WO2012148560A1 - Refractory element, assembly and tundish for transferring molten metal - Google Patents

Refractory element, assembly and tundish for transferring molten metal Download PDF

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Publication number
WO2012148560A1
WO2012148560A1 PCT/US2012/026856 US2012026856W WO2012148560A1 WO 2012148560 A1 WO2012148560 A1 WO 2012148560A1 US 2012026856 W US2012026856 W US 2012026856W WO 2012148560 A1 WO2012148560 A1 WO 2012148560A1
Authority
WO
WIPO (PCT)
Prior art keywords
nozzle
refractory
base
face
periphery
Prior art date
Application number
PCT/US2012/026856
Other languages
English (en)
French (fr)
Inventor
Dominique Janssen
Philippe Guillo
Jose Simoes
Original Assignee
Vesuvius Crucible Company
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
Priority to MX2013012585A priority Critical patent/MX2013012585A/es
Priority to AU2012250255A priority patent/AU2012250255A1/en
Priority to RU2014110706/02A priority patent/RU2014110706A/ru
Priority to KR1020137030321A priority patent/KR20140022418A/ko
Priority to US14/009,545 priority patent/US20140061257A1/en
Priority to JP2014508346A priority patent/JP2014512277A/ja
Application filed by Vesuvius Crucible Company filed Critical Vesuvius Crucible Company
Priority to CA2829302A priority patent/CA2829302A1/en
Priority to CN201280020864.9A priority patent/CN103582535A/zh
Priority to EP12776441.3A priority patent/EP2701868A4/en
Priority to BR112013025791A priority patent/BR112013025791A2/pt
Publication of WO2012148560A1 publication Critical patent/WO2012148560A1/en
Priority to ZA2013/06980A priority patent/ZA201306980B/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/02Linings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50Pouring-nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50Pouring-nozzles
    • B22D41/502Connection arrangements; Sealing means therefor

Definitions

  • the present invention relates to the continuous casting of steel and particularly to the problem of steel reoxidation.
  • the invention relates to a tundish comprising an assembly comprising a nozzle and a surrounding refractory element preventing or limiting steel reoxidation, and preventing oxidation products from entering a casting channel.
  • the invention also relates to an assembly comprising a nozzle and a surrounding refractory element preventing or limiting steel reoxidation, and preventing oxidation products from entering a casting channel.
  • the invention also relates to such a surrounding refractory element and to a continuous steel casting process.
  • Nozzle clogging results in a decreased productivity, because less steel can be cast per unit of time (as result of the decreasing diameter) and due to replacement of nozzles with concurrent casting interruptions. Besides clogging, the presence of reoxidation products may give rise to erosion of the nozzle and to the formation of inclusion defects in the steel.
  • the molten metal stream is generally shrouded with a pouring shroud during its transfer from a casting vessel to a downstream vessel (or mold) to prevent direct contacts between the poured steel and the surrounding atmosphere.
  • Argon is often injected directly at the surface of a pouring nozzle so as to shield the molten metal stream.
  • the surface of the steel melt in a metallurgical vessel (for example a tundish) is generally covered with a liquid slag layer so as to prevent direct contacts between the steel and the surrounding atmosphere.
  • the atmosphere above the tundish can be made inert (by the use of an oxygen scavenger or of an inert gas such as argon).
  • the present invention is based on the hypothesis that, even though the steel can be made relatively clean, it is impossible to keep it clean up to the mold in normal conditions.
  • reoxidation of the steel by chemical reaction between the refractory elements (generally metal oxide) used in the continuous casting (vessel lining, slag, nozzles, stoppers, etc.) can also generate reoxidation products.
  • Another potential source of reoxidation is the oxygen permeating through these refractory elements or through a permeable joint between the bottom wall lining and the nozzle inlet or even the oxygen desorbed from the refractory element.
  • An object of the present invention is therefore to solve the above problems by preventing the reoxidation products from reaching a casting nozzle and/or from forming in the immediate vicinity of or in the casting nozzle.
  • this object is achieved by the use of a surrounding refractory element, an assembly of a nozzle and a surrounding refractory element, or an assembly of a nozzle and a surrounding refractory element housed in a tundish, in which the element has a base having a main surface, a bottom and a periphery surrounding the main surface, in which the periphery has an exterior surface, and interior surface and an upper face, and the intersection of the bottom of the base and the exterior surface of the periphery contains at least one point at which the angle of intersection is not a right angle.
  • FR-A-2394348 discloses a ring intended to retain the steel in the tundish until a sufficient level and thereby a sufficient thermal mass is reached in order to avoid the entry of "cold" steel into the pouring orifice.
  • the prior art fails to disclose an element with a base and a periphery, and the intersection of the bottom of the base and the exterior surface of the periphery contains at least one point at which the angle of intersection is not a right angle.
  • JP-A1 -2003-205360 discloses a tundish for the continuous casting of steel.
  • the well block of this tundish is comprised of two elements.
  • the nozzle is located inside the bottom part of the well block.
  • An additional refractory element is positioned above the upper part of the nozzle to cover and protect the cement joint between the nozzle and the well block.
  • this document fails to disclose a refractory element with a base and a periphery, and the intersection of the bottom of the base and the exterior surface of the periphery contains at least one point at which the angle of intersection is not a right angle.
  • WO2007/009667 discloses an element for use in conjunction with a nozzle in a metallurgical vessel.
  • this document does not disclose a refractory element with a base and a periphery in which the intersection of the bottom of the base and the exterior surface of the periphery contains at least one point at which the angle of intersection is not a right angle.
  • the reoxidation products and/or inclusions present in the metallurgical vessel and which tend to accumulate on the bottom surface of the vessel and are carried down by the molten steel stream cannot reach the inlet of the nozzle.
  • the element surrounding the nozzle can be of any appropriate shape. In function of the metallurgical vessel design; it can be circular, oval or polygonal; its main orifice can be central or eccentric. In an alternate embodiment of the invention, appropriate shapes for the element may exclude circular shapes.
  • the element surrounding the nozzle can also be cut off so as to accommodate those cases when one or more tundish walls are close to the pouring orifice.
  • the main surface of the element can be planar or not (it can be frusto-conical, rippled, inclined).
  • the nozzle can be an inner nozzle (for example in case the molten steel flow is controlled with a slide gate valve or if the installation is equipped with a tube or calibrated nozzle changer) or a submerged entry nozzle or SEN (for example in the case of stopper control).
  • the metallurgical vessel or tundish can be equipped with one or more of such assemblies.
  • the assembly can be supplied as a one-piece pre-assembled article (for example, co-pressed) or as separated articles.
  • the element surrounding the nozzle need not be circular, and as the element may be placed in a vessel that does not have circular symmetry, it may be important to align the element with the nozzle, and therefore with the nozzle's surroundings, to produce desired flow patterns in the vicinity of the nozzle.
  • the element and the nozzle may be constructed with matching visual indicators or markings that, when aligned or placed in contact, produce the desired geometrical arrangement of the element and the nozzle.
  • the element and the nozzle may be constructed with mating geometries so that, when these geometries are mated, the desired geometrical arrangement of the element and nozzle, and of the combined element and nozzle with their surroundings, is produced.
  • the mating geometries may be a matching recess and protrusion, a matching groove and lip, a matching peg and bore, a matching notch and protrusion, a matching dimple and mogul, a matching ridge and groove, aligned threaded receivers, aligned key or bayonet receivers, or matching non-circular surface geometries such as oval or polygonal faces.
  • the mating geometry of the element may be placed within its main orifice or on the bottom of the base.
  • the element may contain, within its main orifice or on its base, one or more orienting geometries, such as pegs, bores, protrusion, recesses, notches, bevels, dimples, moguls, ridges, grooves, housings for screw or bayonet fittings, or shaped or threaded receiver portions.
  • the bore of the element may be asymmetric, oval or polygonal in shape.
  • the element and the nozzle may constitute a single piece.
  • the refractory element comprises a base having a main surface and a periphery surrounding the main surface; the upper face of the periphery being higher than the main surface of the refractory element.
  • a kind of deflecting trap is created in the area surrounding the nozzle.
  • the upper face of the periphery does not need to be planar. It can be waved or have different heights along the periphery (for example higher in area of the periphery close to a vessel lateral wall and lower on the other side).
  • the periphery may contain one or more interruptions or openings.
  • the periphery may contain stepped changes in height, or may contain gradual changes in height.
  • the upper face of the periphery may have a sawtooth configuration, a semicircular notch configuration, a square notch configuration, a wave configuration, a semicircular protrusion configuration or may contain one or more steps.
  • the upper face of the periphery may be in communication with an outwardly protruding lip.
  • the upper face of the periphery may be in communication with an inwardly protruding lip.
  • the upper face of the periphery may be in communication with a plate or dome structure containing at least one port.
  • the periphery may contain one or more ports; these ports may be circular, oval or polygonal in shape, and the ports may have horizontal axes, axes directed upwards and inwardly, axes directed downwards and inwardly, or axes that are not perpendicular to the external surface of the periphery.
  • the ports may be configured to have axes that are mutually tangent to a circle within the periphery. Pairs of ports may be configured to have axes that intersect each other at a circle within the periphery.
  • the ports may be flared.
  • the level of at least one portion of the outer periphery of the refractory element is higher than the surface of the bottom wall of the tundish.
  • the periphery of the refractory element of the present invention may take the form of a wall with measurements that are related to other measurements of the element by particular ratios or ranges of ratios.
  • the maximum height of the wall, measured from the bottom of the base has a ratio of 1 :1 to 6:1 , or 1 .1 :1 to 6:1 , to the minimum height of the wall, measured from the bottom of the base.
  • the maximum height of the wall measured from the bottom of the base, has a ratio of 0.1 :1 to 10:1 , or 0.1 :1 to 8.5:1 , or 0.2:1 to 8.5:1 , or 0.5:1 to 8.5:1 , to the maximum exterior diameter of the base.
  • the wall has a minimum thickness of 2 mm, 5 mm, or 10 mm.
  • the wall has a maximum thickness of 60 mm, 80 mm, or 100 mm.
  • the base has a maximum thickness of 100 mm or 200 mm.
  • the periphery of the refractory element of the present invention may take the form of a wall that has an exterior surface that has a portion that is not vertical. In certain embodiments, the entire exterior surface of this wall is not vertical. In certain embodiments, the entire wall forms an obtuse angle with the main surface, as measured from the interior of the element. In certain embodiments, the angle between the bottom surface of the base and the exterior surface of the wall has an angle lying within the ranges of 45 degrees to 89.5 degrees and 90.5 degrees to 135 degrees. In certain embodiments, the angle between the bottom surface of the base and the exterior surface of the wall may vary around the circumference of the element.
  • the element has non-vertical outer walls, and the element partially encloses a volume with a cross-section that decreases in size with decreasing distance to the nozzle or to a port in which the nozzle may be located.
  • the walls may take the form of a cylinder with an axis that is not orthogonal to the horizontal plane.
  • the walls may take the form of the radial surface of a truncated cone with a projected vertex below the plane of the main surface.
  • the walls may take the form of the radial surface of a truncated cone with a projected vertex above the plane of the main surface.
  • the upper face of the periphery may form a circle, oval, or polygonal figure in a plane that is not parallel to the plane of the main surface.
  • the interior of the wall of the refractory element and the base of the refractory element may communicate, separately or together, with one or more vanes.
  • a vane may be disposed so that a projection of the plane of the vane intersects the axis of the nozzle.
  • a vane may also be disposed so that no projection of a plane of the vane intersects the axis of the nozzle.
  • the vanes may have surfaces and edges; the surfaces may be planar, may be curved in one or two dimensions, and may be smooth or have grooves.
  • the edges of the vanes may be chamfered or have a sawtooth configuration, a semicircular notch configuration, a square notch configuration, a wave configuration, a semicircular protrusion configuration or may contain one or more steps.
  • the exterior of the wall of the refractory element may communicate with one or more vanes.
  • a vane may be disposed so that a projection of the plane of the vane intersects the axis of the nozzle.
  • a vane may also be disposed so that no projection of a plane of the vane intersects the axis of the nozzle.
  • the vanes may have surfaces and edges; the surfaces may be planar, may be curved in one or two dimensions, and may be smooth or have grooves.
  • the edges of the vanes may be chamfered or have a sawtooth configuration, a semicircular notch configuration, a square notch configuration, a wave configuration, a semicircular protrusion configuration or may contain one or more steps.
  • the surrounding refractory element may be made from a gas-impervious material.
  • a gas-impervious material has an open porosity (at the temperature of use) which is lower than 20% (thus lower than the open porosity of conventional lining material which is typically higher than 30%).
  • the permeability is generally related to the porosity. Therefore a low porosity material has a low permeability to gases.
  • oxygen scavenger materials e.g. antioxidants
  • Suitable materials are boron or silicon carbide, or metals (or alloys thereof) such as silicon or aluminum.
  • products generating melting phase for example B2O3
  • materials forming more voluminous new phases can also be included in the material constituting the preformed element. Suitable materials include compositions of alumina and magnesia. Thereby, steel re-oxidation in the area surrounding the nozzle is prevented.
  • the refractory material has a permeability value less than 15cD, 20cD, 25cD or 30cD, according to standard ASTM testing.
  • a material that may be used contains 0.5-1 %, or 1 -5% silica, 0.005% to 0.2% titania, 75% to 95% alumina, 0.1 % to 0.5% iron (III) oxide, 0.5% to 1 % magnesia, 0.1 % to 0.5% sodium oxide, 0.25% to 2% boron oxide, and 1 % to 10% of zirconia + hafnia.
  • a suitable material may have a loss on ignition value of 0 to 5%.
  • the element, the nozzle or a layer of the element or the nozzle may be made from a gas-impervious material.
  • the nozzle or element may be made from refractory oxides (alumina, magnesia, calcia) and may be isostatically pressed.
  • a 100 g sample of the candidate material is placed in a furnace under argon atmosphere (a gentle stream of argon is continuously blown (about 1 l/min) into the furnace) and the temperature is raised to 1000°C. The temperature is then raised progressively to 1500°C (in 1 hour) and is then left at 1500 °C for 2 hours.
  • the loss of weight of the sample between 1000°C and 1500°C is then measured. This loss of weight must be lower than 2% for qualifying the material as gas-impervious. Thereby, not only the inclusion or reoxidation products cannot reach the nozzle but, in addition, they cannot form in the nozzle or the element. This particular combination provides thus a synergistic effect according to which a perfectly inclusion- and reoxidation product-free steel can be cast.
  • the material constituting the nozzle or element can be selected from three different categories of materials:
  • the selected material will present two or three of the above categories.
  • Suitable material of the first category are alumina, mullite, zirconia or magnesia based material (spinel).
  • Suitable materials of the second category are for example pure alumina carbon compositions.
  • these compositions should contain very low amounts of silica or of conventional impurities which are usually found in silica (sodium or
  • the silica and its conventional impurities should be kept under 1 .0 wt. %, preferably under 0.5 wt. %.
  • Suitable materials of the third category comprise for example free metal able to combine with carbon monoxide to form a metal oxide and free carbon.
  • Silicon and aluminum are suitable for this application.
  • These materials can also or alternatively comprise carbides or nitrides able to react with oxygen compound (for example silicon or boron carbides).
  • the selected material will belong to the second or third categories; in certain embodiments of the invention the selected material will belong to the second and third categories.
  • a suitable material constituting the layer which will not produce carbon monoxide at the temperature of use can comprise 60 to 88 wt. % of alumina, 10 to 20 wt. % graphite and 2 to 10 wt. % of silicon carbide.
  • Such a material contains oxygen getters such as non-oxide species such as nitrides or carbides, or non-reducible oxides, which can react with any oxygen present.
  • a liner present at the steel contacting surface is made from such a material.
  • the nozzle and the surrounding element are made integral (one-piece).
  • Conventional mortars have an open porosity of 30 to 50%.
  • the mortar should have an open porosity of less than 20%.
  • the mortar may be made of a composition similar to, and processed in similar fashion to, the element or nozzle.
  • the invention relates to a particular surrounding refractory element which is used in the assembly according to the invention.
  • This surrounding element comprises a main orifice adapted for matching engagement with at least a portion of the outer surface of the nozzle, a main surface surrounding the main orifice and an outer periphery surrounding the main surface, the level of the upper face of the periphery being higher than that of the main surface.
  • the surrounding refractory element is made from a gas-impervious material.
  • a particularly suitable composition to this end is essentially comprised of a high alumina material comprising at least 75 wt.% of AI2O3, less than 1 .0 wt.% of S1O2, less than 5 wt.% of C, the reminder being constituted of refractory oxides or oxides compounds that cannot be reduced by aluminum (particularly aluminum dissolved in molten steel) at the temperature of use (for example calcia and/or spinel.
  • a particularly suitable material is the CRITERION 92SR castable available from VESUVIUS UK Ltd. This material is a high alumina low cement castable material reinforced with fused alumina-magnesia spinel.
  • a typical analysis of this product is the following:
  • the invention is directed to a process for the continuous casting of steel which comprises pouring the molten steel through an element, or a combination of a nozzle and an element, as above described.
  • FIG. 1 shows a cross-section of the bottom wall of a metallurgical vessel provided with an assembly according to the invention
  • FIG. 2 and 3 show respectively top and perspective views of a surrounding element according to the invention
  • FIG. 4 and 5 show skulls collected at the end of the casting operations in the upper part of the nozzle
  • FIG. 6 is a cross-section of an element according to the invention.
  • FIG. 7 is a cross-section of an element according to the invention.
  • FIG. 8 is a cross-section of an element according to the invention.
  • FIG. 9 is a perspective view of an element according to the invention.
  • FIG. 10 is a cross-section of an element according to the invention.
  • FIG. 1 1 is a cross-section of an element according to the invention.
  • FIG. 12 is a cross-section of an element according to the invention.
  • FIG. 13 is a perspective view of an element according to the invention.
  • FIG. 14 is a cross-section of an element according to the invention.
  • FIG. 15 is a perspective view of an element according to the invention.
  • FIG. 16 is a cross-section of an element according to the invention.
  • FIG. 17 is a cross-section of an element according to the invention.
  • FIG. 18 is a cross-section of an element according to the invention.
  • FIG. 19 is a cross-section of an element according to the invention.
  • FIG. 20 is a perspective view of an element according to the invention
  • FIG. 21 is a perspective view of an element according to the invention.
  • FIG. 22 is a perspective view of an element according to the invention
  • FIG. 23 is a perspective view of an element according to the invention
  • FIG. 24 is a perspective view of an element according to the invention.
  • FIG. 25 is a perspective view of an element according to the invention
  • FIG. 26 is a perspective view of an element according to the invention.
  • FIG. 27 is a perspective view of an element according to the invention.
  • - Fig. 28 is a perspective view of an element according to the invention
  • - Fig. 29 is a perspective view of an element according to the invention
  • FIG. 30 is a cross-section of an element according to the invention.
  • FIG. 31 is a cross-section of an element according to the invention.
  • FIG. 32 is a schematic perspective view of an element according to the invention.
  • FIG. 33 is a schematic perspective view of an element according to the invention.
  • FIG. 34 is a top view of an element according to the invention.
  • FIG. 35 is a top view of an element according to the invention.
  • FIG. 36 is a cross section of an element and a metallurgical vessel according to the invention.
  • FIG. 37 is an elevation of a portion of a raised outer periphery of an element according to the invention.
  • FIG. 38 is an elevation of a portion of a raised outer periphery of an element according to the invention.
  • FIG. 39 is an elevation of a portion of a raised outer periphery of an element according to the invention.
  • Fig. 40 is an elevation of a portion of a raised outer periphery of an element according to the invention.
  • FIG. 42 is a perspective drawing of an element according to the invention.
  • the bottom wall 3 of a metallurgical vessel (here a tundish) is generally constituted of a permanent lining 33 made from refractory bricks or castable material.
  • a working layer 32 of castable material is generally present above the permanent lining 33. The surface 31 of the working layer will contact molten steel during the casting operations.
  • a layer of insulating material 34 is normally present under the permanent lining 33 in order to protect the metallic envelope 35 of the metallurgical vessel.
  • a nozzle 1 goes through the bottom of the tundish and serves to the transfer of the molten steel from the tundish to the continuous casting mold. The nozzle is provided with an inlet 1 1 opening into a bore defining thus a passage 2 for the molten steel.
  • Fig. 1 shows a submerged entry shroud or SES but, as explained above other kind of nozzles (such as an inner nozzle) are also encompassed within the scope of the present invention.
  • the continuous casting operation is generally provided with a guillotine 37 to break the nozzle 1 and terminate casting operations.
  • the SEN is maintained in position by a ramming mass 36.
  • the surrounding refractory element 4 surrounds the inlet portion 1 1 of the nozzle 1 .
  • the surrounding element 4 is comprised of a main surface 41 surrounding a main orifice 40.
  • the main surface has been represented frusto-conical at Figs. 1 and planar at Figs. 2 and 3, but, as explained above, other arrangements are possible.
  • a raised outer periphery surrounds the main surface 41 ; the raised outer periphery has an interior face 105.
  • the upper face 42 of the periphery is higher than the level of the main surface 41 .
  • a mortar or cement joint at the junction 5 between the refractory element 4 and the nozzle 1 can be provided for further tightness improvement.
  • FIG. 4 shows such a skull collected in a conventional installation (without the surrounding refractory element) and Fig. 5 shows such a skull collected in an installation according to the invention.
  • the skull 20 of Fig. 4 shows significant disturbance in the region 21 , 21 ' indicating the presence of alumina deposit on the inner wall of the nozzle. This alumina deposit is responsible for the clogging of the nozzle with all the detrimental
  • the skull 20 of Fig. 4 shows also an enlarged portion in the region 22, 22' indicating a severe erosion of the nozzle inlet.
  • the skull 20 shown on Fig. 5 corresponds to the inner shape of the nozzle indicating thereby that the nozzle has neither been subjected to erosion nor to alumina clogging.
  • Fig. 6 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are obtuse angles.
  • the height of the raised outer periphery is constant.
  • Fig. 7 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are obtuse angles.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • Fig. 8 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are obtuse angles.
  • portions of the raised outer periphery with a fixed height are joined by height transition segments 44.
  • Fig. 9 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • all angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Fig. 10 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are acute angles.
  • the height of the raised outer periphery is constant.
  • Fig. 1 1 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are acute angles.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • Fig. 12 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • both of the angles shown in the cross-section representation are acute angles.
  • portions of the raised outer periphery with a fixed height are joined by height transition segments 44.
  • Fig. 13 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • all angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are acute.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • FIG. 14 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • one of the angles shown in the cross-section representation is an acute angle; the other angle shown is an obtuse angle.
  • the height of the raised outer periphery is constant around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are parallel.
  • Fig. 15 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are acute, obtuse and, at two points, are right angles.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Fig. 16 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • one of the angles shown in the cross-section representation is an acute angle; the other angle shown is an obtuse angle.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Fig. 17 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • one of the angles shown in the cross-section representation is an acute angle; the other angle shown is an obtuse angle.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Fig. 18 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • one of the angles shown in the cross-section representation is an acute angle; the other angle shown is an obtuse angle.
  • the raised outer periphery has two portions of constant height; these portions are joined by two height transition segments 44. The planes of the constant height portions of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are parallel.
  • Fig. 19 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40 and base bottom face 104.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • Angles 108 are formed between element base bottom face 104 and exterior face 106 of the raised outer periphery.
  • one of the angles shown in the cross-section representation is an acute angle; the other angle shown is an obtuse angle.
  • the raised outer periphery has two portions of constant height; these portions are joined by two height transition segments 44. The planes of the constant height portions of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are parallel.
  • Fig. 20 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes from the interior face 105 of the raised outer periphery of the element.
  • the fin surface nearest main orifice 40 is at an angle from the vertical.
  • Fig. 21 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Two element fins 120 protrude from the interior face 105 of the raised outer periphery of the element.
  • Fig. 22 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • Three element fins 120 protrude from the interior face 105 of the raised outer periphery of the element.
  • Fig. 23 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes from the interior face 105 of the raised outer periphery of the element.
  • FIG. 24 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes from the interior face 105 of the raised outer periphery of the element. The fin extends upwardly above the maximum height of the upper face 42 of the raised outer periphery of the element.
  • Fig. 25 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes inwardly from the interior face 105 of the raised outer periphery of the element as well as outwardly from the exterior face 106 of the raised outer periphery of the element.
  • the fin extends upwardly above the maximum height of the upper face 42 of the raised outer periphery of the element.
  • Fig. 26 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes outwardly from the exterior face 106 of the raised outer periphery of the element.
  • FIG. 27 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery varies around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are not parallel.
  • An element fin 120 protrudes inwardly from the interior face 105 of the raised outer periphery of the element. The fin extends upwardly above the maximum height of the upper face 42 of the raised outer periphery of the element.
  • Fig. 28 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery is constant around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are parallel.
  • a plurality of lateral ports 124 extends from interior face 105 of raised outer periphery of the element to the exterior face 106 of the raised outer periphery of the element. These ports may be cylindrical, or may be flared at one end or at both ends.
  • Fig. 29 shows a perspective view of an element 4 of the present invention having main orifice 40.
  • a raised outer periphery is joined to the base; the raised outer periphery has an exterior face 106 and an upper face 42.
  • angles formed between the bottom face of the base of the element and the exterior face of the raised outer periphery of the element are obtuse.
  • the height of the raised outer periphery is constant around the course of the element's circumference.
  • the plane of the upper face of the raised outer periphery and the plane of the bottom face of the base of the element are parallel.
  • a plurality of paired lateral ports 128 extends from interior face 105 of raised outer periphery of the element to the exterior face 106 of the raised outer periphery of the element. These ports may be cylindrical, or may be flared at one end or at both ends. These ports may be directed so that the longitudinal axes of each of a pair of ports intersect at a circle within the volume partially enclosed by the element, i.e., the volume partially enclosed by the interior face 105 of the raised outer periphery of the element.
  • Fig. 30 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40.
  • a raised outer periphery 140 is joined to the base; the raised outer periphery has an exterior face 106.
  • an externally directed rim 132 is in communication with the exterior face 106 of the raised outer periphery of the element.
  • externally directed rim 132 is horizontal; it may be directed above or below the horizontal in other embodiments.
  • Fig. 31 shows a cross section of an element 4 of the present invention, in which base 102 contains main orifice 40.
  • a raised outer periphery 140 is joined to the base; the raised outer periphery has an interior face 105.
  • an internally directed rim 134 is in communication with the interior face 106 of the raised outer periphery of the element.
  • the internally directed rim takes a truncated conical form; it may be horizontal in other embodiments.
  • Fig. 32 shows a schematic perspective view of an element 4 of the present invention, in which base 102 contains main orifice 40.
  • a raised outer periphery 140 is joined to the base.
  • the raised outer periphery has a gap.
  • Fig. 33 shows a schematic perspective view of an element 4 of the present invention, in which base 102 contains main orifice 40.
  • a raised outer periphery 140 is joined to the base.
  • the raised outer periphery has two gaps.
  • Fig. 34 shows a top view of an assembly of an element 4 of the present invention with a nozzle 1 .
  • the top view depicts the main surface 41 of the element and the outer periphery surrounding the main surface of the element; the interior face 105 of the raised outer periphery is visible, as is the upper face 42 of the raised outer periphery.
  • the interior of the main orifice 40 of the element has a non-circular geometry configured to mate with the exterior geometry of nozzle 1 .
  • the respective geometries are hexagonal. The corresponding geometries constrain the positioning of the element 4 about the nozzle, so that vertical and horizontal asymmetries of the element can be properly positioned within a metallurgical vessel.
  • Fig. 35 shows a top view of an assembly of an element 4 of the present invention with a nozzle 1 .
  • the top view depicts the main surface 41 of the element and the outer periphery surrounding the main surface of the element; the interior face 105 of the raised outer periphery is visible, as is the upper face 42 of the raised outer periphery.
  • the interior of the main orifice 40 of the element has a non-circular geometry configured to mate with the exterior geometry of nozzle 1 .
  • indentations on the interior of main orifice 40 accept protrusions on the surface of nozzle 1 .
  • the corresponding geometries constrain the positioning of the element 4 about the nozzle, so that vertical and horizontal asymmetries of the element can be properly positioned within a metallurgical vessel.
  • Fig. 36 shows a cross section of an element 4 and the walls 152 of a
  • a stopper rod 154 is positioned to be moved vertically to permit or interrupt flow through main orifice 40.
  • the interior face 105 and the exterior face 106 of the raised outer periphery of the element are indicated.
  • Gaps 162 between the element and the metallurgical vessel wall are indicated.
  • the distance 164 between the interior face 105 and the main orifice 40 is also indicated.
  • the asymmetric design on the element embodiment shown permits gaps of the same size between each metallurgical vessel wall 152 and the top of the element, as well as permitting constant, or nearly constant, distances between the interior face 105 and the main orifice 40, while allowing the stopper rod 154 to be positioned closer to one metallurgical vessel wall than to the other.
  • Fig. 37 shows a portion 170 of the raised outer periphery of element 4.
  • the upper face 42 of raised outer periphery of the element contains a plurality of square notches.
  • Fig. 38 shows a portion 170 of the raised outer periphery of element 4.
  • the upper face 42 of raised outer periphery of the element contains a plurality of
  • Fig. 39 shows a portion 170 of the raised outer periphery of element 4.
  • the upper face 42 of raised outer periphery of the element is formed in a sawtooth pattern.
  • Fig. 40 shows a portion 170 of the raised outer periphery of element 4.
  • the upper face 42 of raised outer periphery of the element contains a plurality of
  • Fig. 41 shows a portion 170 of the raised outer periphery of element 4.
  • the upper face 42 of raised outer periphery of the element is formed in a wave pattern.
  • Fig. 42 is a perspective drawing of an element 4 of the present invention, in which base 102 contains main orifice 40 and in communication with raised outer periphery 140. Raised outer periphery 140 houses upper face 42.
  • the maximum external dimension of the base of the element 202, the minimum external dimension of the base of the element 204, the maximum external dimension of the top of the element 206, the minimum external dimension of the top of the element 208, the thickness of the base of the element 222, the thickness of the raised outer periphery of the element 224, the maximum exterior height of the element 232, the maximum interior height of the element 234, the minimum exterior height of the element 236, and the minimum interior height of the element 238 are indicated.
  • a refractory element may comprise a base having a bottom and a main surface, a main orifice passing through the main surface, and a periphery surrounding the main surface, wherein the main orifice has an interior face, wherein the periphery has an interior face, an exterior face and an upper face, wherein the upper face of the periphery is higher than the main surface of the refractory element, wherein the periphery intersects the bottom of the base, and wherein the exterior face of the periphery forms an angle other than a right angle with the bottom of the base in at least one point in their intersection.
  • the exterior face of the periphery may form a right angle with the bottom of the base at two points in their intersection, may form an acute angle with the bottom of the base at all points in their intersection, or may form an obtuse angle with the bottom of the base at all points in their intersection.
  • the plane of the exterior face of the periphery and the plane of the bottom of the base may be non-parallel planes.
  • the upper face of the periphery comprises an upper level and a lower level joined by two transitional non-vertical, non- horizontal portions.
  • the main surface of the element may have a geometry selected from the group consisting of circular, oval, truncated circular, truncated oval, and polygonal geometry.
  • the element may also comprise one or more fins extending from the inner face of the periphery, or one or more fins extending from the exterior face of the periphery.
  • the element may comprise one or more ports passing from the exterior face to the interior face of the periphery.
  • the element may comprise a feature on its surface, for example on the interior face of the main orifice or on the bottom of the base, which may be a marking, a recess, a protrusion, a groove, a lip, a peg, a bore, a notch, a dimple, a mogul, a ridge, a threaded receiver, a key receiver, a bayonet receiver, a bevel, and a non-circular geometry, or any other device or feature which would constrain movement of the element around an axis.
  • the refractory element of the invention may be composed of single pieces or of multiple pieces.
  • the refractory element of the invention may be produced from a high alumina material comprising at least 75 wt.% of AI2O3, less than 1 .0 wt.% of S1O2, and less than 5 wt.% of C.
  • the refractory element may be constructed so that the periphery of the element has a thickness equal to or less than 100 millimeters, and the base of the element has a thickness equal to or less than 100 millimeters.
  • An assembly of a refractory element and a nozzle according to the invention may be composed of a single piece or multiple pieces.
  • the refractory element may comprise a main orifice having a non-circular geometry, and wherein the refractory nozzle comprises an exterior radial surface having a non-circular geometry configured to mate with the refractory element.
  • the refractory element comprises a main orifice interior face having a mating feature, wherein the refractory nozzle comprises an exterior radial surface having a corresponding mating feature configured to engage with the main orifice interior face mating feature.
  • the mating feature of the nozzle and the mating feature of the element when engaged, may prevent rotational motion of the element around the longitudinal axis of the bore of the nozzle.
  • An assembly of a refractory element and a nozzle according to the present invention may be deployed in a metallurgical vessel for the casting of molten metal.
  • the refractory nozzle may have an inlet portion forming a passage through the bottom wall of the metallurgical vessel and a refractory element as previously described surrounding the inlet portion of the nozzle, wherein the inlet portion of the nozzle has a top outer edge, wherein the inlet portion of the nozzle has a longitudinal axis, wherein the main orifice of the element is adapted for matching engagement with at least a portion of the outer surface of the nozzle, wherein the main surface of the base of the element has a lowest level, the lowest level being lower than the top outer edge of the nozzle inlet portion, and wherein at least a portion of the periphery of the refractory element is higher than the surface of the bottom wall of the tundish.
  • the element may comprise a gas impervious refractory material.
  • a process for the continuous casting of steel may comprise pouring the molten steel from a ladle into a metallurgical vessel housing an assembly of a refractory element and a nozzle as described above, and thence into a casting mold.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
PCT/US2012/026856 2011-04-29 2012-02-28 Refractory element, assembly and tundish for transferring molten metal WO2012148560A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
AU2012250255A AU2012250255A1 (en) 2011-04-29 2012-02-28 Refractory element, assembly and tundish for transferring molten metal
RU2014110706/02A RU2014110706A (ru) 2011-04-29 2012-02-28 Огнеупорный элемент, содержащий его узел и металлургический резервуар для перемещения расплавленного металла
KR1020137030321A KR20140022418A (ko) 2011-04-29 2012-02-28 용융 금속을 전달하기 위한 내화 요소, 조립체 및 턴디쉬
US14/009,545 US20140061257A1 (en) 2011-04-29 2012-02-28 Refractory element, assembly and tundish for transferring molten metal
JP2014508346A JP2014512277A (ja) 2011-04-29 2012-02-28 溶融金属を搬送するための耐火要素、組立体及びタンディッシュ
MX2013012585A MX2013012585A (es) 2011-04-29 2012-02-28 Elemento refractario, ensamble y artesa refractaria para transferir metal fundido.
CA2829302A CA2829302A1 (en) 2011-04-29 2012-02-28 Refractory element, assembly and tundish for transferring molten metal
CN201280020864.9A CN103582535A (zh) 2011-04-29 2012-02-28 用于输送熔融金属的耐火元件、组件和中间包
EP12776441.3A EP2701868A4 (en) 2011-04-29 2012-02-28 FIRE-RESISTANT ELEMENT, ARRANGEMENT AND INTERMEDIATE CONTAINER FOR FILLING A MELTED METAL
BR112013025791A BR112013025791A2 (pt) 2011-04-29 2012-02-28 elemento refratário para transferir metal em fusão, conjunto para a transferência de metal em fusão, vaso metalúrgico para o lingotamento de metal em fusão, e, processo para o lingotamento contínuo de aço
ZA2013/06980A ZA201306980B (en) 2011-04-29 2013-09-17 Refractory element, assembly and tundish for transferring molten metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161481136P 2011-04-29 2011-04-29
US61/481,136 2011-04-29

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WO2012148560A1 true WO2012148560A1 (en) 2012-11-01

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US (1) US20140061257A1 (pt)
EP (1) EP2701868A4 (pt)
JP (1) JP2014512277A (pt)
KR (1) KR20140022418A (pt)
CN (1) CN103582535A (pt)
AR (1) AR086101A1 (pt)
AU (1) AU2012250255A1 (pt)
BR (1) BR112013025791A2 (pt)
CA (1) CA2829302A1 (pt)
CL (1) CL2013003112A1 (pt)
MX (1) MX2013012585A (pt)
RU (1) RU2014110706A (pt)
TW (1) TW201242689A (pt)
WO (1) WO2012148560A1 (pt)
ZA (1) ZA201306980B (pt)

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EP2781607A1 (en) * 2013-03-20 2014-09-24 Heraeus Electro-Nite International N.V. Sampler for molten iron
PL3317034T3 (pl) * 2015-07-02 2020-09-07 Vesuvius U S A Corporation Modyfikator wylotu kadzi
JP6663230B2 (ja) * 2016-01-25 2020-03-11 黒崎播磨株式会社 ノズル構造体
CN107225231B (zh) * 2017-07-14 2022-09-02 山东钢铁股份有限公司 一种连铸中间包环形气幕挡墙及其安装方法
DK3524812T3 (da) 2018-02-09 2021-05-31 Siemens Gamesa Renewable Energy As Rotationsindretning og fremgangsmåde til rotation af en vindmøllegenerator
CN109332594B (zh) * 2018-11-20 2021-01-22 中国航发沈阳黎明航空发动机有限责任公司 一种大型铸件用防夹杂浇口杯的连接方法
CN114643338A (zh) * 2022-03-17 2022-06-21 重庆钢铁股份有限公司 一种提高铸铁分流器流嘴使用次数的方法

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US20140061257A1 (en) 2014-03-06
EP2701868A1 (en) 2014-03-05
ZA201306980B (en) 2014-11-26
TW201242689A (en) 2012-11-01
JP2014512277A (ja) 2014-05-22
EP2701868A4 (en) 2015-06-03
CL2013003112A1 (es) 2014-08-22
RU2014110706A (ru) 2015-09-27
AU2012250255A1 (en) 2013-09-26
BR112013025791A2 (pt) 2017-08-08
AR086101A1 (es) 2013-11-20
CA2829302A1 (en) 2012-11-01
CN103582535A (zh) 2014-02-12
MX2013012585A (es) 2013-12-06
KR20140022418A (ko) 2014-02-24

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