649B1 (ko) 2015-08-06
CA2778433A1 (fr) 2011-06-16
KR20120109484A (ko) 2012-10-08
US20110140318A1 (en) 2011-06-16
US8883070B2 (en) 2014-11-11
JP2013512780A (ja) 2013-04-18
BR112012013775B1 (pt) 2020-09-01
EP2510297A4 (fr) 2014-01-08
EP2510297A1 (fr) 2012-10-17

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