WO2011048279A1 - Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes - Google Patents
Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes Download PDFInfo
- Publication number
- WO2011048279A1 WO2011048279A1 PCT/FR2009/052014 FR2009052014W WO2011048279A1 WO 2011048279 A1 WO2011048279 A1 WO 2011048279A1 FR 2009052014 W FR2009052014 W FR 2009052014W WO 2011048279 A1 WO2011048279 A1 WO 2011048279A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mold
- liquid metal
- receiving
- ingot
- steel
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/06—Ingot moulds or their manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/04—Casting hollow ingots
Definitions
- the present invention relates to the manufacture of a metal ingot having a longitudinal bore and in particular a steel ingot for producing forged annular parts.
- ingots which are either solid ingots, which must then be the object of a forging operation having the drilling of an axial hole, the direct casting of ingots having a central bore which can be transformed directly in the form of ferrule.
- the solid ingots can be cast under vacuum, which allows them to be made of steel which was degassed at the time of vacuum casting, to obtain guaranteed hydrogen contents of less than 1 ppm.
- ingots having a central bore are cast in air source. These ingots are cast using metal or liquid steel which has been degassed during the pocket metallurgy operations, and which generally have a guaranteed hydrogen content of less than 1.5 ppm.
- the steel takes up a quantity of hydrogen of the order of 0.3 ppm, it is therefore difficult to obtain ingots which can be guaranteed, when the steel is in the liquid state in the mold, a hydrogen content of less than 1, 8 ppm.
- solid ingots although having a low hydrogen content and therefore do not require degassing treatments, require a more complicated forging process. Indeed, this process must include at least one step for making a central hole that requires several forging and reheating operations in furnaces.
- An object of the present invention is to overcome these disadvantages by providing a means for obtaining forging ingots having a longitudinal bore, while having a sufficiently low hydrogen content from the beginning, in order to be able to guarantee conditions of hydrogen content. low on the finished parts, without many thermal degassing treatments being necessary.
- the subject of the invention is a method for producing a metal ingot having a longitudinal bore, by casting of liquid metal in a mold comprising a generally annular molding cavity, defined by an ingot mold extending vertically above the mold. a support, the mold having an upwardly open cavity, a vertical core disposed within the cavity of the mold, and a bottom.
- the mold is disposed inside a vacuum casting chamber comprising, at its upper part, a means for introducing liquid metal;
- a means for receiving and distributing liquid metal adapted to receive the liquid steel introduced into the vacuum casting chamber and for redistributing the liquid metal in the molding cavity, is disposed at the upper part of the molding cavity; , and:
- the liquid metal is introduced into the vacuum casting chamber so as to form a first liquid steel jet under vacuum to discharge the liquid metal onto the receiving and distributing means and forming at least a second vacuum liquid steel jet from the receiving and distributing means and terminating in the molding cavity so as to flow the liquid metal into the molding cavity.
- the liquid metal receiving and distribution means is a cup-shaped distributor comprising at least one evacuation channel, opening into the mold cavity.
- the evacuation channel can have different shapes (tube, elbow .%) and different positions (horizontal, inclined %)
- the means for receiving and distributing the liquid metal is a cone made of refractory material whose tip is adapted to receive the first jet of liquid steel;
- the means for receiving and distributing the liquid metal bears on the upper end of the core
- the core consists of a generally cylindrical body of refractory material comprising a metal axial reinforcement
- the armature of the core is a metal tube, for example steel, whose wall comprises a plurality of holes;
- the mold is generally of revolution
- the liquid metal is liquid steel
- the pressure in the vacuum chamber is less than 0.2 Torr.
- the invention further relates to a steel ingot comprising a longitudinal bore has been obtained by vacuum casting.
- the ingot may for example have a generally rotational shape.
- the ingot may have a hydrogen content of less than 1.2 ppm, preferably less than or equal to 1 ppm and more preferably less than or equal to 0.8 ppm.
- the invention also relates to an apparatus for vacuum casting a metal ingot comprising a longitudinal bore, comprising a molding cavity defined by:
- the means for receiving and distributing the liquid metal is a dish-shaped distributor comprising at least one evacuation channel opening into the molding cavity;
- the means for receiving and distributing the liquid metal is a cone made of refractory material whose tip is adapted to receive the first liquid steel jet.
- FIG. 1 shows in section a vacuum casting installation of a metal ingot having a longitudinal bore
- FIG. 2 is a top view of an ingot mold for casting an ingot having a longitudinal bore provided with means for receiving and distributing the liquid metal;
- FIG. 3 is a diagrammatic representation in section of a second embodiment of a liquid metal distribution device at the top of the ingot casting mold having a longitudinal bore;
- FIG. 4 is an enlarged exploded view of the liquid metal receiving and distribution device shown in FIG.
- Figure 1 there is shown an installation for vacuum casting a metal ingot, and in particular a steel ingot, generally of a shape of revolution and having a longitudinal central bore.
- This installation comprises a mold 1 intended to mold the metal ingot, consisting of a cast iron mold 2 known in itself which delimits a cavity 3 inside which is disposed a vertical core 4.
- the whole is arranged in a vacuum casting chamber 5 consisting of a tank 6 closed by a cover 8 having a pipe 7 pumping connected to a pump installation not shown.
- the cover 8 has a means 9 introduction of the liquid metal inside the vacuum chamber which consists of an intermediate bag 10 closed by a drawer nozzle 1 1 disposed at the junction between the intermediate bag 10 and the vacuum chamber 5.
- Such a vacuum casting installation is known in itself and it makes it possible to pour liquid metal and in particular steel which is first poured into the intermediate bag 10, then which can be penetrated into the vacuum chamber 5 by opening the drawer nozzle 1 1 without breaking the vacuum.
- the mold 1 rests on a wedge 17 whose height is adapted so that the mold is completely disposed inside the vacuum casting chamber 5, which vacuum casting chamber 5 rests under the ground 16.
- the mold 1 comprises a bottom marked generally by 27 comprising a wedging means 18 and a cast iron counterplate 20.
- the bottom is adapted to obtain the desired ingot height.
- the wedging means is for example cast iron.
- the space between the wedging means and the side wall of the mold is filled with dry sand 19.
- the counterplate cast iron 20 for receiving the lower portion of the vertical core 4 is surrounded by chromite gaskets.
- the mold 2, the core 4 and the bottom 27 define a generally annular mold cavity 3A intended to receive the liquid metal.
- the vertical core 4 of generally cylindrical shape, is constituted, in its outer part, chromite surrounding a metal frame consisting of a steel tube 42 extending over the entire height and whose wall may optionally have holes.
- This metal reinforcement is intended on the one hand, to ensure the rigidity and strength of the vertical core 4 and on the other hand, to form a chimney through which can evacuate the gases resulting from degassing of the chromite core.
- the chromite core may advantageously be coated with a refractory lining based on zirconium silicate or any equivalent product.
- grinding plates 22 are arranged on the inner wall of the mold and on the wall external of the kernel. Such massaging slabs are known per se to those skilled in the art.
- a means 1 1 A for receiving and distributing the liquid steel which is introduced into the vacuum chamber is disposed at the upper part of the mold.
- This means 1 1 A for receiving and distributing liquids is constituted by a tray-shaped distributor 12 consisting of tabular alumina, which comprises at its periphery channels 13 opening vertically above the molding cavity 3A.
- the channels 13 are intended to drive the liquid steel which is contained inside the distributor 12 in the molding cavity 3A.
- These channels 13 are of refractory material and are contained in housings 14 filled with sand. They rest on a support plate 15 which bears on the upper part of the vertical core 4 and on the upper face of the mold 2.
- the distributor 12 comprises an inner bowl 121 from which four channels 13 are located which are contained in four holding boxes containing sand 14 and which are supported by the arms 122 of the support plate 15. These arms 122, which are arranged in a cross, rest on the top of the mold 2.
- the mold 1 comprises massaging plates 22 which surround a on the other hand, the mold 2.
- massing plates 22 are known in themselves to those skilled in the art.
- the vacuum casting chamber 5 is evacuated by pumping through the pipe 7 using a vacuum pumping installation known in itself. Even of the skilled person. Thus, the pressure of the atmosphere within the vacuum chamber 5 is lowered to a value that can fall below 0.5 Torr, and better below 0.2 Torr, and better still below 0, 1 Torr.
- the vacuum is achieved in the enclosure, there is a steel pocket above the intermediate pocket 10, it pours liquid steel in the pocket intermediate 10.
- the intermediate bag 10 is sufficiently filled with steel, it opens the drawer nozzle 1 1, which allows to introduce liquid steel inside the vacuum chamber 5.
- This liquid steel forms a first jet 50 which forms a reserve 51 of liquid steel in the bowl 121 of the distributor 12.
- the reserve 51 of liquid steel then flows through the channels 13 to form secondary jets 52 which introduce liquid steel inside the molding cavity 3A and which gradually fill this molding cavity 3 forming a volume of liquid steel 53 inside the molding cavity 3A.
- an ingot may be obtained having a longitudinal bore which, when still in the liquid state inside the mold, may have a hydrogen content substantially less than 0.8 ppm.
- it may however start from a liquid steel having a hydrogen content greater than 1.5 ppm, while still obtaining an ingot whose hydrogen content will be substantially less than 0.8 ppm.
- the molding cavity 3A filled with liquid steel it proceeds in a known manner by allowing the ingot to solidify inside the vacuum casting chamber 5.
- the vacuum casting chamber 5 can then be opened by removing the cover 8, then removing the receiving and distributing means 11, and then demolding the ingot in a manner known in itself to the man of the job.
- a metal ingot in particular a steel ingot, and in particular low alloy steel, having high metal properties, which can be used to manufacture forgings for heavy equipment, such as plant vessels, is obtained.
- the ingot has a very low hydrogen content, which can be guaranteed less than 1, 2 ppm and even less than 1 ppm, and better still, possibly lower than 0.8 ppm.
- the means 1 1 A for receiving and distributing the liquid metal consists of a distributor 12 comprising a bowl and which bears on the central core 4.
- a distributor 12 comprising a bowl and which bears on the central core 4.
- Other modes of realization are possible, the main thing being to achieve at least the formation of two successive streams of liquid metal, under vacuum, which can burst so as to provide two successive degassing operations.
- FIG 3 there is shown another possible embodiment in which the mold 2 is surmounted by a receiving means and distribution 1 1 'of the jet 50 of liquid metal which is introduced into the vacuum casting chamber.
- This means 1 1 ' is constituted by a cone 1 10 bearing on the central core 4.
- the liquid metal which comes from the jet 50 flows on an area 51' which is on the outer periphery of the cone 1 10, and then opens into the molding cavity 3A forming jets 52 'which are exploded and which can ensure a very good degassing.
- FIG. 4 the cone 1 10 of the liquid steel receiving and distribution means is shown, which is completed by a U-shaped rider 1 1 1 which is intended to hold the cone 1 10.
- the mold may consist of several assembled segments.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Continuous Casting (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
Claims
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2778193A CA2778193C (fr) | 2009-10-21 | 2009-10-21 | Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes |
EP09768538.2A EP2490842B1 (fr) | 2009-10-21 | 2009-10-21 | Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes |
US13/503,115 US8875776B2 (en) | 2009-10-21 | 2009-10-21 | Method for manufacturing a metal ingot comprising a bore, and associated ingot and molding device |
JP2012534735A JP5552170B2 (ja) | 2009-10-21 | 2009-10-21 | 縦方向の穴を含む金属製インゴットを製造する方法および真空鋳造する装置 |
PL09768538T PL2490842T3 (pl) | 2009-10-21 | 2009-10-21 | Sposób wytwarzania metalowego wlewka zawierającego otwór, odpowiedni wlewek i urządzenie do odlewania |
BR112012009542-0A BR112012009542A2 (pt) | 2009-10-21 | 2009-10-21 | processo para fabricar um lingote metálico, lingote de aço e dispositivo de moldagem |
CN200980162469.2A CN102655965B (zh) | 2009-10-21 | 2009-10-21 | 制造包括镗孔的金属铸锭的方法、铸锭和相关的铸造装置 |
PCT/FR2009/052014 WO2011048279A1 (fr) | 2009-10-21 | 2009-10-21 | Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes |
SI200930846T SI2490842T1 (sl) | 2009-10-21 | 2009-10-21 | Postopek izdelave kovinskega ingota, obsegajočega luknjo, tovrsten ingot in livarska priprava za izdelavo |
RU2012120723/02A RU2526649C2 (ru) | 2009-10-21 | 2009-10-21 | Способ изготовления металлического слитка, содержащего отверстие, соответствующие слиток и устройство литья |
UAA201206016A UA104222C2 (ru) | 2009-10-21 | 2009-10-21 | Способ изготовления металлического или стального бруска, содержащего отверстие, соответствующий брусок и формовочное устройство |
ES09768538.2T ES2448547T3 (es) | 2009-10-21 | 2009-10-21 | Procedimiento para fabricar un lingote metálico que comprende un orificio mecanizado, lingote y dispositivo de moldeo asociados |
KR1020127012898A KR101443469B1 (ko) | 2009-10-21 | 2009-10-21 | 보어를 포함하는 금속 잉곳을 제조하는 방법, 및 이에 관한 잉곳 및 주조 장치 |
US14/500,018 US9586258B2 (en) | 2009-10-21 | 2014-09-29 | Molding device for a metal ingot comprising a bore |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/FR2009/052014 WO2011048279A1 (fr) | 2009-10-21 | 2009-10-21 | Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/503,115 A-371-Of-International US8875776B2 (en) | 2009-10-21 | 2009-10-21 | Method for manufacturing a metal ingot comprising a bore, and associated ingot and molding device |
US14/500,018 Division US9586258B2 (en) | 2009-10-21 | 2014-09-29 | Molding device for a metal ingot comprising a bore |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011048279A1 true WO2011048279A1 (fr) | 2011-04-28 |
Family
ID=42497515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2009/052014 WO2011048279A1 (fr) | 2009-10-21 | 2009-10-21 | Procede pour fabriquer un lingot metallique comportant un alesage, lingot et dispositif de moulage associes |
Country Status (13)
Country | Link |
---|---|
US (2) | US8875776B2 (fr) |
EP (1) | EP2490842B1 (fr) |
JP (1) | JP5552170B2 (fr) |
KR (1) | KR101443469B1 (fr) |
CN (1) | CN102655965B (fr) |
BR (1) | BR112012009542A2 (fr) |
CA (1) | CA2778193C (fr) |
ES (1) | ES2448547T3 (fr) |
PL (1) | PL2490842T3 (fr) |
RU (1) | RU2526649C2 (fr) |
SI (1) | SI2490842T1 (fr) |
UA (1) | UA104222C2 (fr) |
WO (1) | WO2011048279A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112012009542A2 (pt) * | 2009-10-21 | 2020-08-18 | Arcelormittal Investigación Y Desarollo Sl | processo para fabricar um lingote metálico, lingote de aço e dispositivo de moldagem |
CN104275450B (zh) * | 2014-10-11 | 2016-05-18 | 清华大学 | 一种底注式浇注铸锭的方法及专用装置 |
CN104785757B (zh) * | 2015-03-27 | 2016-11-30 | 辽宁科技大学 | 一种多芯还原多包共浇复合浇铸大型钢锭的方法及装置 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3310850A (en) * | 1963-12-13 | 1967-03-28 | Rheinstahl Huettenwerke Ag | Method and apparatus for degassing and casting metals in a vacuum |
FR2422459A1 (fr) * | 1978-04-11 | 1979-11-09 | Kawasaki Steel Co | Procede de fabrication d'un lingot d'acier creux et dispositif pour mettre en oeuvre le procede |
US5052469A (en) * | 1988-09-20 | 1991-10-01 | Showa Denko Kabushiki Kaisha | Method for continuous casting of a hollow metallic ingot and apparatus therefor |
FR2676670A1 (fr) * | 1991-05-23 | 1992-11-27 | Creusot Loire | Procede et dispositif de coulee d'un lingot creux metallique. |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5028898B1 (fr) * | 1970-01-20 | 1975-09-19 | ||
JPS5638295B2 (fr) * | 1974-05-01 | 1981-09-05 | ||
JPS54134034A (en) * | 1978-04-11 | 1979-10-18 | Kawasaki Steel Co | Production of hollow steel block |
JPS54143703A (en) * | 1978-04-28 | 1979-11-09 | Kobe Steel Ltd | Vacuum induction melting apparauts |
JPS5633164A (en) * | 1979-08-22 | 1981-04-03 | Mitsubishi Steel Mfg Co Ltd | Manufacture of steel ingot by remelting |
SU1088868A1 (ru) * | 1983-02-14 | 1984-04-30 | Предприятие П/Я А-3681 | Способ получени полого слитка |
SU1359062A1 (ru) * | 1986-05-05 | 1987-12-15 | Волгоградский Политехнический Институт | Устройство дл получени полых слитков |
FR2676671B1 (fr) * | 1991-05-23 | 1994-01-14 | Creusot Loire Industrie | Procede et dispositif de coulee d'un lingot creux utilisant un noyau refroidi de maniere reglable. |
JPH05318027A (ja) * | 1992-05-25 | 1993-12-03 | Kobe Steel Ltd | 鋳造方法 |
JPH06190538A (ja) * | 1992-12-24 | 1994-07-12 | Hitachi Ltd | 低水素鋼塊の製造方法 |
JP4427439B2 (ja) * | 2004-12-02 | 2010-03-10 | 株式会社神戸製鋼所 | 中空状の鍛造用鋼材の製法および筒状鍛造品の製法 |
JP4443430B2 (ja) * | 2005-01-25 | 2010-03-31 | 東邦チタニウム株式会社 | 電子ビーム溶解装置 |
BR112012009542A2 (pt) * | 2009-10-21 | 2020-08-18 | Arcelormittal Investigación Y Desarollo Sl | processo para fabricar um lingote metálico, lingote de aço e dispositivo de moldagem |
-
2009
- 2009-10-21 BR BR112012009542-0A patent/BR112012009542A2/pt active Search and Examination
- 2009-10-21 EP EP09768538.2A patent/EP2490842B1/fr not_active Not-in-force
- 2009-10-21 WO PCT/FR2009/052014 patent/WO2011048279A1/fr active Application Filing
- 2009-10-21 US US13/503,115 patent/US8875776B2/en not_active Expired - Fee Related
- 2009-10-21 RU RU2012120723/02A patent/RU2526649C2/ru active
- 2009-10-21 JP JP2012534735A patent/JP5552170B2/ja not_active Expired - Fee Related
- 2009-10-21 KR KR1020127012898A patent/KR101443469B1/ko active IP Right Grant
- 2009-10-21 UA UAA201206016A patent/UA104222C2/ru unknown
- 2009-10-21 SI SI200930846T patent/SI2490842T1/sl unknown
- 2009-10-21 ES ES09768538.2T patent/ES2448547T3/es active Active
- 2009-10-21 PL PL09768538T patent/PL2490842T3/pl unknown
- 2009-10-21 CN CN200980162469.2A patent/CN102655965B/zh not_active Expired - Fee Related
- 2009-10-21 CA CA2778193A patent/CA2778193C/fr not_active Expired - Fee Related
-
2014
- 2014-09-29 US US14/500,018 patent/US9586258B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3310850A (en) * | 1963-12-13 | 1967-03-28 | Rheinstahl Huettenwerke Ag | Method and apparatus for degassing and casting metals in a vacuum |
FR2422459A1 (fr) * | 1978-04-11 | 1979-11-09 | Kawasaki Steel Co | Procede de fabrication d'un lingot d'acier creux et dispositif pour mettre en oeuvre le procede |
US5052469A (en) * | 1988-09-20 | 1991-10-01 | Showa Denko Kabushiki Kaisha | Method for continuous casting of a hollow metallic ingot and apparatus therefor |
FR2676670A1 (fr) * | 1991-05-23 | 1992-11-27 | Creusot Loire | Procede et dispositif de coulee d'un lingot creux metallique. |
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Title |
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ASO KAZUO ET AL: "MANUFACTURE OF FORGED SHELL RINGS FOR PWR NUCLEAR REACTOR VESSELS.", KAWASAKI STEEL TECHNICAL REPORT 1986 OCT, no. 15, October 1986 (1986-10-01), pages 65 - 73, XP002596087 * |
MIKIO KUSUHASHI ET AL (THE JAPAN STEEL WORKS LTD, JAPAN): "Manufacturing of Low Neutron Irradiation Einbrittlement Sensitivity Core Region Shells for Nuclear Reactor Pressure Vessels", EJAM - E-JOURNAL OF ADVANCED MAINTENANCE, vol. 1, 3 February 2009 (2009-02-03), JAPAN, pages 87 - 98, XP002596086 * |
OHASHI NOBUO ET AL (KAWASAKI STEEL CORP.): "Manufacturing process and properties of nuclear RPV shell ring forced from hollow ingot", NUCLEAR ENGINEERING AND DESIGN, vol. 81, no. 2, September 1984 (1984-09-01), pages 193 - 205, XP002596085, DOI: 10.1016/0029-5493(84)90007-4 * |
Also Published As
Publication number | Publication date |
---|---|
SI2490842T1 (sl) | 2014-03-31 |
US20150013931A1 (en) | 2015-01-15 |
EP2490842A1 (fr) | 2012-08-29 |
US8875776B2 (en) | 2014-11-04 |
RU2526649C2 (ru) | 2014-08-27 |
JP2013508162A (ja) | 2013-03-07 |
UA104222C2 (ru) | 2014-01-10 |
US20120269672A1 (en) | 2012-10-25 |
KR101443469B1 (ko) | 2014-10-14 |
CN102655965A (zh) | 2012-09-05 |
PL2490842T3 (pl) | 2014-05-30 |
EP2490842B1 (fr) | 2013-12-11 |
CA2778193C (fr) | 2014-10-14 |
US9586258B2 (en) | 2017-03-07 |
BR112012009542A2 (pt) | 2020-08-18 |
JP5552170B2 (ja) | 2014-07-16 |
RU2012120723A (ru) | 2013-11-27 |
KR20120080637A (ko) | 2012-07-17 |
CN102655965B (zh) | 2016-02-24 |
ES2448547T3 (es) | 2014-03-14 |
CA2778193A1 (fr) | 2011-04-28 |
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