EP2686123A1 - Procede pour fabriquer une piece metallique de revolution monobloc a partir de structures fibreuses composites - Google Patents
Procede pour fabriquer une piece metallique de revolution monobloc a partir de structures fibreuses compositesInfo
- Publication number
- EP2686123A1 EP2686123A1 EP12714793.2A EP12714793A EP2686123A1 EP 2686123 A1 EP2686123 A1 EP 2686123A1 EP 12714793 A EP12714793 A EP 12714793A EP 2686123 A1 EP2686123 A1 EP 2686123A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wire
- mandrel
- fibrous structure
- internal
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
-
- 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
- B22F3/002—Manufacture of articles essentially made from metallic fibres
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/02—Pretreatment of the fibres or filaments
- C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
- C22C47/062—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element from wires or filaments only
- C22C47/064—Winding wires
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
- Y10T29/49988—Metal casting
- Y10T29/49989—Followed by cutting or removing material
Definitions
- the present invention relates to a method for manufacturing a metal piece of one-piece revolution from composite fiber structures in the form of fibers, fiber webs, fiber fabrics and the like, coated with metal.
- such a structure comprises metal composite fibers composed of a metal alloy matrix, for example titanium alloy Ti, within which fibers extend, for example ceramic fibers of SiC silicon carbide.
- a metal alloy matrix for example titanium alloy Ti
- Such fibers have a tensile strength much higher than that of titanium (typically 4000 MPa against 1000 MPa). It is therefore the fibers that take up the efforts, the metal alloy matrix providing a binder function for the part, as well as protection and insulation of the fibers, which must not come into contact with each other.
- the ceramic fibers are resistant to erosion, but must necessarily be reinforced with metal.
- These composite materials can be used to produce annular parts of gas turbine revolution for aircraft or other industrial application, such as rings, shafts, cylinder bodies, housings, spacers, reinforcements of monolithic parts such as blades.
- the known methods for producing such pieces of one-piece revolution consist in superimposing, around a rotating cylindrical mandrel, fibrous structures (fibers, sheet of fibers or fiber fabric) in succession and then arranging the fibrous structures. wound composites and mandrel outlets, in a specific receiving tool to heat treat them and finally get the piece of revolution composite material.
- one of the superposed fibrous structures is oriented in a first direction of winding with respect to the longitudinal axis of the mandrel, then the other fibrous structure is wound on the preceding one in a second direction of winding different from the first, so as to obtain two composite fibrous structures having cross winding directions.
- the present invention aims to overcome these disadvantages.
- the method of manufacturing a part of one-piece revolution by superposition, around a rotary cylindrical mandrel, of at least two composite fibrous structures coated with metal, respectively internal and external, wound in first and second directions crossed on said mandrel is remarkable in that it consists of:
- the wire layer acts as an interface between the superposed and crossed fibrous structures and increases the metallic thickness between the structures, so that the over-stresses between the composite fibers of the structures no longer occur.
- the wire is obtained, for example, by wire drawing and is of the same nature as the metal of the composite fibrous structures, so that after passing through the tooling, an intermediate and homogeneous metallic layer having an appropriate thickness is obtained. between the fibers of the structures.
- Wire wire means both a continuous wire and a plurality of son put end to end.
- the wire may also be individual or be in the form of a sheet or ribbon of several parallel or interlaced son, a cable, a fabric of unidirectional son, etc .. without departing from the scope of the invention.
- the superposed winding layers of the wire and the fibrous structures are carried out cold at room temperature, which does not require a complex installation for the implementation of the relevant steps of the process.
- the wire is wound substantially orthogonally to the longitudinal axis of the rotating cylindrical mandrel to form the layer of contiguous turns.
- At least one layer of wire may be arranged around the outer fibrous structure, so that the part obtained superficially presents an outer and inner layer of metal layers.
- the first winding direction of the internal fibrous structure is oriented angularly with respect to the longitudinal axis of the cylindrical mandrel, the second winding direction of the outer fibrous structure then being oriented symmetrically to the first by relative to a radial direction of the mandrel, perpendicular to its longitudinal axis.
- the winding direction of the internal fibrous structure is between 30 ° - 60 ° with respect to the longitudinal axis of the mandrel, the winding direction of the external structure will be between 30 ° - 60 ° + ⁇ / 2.
- the internal and external fibrous structures may be in the form of individual and parallel fibers successively wound around the mandrel, or in the form of parallel sheets or ribbons of fibers, or in the form of parallel fiber fabrics, said structures being arranged with crosswise on the mandrel.
- the first winding direction of the internal fibrous structure is parallel to the longitudinal axis of the cylindrical mandrel, the second winding direction of the outer fibrous structure then being oriented angularly with respect to the axis. longitudinal axis of the mandrel.
- the internal fibrous structure may be in the form of a fabric of fibers parallel to each other and wound around the cylindrical mandrel parallel to its longitudinal axis
- the external fibrous structure may be any, but, of course, with the oriented fibers. angularly with respect to those of the internal structure which are parallel to the mandrel.
- the metal son used may have different diameters, and multilayered superimposed layers of these son may be provided alternately with the superimposed fibrous structures whose number may be greater than two.
- identical references designate similar elements.
- FIGS. 1, 2, 3, 4A, 4B, 4C1, 4C2, 5, 6A, 6B and 7 show schematically the main steps of the method according to the invention, for manufacturing a piece of integral revolution from composite fibrous structures
- FIGS. 4A, 4B, 4C1 and 4C2 proposing different possibilities of external fibrous structures used after the process step illustrated in FIG. 3, while FIGS. 6A and 6B show schematically processing tools of the blank to obtain the part .
- the object of the method is to manufacture a piece of annular, one-piece revolution 1 shown in FIG. 7 only from elongated elements in the form of wires, fibers or the like, as will be seen hereinafter.
- the method consists in using a rotary cylindrical mandrel 2 of longitudinal axis X and firstly wound around the lateral surface 3 thereof in a first step illustrated in FIG. 1, at least one wire 4.
- the wire 4 is made in particular of a titanium alloy of TA6V or 6242 type ensuring thermomechanical strength and lightness, and is obtained in this non-limiting example by wire drawing so that it can be available as a reel or reel from which the wire is drawn.
- its diameter depends on the part to be obtained and perhaps, for example, of the order of a few tenths of a millimeter.
- the wire drawn wire 4 is derived from a not shown spool and is driven substantially perpendicularly to the X axis around the lateral surface 3 of the cylindrical mandrel 2 over an extended area.
- predetermined amount corresponding to the length that it is desired to obtain, after manufacture, for the part of revolution 1, thus forming several contiguous turns 5, and on several predetermined superposed layers 6.
- Figure 2 the three layers 6 formed by the windings of contiguous turns 5 of the same wire 4 around the mandrel.
- a wire 4 ' such as that shown in section in FIG. 1, with a different diameter, which in this case is less than the diameter of the wire 4. This is to show that metal wires having different diameters.
- the method continues with a second step shown in FIG. 2 and consisting in arranging a composite fibrous structure 7 around the wire drawn wire 4.
- the composite fibrous structure 7 is in the form of a fabric 8 of fibers 9 associated parallel to each other and made of ceramic (SiC) or a similar material coated with metal.
- the latter and the metal of the drawn wire are identical in nature (for example in TA6V or 6242 type titanium alloy) to optimize the subsequent step of the process relating to the operation of hot isostatic compaction or isothermal forging .
- a single layer 10 of the fabric 8 is formed around the yarn 4.
- a multiple layer winding 10 could be provided from the same fabric, or even from one or more other tissues. distinctly wound concentrically.
- the wire 1 1 forms a single layer 12 of contiguous turns 13 around the fabric 8.
- a winding of several layers is also possible, depending on the diameter of the wire used, and the separation to be given between the fibrous structure internal composite 7 and a then external composite fibrous structure 14 to be superposed as will be seen below.
- the drawn wire 11 may be the same (diameter, nature) as that used to form the layers 6 on the mandrel 2 and come from the same coil. But, it could also have a different diameter.
- the outer fibrous structure 14 is composed of ceramic composite fibers coated with metal, which may or may not be identical to the preceding fibers. These fibers 15 are wound successively around the turns 13 of the layer 12 of intermediate wire 11, which is according to the invention between the two fibrous structures 7 and 14.
- the fibers 15 are joined and oriented in a second direction D2 by relative to the X axis of the mandrel 2, forming a helix angle A with respect thereto.
- the wound fibers 15 and the fibers 9 of the fabric 8 have different orientation directions D1 and D2 different and cross to allow the realization of rigid monobloc composite parts revolution. Some of the fibers are only partially represented.
- the number of coiled fibers 15 is variable and is a function of the helix angle A to be given, which is for example of the order of 30 ° to 60 °, and the diameter of the fibers.
- a single layer 16 of the fibers 15 is made around the wire 11. Nevertheless, several layers are possible.
- the two internal and external fibrous structures 7 are not in direct contact with each other, being separated by the winding layer of the intermediate metal wire drawn wire 1 acting as an interface, in order to eliminate any over-stress that may appear between them during the cooling of the blank E formed by the structures and the metal wires.
- the outer fibrous structure 14 can consist of the successive winding of plies or ribbons 17 each composed of parallel composite fibers 18 (six in this example), that is to say having a ceramic core or a similar material coated with metal, preferably identical to the wire drawn 1 1.
- transverse metallic weaving threads 19 of identical nature to the drawn wire are regularly spaced apart.
- the number of layers 17 to cover the layer 12 of intermediate wire 11 is a function of the width of the sheet and the helix angle A thereof relative to the winding axis X 2.
- the helix angle A of the plies defines the second direction D2 of the outer fibrous structure 14, crossing the direction D1 of the internal fibrous structure 7. It can be seen in FIG. 4B that two successive identical plies 17 are used to form a single layer 20 of the outer fibrous structure 14. More than one layer 20 could of course be envisaged. And it goes without saying that the outer fibrous structure 14 covers the entire layer of wire 1 January.
- the outer fibrous structure 14 is in the form of a fabric 21 with metal composite fibers 22, assembled parallel to each other.
- the fibers 22 are oriented obliquely with respect to the perpendicular sides 23, 24 of the fabric 21 in the form of a rectangular strip.
- the fabric 21 is presented by its corresponding side 23 (short side) parallel to the longitudinal axis X of the cylindrical mandrel 2, it is wound, by the rotation of the latter, on the layer 12 of wire drawn intermediate 11 and these oblique parallel composite fibers 22 form the desired helix angle A defining the second direction D2 of the outer fibrous structure 14, crossed with the first direction D1 of the internal fibrous structure 7.
- the dimension of the fabric 21 is sufficient to completely cover the layer of drawn wire.
- a layer 25 (or more layers if necessary) of fabric 21 is thus wound on the intermediate wire drawn 1 1.
- the fibers 22 are parallel to the side 23 of the fabric 21 to be wound and are interconnected by son 27. Also, to have a direction of orientation D2 fibers different from that D1 of the internal structure, the fabric 21 itself is obliquely presented by one of its corners 26 relative to the rotating cylindrical mandrel 2, so as to form the desired helix angle A. Thus, the parallel fibers 22 of the fabric 21 are wrapped around the layer 12 of wire drawn 1 1 in the second desired direction D2 crossed with the first direction D1 of the internal fibrous structure 7, parallel to the axis X of the cylindrical mandrel 2. The size of the fabric 21 is such as to completely cover the layer 12 of wire drawn by the winding of said fabric on one or more layers 25.
- the two fibrous structures 7 and 14 have directions D1, D2 crossed and are separated from each other by at least one layer 12 of contiguous turns 13 of the wire 1 1 playing the interface role, according to the invention.
- the successive layers composing the two fibrous structures 7 and 14 their fibers are always parallel from one layer to another with an orientation D1 or D2.
- a subsequent step of the method consists in winding, on the outer fibrous structure 14, at least one layer 28 of drawn wire 29 which may be from the same feed reel as previously .
- a winding with contiguous turns 30 of the wire 29, made substantially orthogonal to the axis X of the cylindrical mandrel 2 is obtained (as a reminder, wire and / or fabric of metal wires).
- other superposed fibrous structures could be arranged taking care to alternate between them, according to the invention, layers of intermediate wire.
- a blank E is obtained from the piece of revolution to be produced, which consists solely of wire drawn wires 4, 1 1, 29 and internal and external structures 7, 14 with composite fibers in individual form, in sheet, in fabric Or other.
- the blank E is transferred to a compaction tooling 31, schematically represented, in which the hot isostatic pressing (CIC) step is carried out in an isothermal press or in an autoclave (the choice depends on the number of pieces to be produced).
- CIC hot isostatic pressing
- FIG. 6A After the transfer and the placement of the blank E in the vacuum press tooling 31, FIG. 6A, more particularly in an open cylindrical receptacle 32 of the press, whose reception volume, defined by its walls 33, corresponds to that of the part to be obtained, the receptacle is closed by a lid 34 of complementary shape to the opening of the receptacle and the transverse face of the blank E opposite.
- the identical metal of the drawn wire 4, 1 1, 29 and the coating of the fibers composite structures 7, 14 becomes pasty eliminating all the empty spaces between the compressed turns, and finally densifying the part being obtained by moving the cover relative to the receptacle, without acting on the silicon carbide matrices of the fibers .
- the receptacle 32 and the cover 34 with the blank E inside are placed in a deformable pouch 36 made of mild steel which is then introduced into the autoclave of tools 31.
- this autoclave is brought to an isostatic pressure of 1000 bar and a temperature of 940 ° C (for the TA6V), so that the whole of the pocket 36 is deformed, arrows F1, retracting by evacuation of the air expelled via the hole 37 and is applied against the receptacle 32 and the cover 34 which, in turn, compress under a uniform pressure the windings of son and fibers until the creep of the metal constituting them (welding diffusion), as before.
- the piece of composite monoblock revolution 1 represented in FIG. 7, is obtained which is made of titanium alloy of the TA6V or 6242 type, with in its core the dies made of ceramic (silicon carbon, for example) fibers 9-15 or 18 or 22 forming cross reinforcement inserts, but separated by the metal layer from the intermediate wire, and whose thickness is such that it avoids the appearance stress between the crossed ceramic fibers, superimposed.
- the part 1 can of course undergo machining operations subsequent to the CIC treatment.
- the orientation direction of the fibers of the internal structure could be different from that described above (parallel to the axis of the mandrel), as well as the choice of a fabric as an internal fibrous structure is not mandatory, any other choice may be considered.
- the winding steps son and fibrous structures are carried out at room temperature without resorting to a complex installation.
- the coated composite fibers may be, in addition to SiC / Ti as described above, SiC / Al, SiC / SiC, SiC / B, etc.
- the minimum radius of the mandrel is a function of the diameter of the wire and must be greater than the latter.
- the length of the piece it can reach several meters if necessary.
Landscapes
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Laminated Bodies (AREA)
- Powder Metallurgy (AREA)
- Moulding By Coating Moulds (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Woven Fabrics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1152129A FR2972661B1 (fr) | 2011-03-15 | 2011-03-15 | Procede pour fabriquer une piece metallique de revolution monobloc a partir de structures fibreuses composites |
| PCT/FR2012/050550 WO2012123686A1 (fr) | 2011-03-15 | 2012-03-15 | Procede pour fabriquer une piece metallique de revolution monobloc a partir de structures fibreuses composites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2686123A1 true EP2686123A1 (fr) | 2014-01-22 |
| EP2686123B1 EP2686123B1 (fr) | 2017-11-01 |
Family
ID=44343260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12714793.2A Active EP2686123B1 (fr) | 2011-03-15 | 2012-03-15 | Procede pour fabriquer une piece metallique de revolution monobloc a partir de structures fibreuses composites |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9321106B2 (fr) |
| EP (1) | EP2686123B1 (fr) |
| CN (1) | CN103459067B (fr) |
| BR (1) | BR112013023463B8 (fr) |
| CA (1) | CA2829012C (fr) |
| FR (1) | FR2972661B1 (fr) |
| RU (1) | RU2584106C2 (fr) |
| WO (1) | WO2012123686A1 (fr) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2970715B1 (fr) * | 2011-01-21 | 2014-10-17 | Snecma | Structure fibreuse tissee multicouches ayant une partie tubulaire creuse, procede de fabrication et piece composite la comportant |
| RU2542221C2 (ru) * | 2013-06-25 | 2015-02-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Способ получения цилиндрической заготовки в виде прутка из металлического армированного композиционного материала |
| CN110640100B (zh) * | 2019-11-20 | 2025-02-07 | 太原科技大学 | 一种连续纤维增强交叉肋金属板成型设备及方法 |
| CN119501488B (zh) * | 2024-11-22 | 2025-10-03 | 中国机械总院集团郑州机械研究所有限公司 | 一种中间合金及其制备方法和应用 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256869A (ja) * | 1993-03-02 | 1994-09-13 | Fuji Heavy Ind Ltd | 繊維強化金属製円筒製品 |
| US5762843A (en) * | 1994-12-23 | 1998-06-09 | Kennametal Inc. | Method of making composite cermet articles |
| ATE322560T1 (de) * | 1999-11-04 | 2006-04-15 | Avio Spa | Verfahren zur herstellung eines bauteiles aus verbundwerkstoff |
| GB0119636D0 (en) * | 2001-08-11 | 2001-10-03 | Rolls Royce Plc | a method of manufacturing a fibre reinforced metal component |
| RU2215816C2 (ru) * | 2001-12-26 | 2003-11-10 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Способ получения композиционного материала на основе интерметаллида титана и изделие, полученное этим способом |
| FR2886181B1 (fr) * | 2005-05-27 | 2008-12-26 | Snecma Moteurs Sa | Procede de fabrication d'une piece tubulaire avec un insert en materiau composite a matrice metallique |
| FR2913053B1 (fr) * | 2007-02-23 | 2009-05-22 | Snecma Sa | Procede de fabrication d'un carter de turbine a gaz en materiau composite et carter ainsi obtenu |
| FR2925895B1 (fr) * | 2007-12-28 | 2010-02-05 | Messier Dowty Sa | Procede de fabrication d'une piece metallique renforcee de fibres ceramiques |
-
2011
- 2011-03-15 FR FR1152129A patent/FR2972661B1/fr active Active
-
2012
- 2012-03-15 WO PCT/FR2012/050550 patent/WO2012123686A1/fr not_active Ceased
- 2012-03-15 US US14/004,555 patent/US9321106B2/en active Active
- 2012-03-15 CA CA2829012A patent/CA2829012C/fr active Active
- 2012-03-15 BR BR112013023463A patent/BR112013023463B8/pt active IP Right Grant
- 2012-03-15 RU RU2013142130/02A patent/RU2584106C2/ru active
- 2012-03-15 EP EP12714793.2A patent/EP2686123B1/fr active Active
- 2012-03-15 CN CN201280013001.9A patent/CN103459067B/zh active Active
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2012123686A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013023463B1 (pt) | 2019-01-02 |
| FR2972661A1 (fr) | 2012-09-21 |
| FR2972661B1 (fr) | 2013-04-12 |
| CA2829012C (fr) | 2018-10-16 |
| EP2686123B1 (fr) | 2017-11-01 |
| CA2829012A1 (fr) | 2012-09-20 |
| US20130340241A1 (en) | 2013-12-26 |
| BR112013023463B8 (pt) | 2019-10-08 |
| BR112013023463A2 (pt) | 2017-08-08 |
| CN103459067B (zh) | 2016-10-12 |
| CN103459067A (zh) | 2013-12-18 |
| RU2584106C2 (ru) | 2016-05-20 |
| WO2012123686A1 (fr) | 2012-09-20 |
| US9321106B2 (en) | 2016-04-26 |
| RU2013142130A (ru) | 2015-04-20 |
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