WO2012026823A1 - Brazing pre-flux coating - Google Patents
Brazing pre-flux coating Download PDFInfo
- Publication number
- WO2012026823A1 WO2012026823A1 PCT/NO2011/000228 NO2011000228W WO2012026823A1 WO 2012026823 A1 WO2012026823 A1 WO 2012026823A1 NO 2011000228 W NO2011000228 W NO 2011000228W WO 2012026823 A1 WO2012026823 A1 WO 2012026823A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- flux
- binder
- solvent
- filler material
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing heat exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/203—Fluxing, i.e. applying flux onto surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3603—Halide salts
- B23K35/3605—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/04—Tubular or hollow articles
- B23K2101/14—Heat exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- the present invention is related to a pre-flux coating for the manufacturing of components by brazing, in particular manufacturing of heat exchangers of aluminium components including one or more fluxes and filler material(s).
- Heat exchangers can either be mechanically assembled or they can be brazed. It is state of the art to braze aluminium heat exchanger in so-called CAB process which stands for Controlled Atmosphere Brazing. It is called Controlled Atmosphere as the brazing takes place under the protection of inert gas. Typically this is nitrogen.
- the known pre-flux coatings are combination of a flux and filler material. Flux is required to clean the surfaces of the aluminium parts from oxides and the filler metal is required for the metallic bonding.
- non-corrosive fluxes are mainly comprised of aluminium fluorides such as potassium aluminium fluoride.
- the required filler metal is usually a low melting aluminium alloy from AA4xxx series (containing silicon).
- aluminium heat exchangers are commonly used for automotive applications. Such heat exchangers are commonly used in air conditioning system, engine cooling system, engine oil cooling system and in automotive engine turbo- charger systems.
- aluminium heat exchangers are now to an increasing extent being used for non-automotive applications such as industrial and residential applications performing similar functions as in automotive applications
- the flux typically potassium aluminium fluoride
- the process parameters are modified depending on the type/size of heat exchanger to be brazed as well as the types of filler metal and flux compounds used.
- a new type of braze coating does away with the requirement of having one of the components made from clad material (AISi material).
- This coating type is called SilfluxTM (made by Solvay), which has been introduced by the applicant under the trade name HYBRAZTM' ® .
- SilfluxTM made by Solvay
- HYBRAZ simplifies the heat exchanger manufacturing process by doing away with the need of general flux application. Besides simplifying the manufacturing process, HYBRAZ also offers several benefits to the finished heat exchanger. Some benefits are: The elimination of plugged fin louvers associated with general flux application that reduces heat exchanger performance. Less flux residue on the fin and tube allowing for the application of post braze hydrophilic coatings. The benefits of the HYBRAZ coating are evident in the market due to the increased demand for
- HYBRAZ can be used for other components that make up a heat exchanger design such as welded tubes or folded tubes).
- the tube can be coated using the HYBRAZ process with materials containing fluxes and/or filler alloy.
- the protective layer can in general be of the following two types:
- a passive layer is a coating that is chemically passive (dead) and covers the surface.
- a sacrificial layer is a layer which is less noble than the core material. It will result in lateral corrosion when exposed to aggressive environment.
- a typical sacrificial layer on aluminium is the application of a zinc layer. This zinc layer can be applied to the aluminium surface by zinc arc spraying. Metallic zinc is applied to the MPE surface typically in line during the extrusion process. Full corrosion protection occurs after the tube has passed through a brazing cycle and a zinc diffusion gradient is formed into the tube.
- the HYBRAZTM /@ coated products containing reactive Zn flux will provide flux for brazing as well as a Zn diffusion gradient into the tube for corrosion protection.
- Zn flux is a so called reactive flux from potassium fluorozudie type, generating brazing flux and metallic zinc during the brazing cycle.
- the metallic zinc forms a Zn gradient into the Al tube as a sacrificial layer.
- clad fin is needed to braze the fin-tube joints.
- the invention is characterized by the features as defined in the attached independent claim 1 .
- the pre-flux coating according to the present invention is based on a mixture of flux particles from different fluxes with different properties, as well as Si particles as filler material and including a solvent and binder. More precisely the present invention is composed of fluxes in the form of potassium aluminum fluoride (K-i -3 AIF 4-6 ), potassium trifluoro zincate (KZnF 3 ), lithium aluminum fluoride L13AIF6, filler material in the form of metallic Si particles, Al-Si particles and/or potassium fluoro silicate K 2 SiF 6 , and solvent and binder containing at least 10% by weight of a synthetic resin which is based, as its main constituent, on methacrylate homopolymer or methacrylate copolymer.
- K-i -3 AIF 4-6 potassium trifluoro zincate
- Li aluminum fluoride L13AIF6 lithium aluminum fluoride L13AIF6
- the potassium aluminium fluoride (KI-3AIF 4 -6) as mentioned above can be KAIF 4 and K2AIF5 and K3AIF6 or a combination of these. This is a product from a real synthesis. Potassium trifluoro zincate, KZnF 3 is added for corrosion protection.
- the potassium fluoro silicate K 2 SiF6 reacts with Al and generates Si metal, which forms AISM 2 as filler metal. Further, lithium aluminium fluoride Li 3 AIF 6 is added for limiting water solubility of flux residues and therefore limited attack from stationary water.
- optionally potassium aluminum fluoride (see above) plus cesium aluminium fluoride CsAIF 4 , mechanically blended, may be added.
- the content of solvent may preferably be approximately 30wt % depending on the desired application properties. Further the ratio of particles and binder may vary from 3:1 to 4:1.
- Additional thickener might be added to the coating material (cellulose), content approx. 14wt% related to acrylic binder.
- the ratio of particles of the different fluxes may vary as is apparent from the table below.
- the coating as applied on an aluminium component may further vary with different total load between 8 g/m 2 and 16 g/m 2 . See as well in this connection the table below.
- the coating is produced by mixing based on the following sequence:
- the coating is again subjected to stirring to guarantee a homogenous coating material.
- viscosity of the coating is adjusted according to the application process and equipment.
- Drying of coated components may take place in a separate drying process, e.g. using IR light or other heating sources.
- the coating may be blended and applied as a one layer coating or a multi layer coating.
- One layer coating represents the preferred embodiment of the invention and implies that all flux components are mixed with binder and solvent and are applied in one step to the aluminium surface.
- the coating is mixed as separate coatings with binder and solvent and can be applied in 2, 3 or 4 layers as follows:
- potassium aluminum fluoride In a first layer flux, potassium aluminum fluoride, and filler material or filler generating material are applied to the aluminium surface.
- the coating with Li flux content can be applied either in the first or in the second layer.
- the Li content can be applied within each of the coating layers
- the Li content is applied as a single layer as well.
- the pre-flux coating may be provided on an aluminium component
- any technique may be used such as roll coating, dip coating, spray coating or even screen printing.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Details Of Heat-Exchange And Heat-Transfer (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11820230.8A EP2608919A4 (en) | 2010-08-23 | 2011-08-22 | Brazing pre-flux coating |
JP2013525857A JP2013536085A (en) | 2010-08-23 | 2011-08-22 | Pre-flux coating for brazing |
BR112013003985A BR112013003985A2 (en) | 2010-08-23 | 2011-08-22 | "preflow coating for the fabrication of components by brazing, and coating application". |
US13/817,834 US20130299564A1 (en) | 2010-08-23 | 2011-08-22 | Brazing pre-flux coating |
KR20137004367A KR20140005855A (en) | 2010-08-23 | 2011-08-22 | Brazing pre-flux coating |
CN2011800409499A CN103354769A (en) | 2010-08-23 | 2011-08-22 | Brazing pre-flux coating |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO20101172 | 2010-08-23 | ||
NO20101172 | 2010-08-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012026823A1 true WO2012026823A1 (en) | 2012-03-01 |
Family
ID=45723649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NO2011/000228 WO2012026823A1 (en) | 2010-08-23 | 2011-08-22 | Brazing pre-flux coating |
Country Status (7)
Country | Link |
---|---|
US (1) | US20130299564A1 (en) |
EP (1) | EP2608919A4 (en) |
JP (1) | JP2013536085A (en) |
KR (1) | KR20140005855A (en) |
CN (1) | CN103354769A (en) |
BR (1) | BR112013003985A2 (en) |
WO (1) | WO2012026823A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014065074A1 (en) * | 2012-10-24 | 2014-05-01 | ハリマ化成株式会社 | Brazing composition, tube for heat exchanger, and heat exchanger |
US11346608B2 (en) | 2016-01-29 | 2022-05-31 | Deere & Company | Heat exchanger with improved plugging resistance |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6749244B2 (en) * | 2014-03-11 | 2020-09-02 | ソルヴェイ(ソシエテ アノニム) | Brazing flux |
TWI660913B (en) * | 2014-04-16 | 2019-06-01 | 比利時商首威公司 | Process for brazing of aluminium alloys and a flux |
FR3021285B1 (en) * | 2014-05-20 | 2016-05-13 | Renault Sa | MOTOR VEHICLE ROOF PAVILION SOUDO-BRASE WITH COTES OF CAISSE |
EP3176273B1 (en) | 2014-07-30 | 2018-12-19 | UACJ Corporation | Aluminium alloy brazing sheet |
FR3028023B1 (en) * | 2014-10-29 | 2019-05-24 | Fives Cryo | CORROSION RESISTANT HEAT EXCHANGER MATRIX AND METHOD FOR MANUFACTURING SUCH MATRIX |
CN104588909A (en) * | 2014-12-11 | 2015-05-06 | 徐国华 | Environment-friendly lead-free solder and preparation method |
WO2016093017A1 (en) | 2014-12-11 | 2016-06-16 | 株式会社Uacj | Brazing method |
CN106181126A (en) * | 2015-05-05 | 2016-12-07 | 播磨化成株式会社 | Heat exchanger component, soldering compositions and heat exchanger |
JP6186455B2 (en) | 2016-01-14 | 2017-08-23 | 株式会社Uacj | Heat exchanger and manufacturing method thereof |
CN105679989B (en) * | 2016-03-16 | 2019-01-04 | 惠州亿纬控股有限公司 | A kind of battery electrode terminal production method |
EP3442792B1 (en) * | 2016-04-12 | 2022-02-23 | Gränges AB | Method for manufacturing a clad sheet product |
JP6312968B1 (en) | 2016-11-29 | 2018-04-18 | 株式会社Uacj | Brazing sheet and method for producing the same |
JP7053281B2 (en) | 2017-03-30 | 2022-04-12 | 株式会社Uacj | Aluminum alloy clad material and its manufacturing method |
DE102019106291A1 (en) * | 2019-03-12 | 2020-09-17 | Mahle International Gmbh | Method for manufacturing a component of a temperature control circuit |
Citations (4)
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WO2001038040A1 (en) * | 1999-11-23 | 2001-05-31 | Norsk Hydro Asa | Aluminium product with excellent brazing characteristics |
WO2003001579A1 (en) * | 2001-06-25 | 2003-01-03 | Tokyo Electron Limited | Substrate treating device and substrate treating method |
JP2006348372A (en) * | 2005-06-20 | 2006-12-28 | Mitsubishi Alum Co Ltd | High strength aluminum alloy material for automobile heat-exchanger |
WO2010060869A1 (en) * | 2008-11-25 | 2010-06-03 | Solvay Fluor Gmbh | Anticorrosive flux |
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JPS58167097A (en) * | 1982-03-29 | 1983-10-03 | Nikkei Giken:Kk | Flux for brazing |
JP3419062B2 (en) * | 1994-02-24 | 2003-06-23 | 日本軽金属株式会社 | Aluminum brazing method |
JP3337416B2 (en) * | 1998-02-24 | 2002-10-21 | 株式会社デンソー | Aluminum extruded porous flat tube with excellent brazing properties for automotive heat exchangers and method for producing the same |
JPH11291028A (en) * | 1998-04-09 | 1999-10-26 | Furukawa Electric Co Ltd:The | Manufacture of metal covering with brazing filler metal |
NO20013961D0 (en) * | 2001-08-15 | 2001-08-15 | Norsk Hydro As | Aluminum product and process for making the same |
AU2003234143A1 (en) * | 2002-04-22 | 2003-11-03 | Alcoa Inc. | Flux coated brazing sheet |
JP4611797B2 (en) * | 2005-04-28 | 2011-01-12 | 三菱アルミニウム株式会社 | Aluminum alloy plate material for radiator tubes with excellent brazeability, and radiator tube and heat exchanger provided with the same |
EP1808255A1 (en) * | 2006-01-11 | 2007-07-18 | Corus Aluminium Walzprodukte GmbH | Method of manufacturing a brazed assembly |
-
2011
- 2011-08-22 CN CN2011800409499A patent/CN103354769A/en active Pending
- 2011-08-22 WO PCT/NO2011/000228 patent/WO2012026823A1/en active Application Filing
- 2011-08-22 US US13/817,834 patent/US20130299564A1/en not_active Abandoned
- 2011-08-22 EP EP11820230.8A patent/EP2608919A4/en not_active Withdrawn
- 2011-08-22 KR KR20137004367A patent/KR20140005855A/en not_active Application Discontinuation
- 2011-08-22 JP JP2013525857A patent/JP2013536085A/en active Pending
- 2011-08-22 BR BR112013003985A patent/BR112013003985A2/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001038040A1 (en) * | 1999-11-23 | 2001-05-31 | Norsk Hydro Asa | Aluminium product with excellent brazing characteristics |
WO2003001579A1 (en) * | 2001-06-25 | 2003-01-03 | Tokyo Electron Limited | Substrate treating device and substrate treating method |
JP2006348372A (en) * | 2005-06-20 | 2006-12-28 | Mitsubishi Alum Co Ltd | High strength aluminum alloy material for automobile heat-exchanger |
WO2010060869A1 (en) * | 2008-11-25 | 2010-06-03 | Solvay Fluor Gmbh | Anticorrosive flux |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014065074A1 (en) * | 2012-10-24 | 2014-05-01 | ハリマ化成株式会社 | Brazing composition, tube for heat exchanger, and heat exchanger |
JP2014083570A (en) * | 2012-10-24 | 2014-05-12 | Harima Chemicals Inc | Brazing composition, tube for heat exchanger and heat exchanger |
CN104755222A (en) * | 2012-10-24 | 2015-07-01 | 播磨化成株式会社 | Brazing composition, tube for heat exchanger, and heat exchanger |
CN104755222B (en) * | 2012-10-24 | 2016-11-16 | 播磨化成株式会社 | Soldering compositions, heat exchanger pipe and heat exchanger |
US10092983B2 (en) | 2012-10-24 | 2018-10-09 | Harima Chemicals, Incorporated | Brazing composition, heat exchanger tube, and heat exchanger |
US11346608B2 (en) | 2016-01-29 | 2022-05-31 | Deere & Company | Heat exchanger with improved plugging resistance |
Also Published As
Publication number | Publication date |
---|---|
BR112013003985A2 (en) | 2018-10-16 |
KR20140005855A (en) | 2014-01-15 |
US20130299564A1 (en) | 2013-11-14 |
JP2013536085A (en) | 2013-09-19 |
CN103354769A (en) | 2013-10-16 |
EP2608919A1 (en) | 2013-07-03 |
EP2608919A4 (en) | 2014-07-23 |
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