WO2012160275A1 - Procede de fabrication d'une mousse. metallique munie de conduits et mousse metallique ainsi obtenue - Google Patents
Procede de fabrication d'une mousse. metallique munie de conduits et mousse metallique ainsi obtenue Download PDFInfo
- Publication number
- WO2012160275A1 WO2012160275A1 PCT/FR2012/000206 FR2012000206W WO2012160275A1 WO 2012160275 A1 WO2012160275 A1 WO 2012160275A1 FR 2012000206 W FR2012000206 W FR 2012000206W WO 2012160275 A1 WO2012160275 A1 WO 2012160275A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- core
- metal foam
- coating
- preform
- conduit
- 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
- B22D25/00—Special casting characterised by the nature of the product
- B22D25/005—Casting metal foams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
- B22C7/02—Lost patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
- B22C9/043—Removing the consumable pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
- B22C9/105—Salt cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D25/00—Special casting characterised by the nature of the product
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/003—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by using permeable mass, perforated or porous materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
Definitions
- the technical sector of the present invention is that of the manufacture of metal foams incorporating ducts opening on either side.
- metal foams can be used in particular in heat exchangers to dissipate or diffuse heat. However, it is important to have one or more conduits passing right through the metal foam to achieve more complex exchangers for the circulation of a second fluid within the exchanger or to make preferential passages (known under the name of "Bypass").
- Patent EP-1808241 describes a process for producing ducts in a metal foam according to which the metal tubes are inserted beforehand into the preform before the casting of the molten aluminum or aluminum alloy or after the casting. This system therefore provides for the insertion of a preformed tube.
- EP-1808241, US-3236706 and EP-2118328 which advocate the manufacture of a preform in the form of granules from a salt, such as sodium chloride. After filling the free space between granules using a molten metal, the salt is dissolved to recover the metal foam.
- the object of the present invention is to provide a metal foam incorporating a through tube obtained during the manufacture of the foam itself.
- the manufacture of the foam is carried out in a conventional manner from a preform of granules as described for example in the document cited below.
- patent EP-2118328 describes a particularly interesting method by proposing to manufacture a preform with granules based on grain meal. This preform is then fired before pouring the metal in order to destroy the carbon chains of the granules.
- This patent therefore provides firstly the manufacture of a paste consisting of flour, sodium chloride and water. From this paste, granules are prepared which are then used to make the preform.
- the subject of the invention is therefore a method for manufacturing a metal foam provided with at least one duct and intended in particular for producing a heat exchanger from a ball preform, characterized in that it disposes in a casting mold a core consisting of a core and a coating of fuse material at low temperature, then the preform is arranged around the core by making intimate contact with the core, and is then caused by heating the removal of the material fuse at low temperature, then pouring the molten metal mass into the mold to fill the free spaces between the balls and between the balls and the core and finally eliminating the balls.
- the conduit is formed, after casting of the metal mass, by the metallic mass replacing the coating of wax.
- the core core is made of ceramic, steel, sand, a soluble material or a material identical to that constituting the preform.
- the core consists of three elements, a first element constituted by the core of ceramic, steel or sand, a second element constituted by a peripheral layer of refractory material and a third element constituted by a coating of material fuse at low temperature.
- the core consists of four elements, a first element constituted by the ceramic core, steel or sand, a second element constituted by a peripheral layer of a refractory material, a third element constituted by a layer of a ceramic material and a fourth layer constituted by the coating of fuse material at low temperature.
- the core is rectilinear.
- the core is provided with curvatures.
- the soul is tubular.
- the fuse material at low temperature is a wax.
- the coating comprises at its inner surface continuous or discontinuous protuberances.
- the invention also relates to the metal foam obtained according to the method according to the invention being provided with at least one conduit.
- the conduit is tubular rectilinear or curved.
- the conduit and the foam are based on aluminum or an aluminum alloy.
- a first advantage of the present invention lies in obtaining a foam incorporating a conduit of the same nature than the metal foam itself.
- Another advantage of the invention lies in obtaining for the first time and simultaneously the metal foam and the duct or ducts.
- Another advantage of the invention lies in the fact of obtaining a conduit of any shape, for example rectilinear, curved, or other.
- Yet another advantage of the invention lies in the elimination of any problem of mechanical strength or thermal conductivity between the duct or ducts and the metal foam.
- FIG. 1 is a view showing a preform into which a core is inserted
- FIGS. 2-6 illustrate sections showing various embodiments of a core
- Fig. 7 is a sectional view showing another embodiment of a core.
- Figures 8 and 9 are sections of the metal foam with a conduit made in situ.
- the preform is made in a known manner, that is to say from agglomerated beads and that this preform is used in a known manner to manufacture a metal foam.
- the material constituting the metal foam is also known and may be mentioned by way of example aluminum, aluminum alloys and all known materials used in foundry. For more precision, reference may be made to the aforementioned patent.
- a core is inserted according to the invention within the preform which it is possible to prepare in different ways.
- the invention is based on the replacement of a fusible coating layer by the same material of the metal foam to make the conduit in situ.
- a preform consisting of the balls 1, compressed or not, in which a core 2 is disposed.
- This core consists of a core 3 and a coating 4.
- a preform 6 to extract its mold for reasons of clarity.
- This preform is. of parallelepipedal shape in which the core 2 has been inserted according to FIG. 1. It can be seen that all the balls 1 are in intimate contact with one another. The end of the coating 4 comes flush with the side wall of the preform while the core 3 is protruding.
- This representation is in no way limiting and the invention may also be achieved by passing the wax to create a skin or obtain a protruding tube relative to the foam.
- the injection mold of the molten metal it first has the core 2 with a straight or inclined position according to the needs of the user and then poured the balls.
- the foam is then made according to known technology that is not necessary to describe in detail. It goes without saying that it is possible to have several cores to obtain several conduits.
- FIG. 2 shows in section a first embodiment of the core 2 consisting of the core 3 and the coating 4.
- the core 3 consists for example of a ceramic material, steel or sand commonly used in foundry technology.
- the coating here consists of a layer of wax or other low temperature fusible material.
- low-temperature fuse material is meant a material having a melting point of 40 ° C to 150 ° C.
- the diameter of the core and the thickness of the coating layer are dictated by the envisaged applications of the metal foam.
- core diameters greater than 2 mm can be envisaged and a coating thickness of 0.5 mm to 10 mm (preferably 0.5 to 3 mm) can be adopted.
- a straight core there is shown a straight core. But it goes without saying that a nucleus of any form can be realized. In this case, we will favor a soul in sand.
- This preform 1 incorporating the core 2 is processed in a conventional manner to manufacture the metal foam.
- the beads are agglomerated together to create the rigid preform, then the coating 4 melted and removed by simple fluid flow.
- the molten metal is injected in a known manner that will occupy the interstitial spaces between the balls and the free space left by the coating between the preform and the remaining core to form the conduit.
- the core 3 is extracted or removed if it is sand to leave free the duct formed.
- FIG. 3 shows in section an alternative embodiment of the core 2 in three parts, namely the core 3 on which a layer 5 of a refractory material is applied and finally the coating 4 of wax or fusible material. at low temperature.
- the interest of this refractory material is to facilitate the release of the core after casting of the metal while the rigidity is provided by the core 3.
- This refractory material also increases the diameter of the final conduit without modifying the core.
- FIG. 4 shows the core 2 according to FIG. 3, the core 3 of which is recessed longitudinally to present a channel 6.
- the advantage of this embodiment lies in the reduction of the material constituting the core 3.
- Another Advantage of such an embodiment remains in the possibility of circulating a flow of air to improve cooling after casting.
- the soul is then in the form of a tube of greater or lesser thickness.
- FIG 5 there is shown in section another embodiment of the core 2 in four parts.
- the core 3 is covered with a layer 5 of a refractory material, itself covered with a layer of a ceramic material 7 and finally the coating layer 4.
- the use of the ceramic material makes it possible to increase the rigidity of the refractory material and to eliminate the potential infiltrations melted aluminum in the refractory and thus avoid micro-cracks.
- FIG. 6 which shows a variant of the embodiment according to FIG. 5, a hollow core 3 is provided in the form of a tube.
- This embodiment allows a material saving of the material constituting the soul.
- All the cores previously described in connection with the figures are inserted in a preform in order to produce one or more conduits inside the metal foam.
- the core is placed in the mold for manufacturing the foam and then the balls are introduced ensuring a good compactness that will promote contact between all the balls. If necessary the preform is compressed.
- All these cores may comprise a core of ceramic material, steel, or sand, and more generally any material used in the field of foundry. It goes without saying that when the core is made of ceramic material or steel it is in the form of a straight bar to ensure its extraction, the duct obtained being rectilinear. The core can occupy any position inside the preform and the tube can then emerge at any point of the metal foam inlet and outlet.
- the core 9 has a plurality of curvatures and covered with a coating 4 of wax or a fuse material at low temperature.
- the core 9 is made of sand or of a friable material.
- the duct obtained within the foam makes it possible to obtain a greater contact area between the fluid flowing in the metal foam and the fluid circulating in the duct.
- FIG. 8 shows a section of a block of metal foam 10 constituted by a wire mesh 11 in which the tubular conduit 12 is formed in the free space between the balls and the core after melting of the coating. It is understood that the thickness of the duct 12 is substantially equal to the thickness of the coating layer.
- FIGs 10 and 11 there is shown an alternative embodiment of making grooves or notches on the outer surface of the core 3 (or refractory material). Said grooves or notches being filled by means of the coating 4, thus producing continuous or discontinuous protuberances 13 at the inner surface of the coating 4, which makes it possible, during the casting of metal, to create an exchange surface arranged inside the duct to improve heat exchange.
- These protuberances 13 are here represented for illustrative and non-exhaustive, in the form of triangular and rectangular sections. It is obvious to those skilled in the art that they may be in other forms to promote heat exchange while preserving the flow of fluid within the conduit.
- An advantage of this embodiment lies in the increase of the exchange surface inside the conduit and therefore the effectiveness of the device.
- Foams according to the invention are particularly suitable for the production of heat exchangers, whatever these exchangers, liquid / liquid, or liquid / gas, or gas / gas, or phase change fluids (liquid ⁇ gas).
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280033638.4A CN103930223B (zh) | 2011-05-25 | 2012-05-23 | 制造具有通道的金属泡沫材料的方法及如此获得的金属泡沫材料 |
CA2837151A CA2837151A1 (fr) | 2011-05-25 | 2012-05-23 | Procede de fabrication d'une mousse metallique munie de conduits et mousse metallique ainsi obtenue |
US14/119,736 US20140186652A1 (en) | 2011-05-25 | 2012-05-23 | Process to manufacture a metal foam provided with channels and metal foam thus produced |
EP12729668.9A EP2714303B1 (fr) | 2011-05-25 | 2012-05-23 | Procede de fabrication d'une mousse. metallique munie de conduits et mousse metallique ainsi obtenue |
BR112013030172A BR112013030172A2 (pt) | 2011-05-25 | 2012-05-23 | processo de fabricação de uma espuma metálica munida de condutos e espuma metálica assim obtida |
KR1020137034399A KR20140033163A (ko) | 2011-05-25 | 2012-05-23 | 채널을 구비하는 메탈 폼의 제조 방법 및 이에 의해 제조된 메탈 폼 |
JP2014511926A JP2014515989A (ja) | 2011-05-25 | 2012-05-23 | チャンネルを備えた金属フォームを製造する方法およびこのようにして製造された金属フォーム |
MX2013013665A MX2013013665A (es) | 2011-05-25 | 2012-05-23 | Método para fabricación de una esponja de metal provista con canales y esponja de metal resultante. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR11.01610 | 2011-05-25 | ||
FR1101610A FR2975613B1 (fr) | 2011-05-25 | 2011-05-25 | Procede de fabrication d'une mousse metallique munie de conduits et mousse metallique ainsi obtenue |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012160275A1 true WO2012160275A1 (fr) | 2012-11-29 |
Family
ID=46354391
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2012/000206 WO2012160275A1 (fr) | 2011-05-25 | 2012-05-23 | Procede de fabrication d'une mousse. metallique munie de conduits et mousse metallique ainsi obtenue |
Country Status (10)
Country | Link |
---|---|
US (1) | US20140186652A1 (fr) |
EP (1) | EP2714303B1 (fr) |
JP (1) | JP2014515989A (fr) |
KR (1) | KR20140033163A (fr) |
CN (1) | CN103930223B (fr) |
BR (1) | BR112013030172A2 (fr) |
CA (1) | CA2837151A1 (fr) |
FR (1) | FR2975613B1 (fr) |
MX (1) | MX2013013665A (fr) |
WO (1) | WO2012160275A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016002870A1 (fr) * | 2014-07-02 | 2016-01-07 | 三菱マテリアル株式会社 | Élément d'échange de chaleur en aluminium poreux |
EP2759359A3 (fr) * | 2013-01-23 | 2018-01-03 | Sikorsky Aircraft Corporation | Noyau quasi autodestructeur pour moulage de précision |
CN110976758A (zh) * | 2019-11-12 | 2020-04-10 | 安徽索立德铸业有限公司 | 一种消失模实型铸造工艺 |
CN111496194A (zh) * | 2020-04-22 | 2020-08-07 | 陈万红 | 一种多孔浇筑构件及其生产工艺 |
US10981230B2 (en) | 2014-05-30 | 2021-04-20 | Mitsubishi Materials Corporation | Porous aluminum complex and method of producing porous aluminum complex |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9623480B2 (en) | 2014-12-19 | 2017-04-18 | Hathibelagal M. Roshan | Steel foam and method for manufacturing steel foam |
US10493522B2 (en) | 2014-12-19 | 2019-12-03 | Maynard Steel Casting Company | Steel foam and method for manufacturing steel foam |
US10137499B2 (en) * | 2015-12-17 | 2018-11-27 | General Electric Company | Method and assembly for forming components having an internal passage defined therein |
CN107520404B (zh) * | 2017-08-03 | 2019-06-14 | 日照市方进金属制品有限公司 | 一种用于消失模的预制金属件 |
CN109252062B (zh) * | 2018-11-07 | 2020-06-30 | 三峡大学 | 一种基于p曲面空间结构的泡沫镍的制备方法 |
KR102174238B1 (ko) | 2019-11-19 | 2020-11-05 | 엠에이치기술개발 주식회사 | 다중코어 및 다중코어를 이용한 중공제품 제조방법 |
KR102412877B1 (ko) * | 2020-12-29 | 2022-06-27 | 엠에이치기술개발 주식회사 | 중공관용 충전모듈 및 이를 이용한 중공관 충전 방법 |
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US3236706A (en) | 1961-11-17 | 1966-02-22 | Dow Chemical Co | Method of making porous metallic article |
WO2003031252A1 (fr) * | 2001-10-05 | 2003-04-17 | Daimlerchrysler Ag | Element support coule pour carrosserie de vehicule |
EP1808241A1 (fr) | 2006-01-16 | 2007-07-18 | Kurtz GmbH | Procédé destiné à la fabrication de composants à pores ouverts en métal, plastique ou céramique |
US20090084520A1 (en) * | 2007-09-28 | 2009-04-02 | Caterpillar Inc. | Heat exchanger with conduit surrounded by metal foam |
US20090085520A1 (en) | 2007-09-27 | 2009-04-02 | Sanyo Electric Co., Ltd. | State of charge optimizing device and assembled battery system including same |
FR2927269A1 (fr) * | 2008-02-13 | 2009-08-14 | C T I F Ct Tech Des Ind De La | Preforme et procede pour la fabrication d'une piece dont une partie interieure est en mousse metallique |
EP2118328B1 (fr) | 2007-02-16 | 2011-03-16 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Procédé de production d'un article en métal poreux |
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2011
- 2011-05-25 FR FR1101610A patent/FR2975613B1/fr not_active Expired - Fee Related
-
2012
- 2012-05-23 KR KR1020137034399A patent/KR20140033163A/ko not_active Application Discontinuation
- 2012-05-23 CA CA2837151A patent/CA2837151A1/fr not_active Abandoned
- 2012-05-23 JP JP2014511926A patent/JP2014515989A/ja not_active Ceased
- 2012-05-23 WO PCT/FR2012/000206 patent/WO2012160275A1/fr active Application Filing
- 2012-05-23 CN CN201280033638.4A patent/CN103930223B/zh not_active Expired - Fee Related
- 2012-05-23 MX MX2013013665A patent/MX2013013665A/es not_active Application Discontinuation
- 2012-05-23 EP EP12729668.9A patent/EP2714303B1/fr not_active Not-in-force
- 2012-05-23 BR BR112013030172A patent/BR112013030172A2/pt not_active IP Right Cessation
- 2012-05-23 US US14/119,736 patent/US20140186652A1/en not_active Abandoned
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US3236706A (en) | 1961-11-17 | 1966-02-22 | Dow Chemical Co | Method of making porous metallic article |
WO2003031252A1 (fr) * | 2001-10-05 | 2003-04-17 | Daimlerchrysler Ag | Element support coule pour carrosserie de vehicule |
EP1808241A1 (fr) | 2006-01-16 | 2007-07-18 | Kurtz GmbH | Procédé destiné à la fabrication de composants à pores ouverts en métal, plastique ou céramique |
EP2118328B1 (fr) | 2007-02-16 | 2011-03-16 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Procédé de production d'un article en métal poreux |
US20090085520A1 (en) | 2007-09-27 | 2009-04-02 | Sanyo Electric Co., Ltd. | State of charge optimizing device and assembled battery system including same |
US20090084520A1 (en) * | 2007-09-28 | 2009-04-02 | Caterpillar Inc. | Heat exchanger with conduit surrounded by metal foam |
FR2927269A1 (fr) * | 2008-02-13 | 2009-08-14 | C T I F Ct Tech Des Ind De La | Preforme et procede pour la fabrication d'une piece dont une partie interieure est en mousse metallique |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2759359A3 (fr) * | 2013-01-23 | 2018-01-03 | Sikorsky Aircraft Corporation | Noyau quasi autodestructeur pour moulage de précision |
US10981230B2 (en) | 2014-05-30 | 2021-04-20 | Mitsubishi Materials Corporation | Porous aluminum complex and method of producing porous aluminum complex |
WO2016002870A1 (fr) * | 2014-07-02 | 2016-01-07 | 三菱マテリアル株式会社 | Élément d'échange de chaleur en aluminium poreux |
JP2016014508A (ja) * | 2014-07-02 | 2016-01-28 | 三菱マテリアル株式会社 | 多孔質アルミニウム熱交換部材 |
US10598446B2 (en) | 2014-07-02 | 2020-03-24 | Mitsubishi Materials Corporation | Porous aluminum heat exchange member |
CN110976758A (zh) * | 2019-11-12 | 2020-04-10 | 安徽索立德铸业有限公司 | 一种消失模实型铸造工艺 |
CN111496194A (zh) * | 2020-04-22 | 2020-08-07 | 陈万红 | 一种多孔浇筑构件及其生产工艺 |
CN111496194B (zh) * | 2020-04-22 | 2023-07-11 | 陈万红 | 一种多孔浇筑构件及其生产工艺 |
Also Published As
Publication number | Publication date |
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FR2975613B1 (fr) | 2013-06-21 |
CN103930223B (zh) | 2015-11-25 |
MX2013013665A (es) | 2014-09-01 |
CN103930223A (zh) | 2014-07-16 |
JP2014515989A (ja) | 2014-07-07 |
EP2714303A1 (fr) | 2014-04-09 |
FR2975613A1 (fr) | 2012-11-30 |
BR112013030172A2 (pt) | 2016-12-06 |
US20140186652A1 (en) | 2014-07-03 |
KR20140033163A (ko) | 2014-03-17 |
CA2837151A1 (fr) | 2012-11-29 |
EP2714303B1 (fr) | 2015-07-08 |
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