WO2006117425A1 - Method for forming a tight-fitting silver surface on an aluminium piece - Google Patents
Method for forming a tight-fitting silver surface on an aluminium piece Download PDFInfo
- Publication number
- WO2006117425A1 WO2006117425A1 PCT/FI2006/000132 FI2006000132W WO2006117425A1 WO 2006117425 A1 WO2006117425 A1 WO 2006117425A1 FI 2006000132 W FI2006000132 W FI 2006000132W WO 2006117425 A1 WO2006117425 A1 WO 2006117425A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heating
- aluminium
- piece
- silver
- temperature
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
Definitions
- the invention relates to a method for forming a highly electroconductive surface on an aluminium piece.
- a highly electroconductive layer of silver is formed on the piece by means of a eutectic join.
- the temperature of the aluminium piece is raised gradually and the oxide layer formed on the surface of the piece is removed.
- the silver piece that is to be attached is transferred to the cleaned surface and, by simultaneously applying loading to the contact point, it is heated to a temperature where an alloy consistent with the eutectic point is generated between the aluminium and silver, which goes on to form a metallurgical join as it solidifies.
- Aluminium is a metal used a lot in electricity-conducting structures, because its conductivity is so good.
- aluminium forms an oxide layer on its surface in an air atmosphere, which considerably hampers the conductivity of electricity to or from the aluminium piece. From time to time it is necessary to improve the electrical conductivity of the aluminium piece locally, and this is performed for instance by joining copper pieces to the aluminium piece.
- methods are also known where an aluminium and silver join has been made, although not always for reasons of improving conductivity.
- the greatest problem is generally the immediate oxidation of the aluminium in the air atmosphere.
- the aluminium oxide that is generated is difficult to remove permanently in connection with normal soldering methods.
- commercial cadmium- and fluoride-containing fluxing agents do not remove oxides in sufficient quantities and the join formed by soldering remains porous and weak.
- a method is known from WO application 2004/042121 , in which a silver coating layer is formed on an aluminium electrode support bar.
- the contact between the aluminium and the coating material is achieved in particular with a thermal spray coating method.
- the thermal spraying technique breaks the passivation layer of the aluminium i.e. the oxide layer, so that the contact of the metals is good enough for a metallurgical join to form and for the coating to attach to its substrate.
- a hermetic coating on the surface of the aluminium can be achieved with thermal spraying methods, but the equipment required by the methods is rather expensive as yet.
- thermal spraying methods typically in thermal spraying methods, not all of the coating material ends up on the surface of the piece to be coated, and instead, some of the coating material is wasted with regard to the efficiency of the method.
- EP patent publication 28763 describes a method for joining metal pieces to each other.
- the pieces may be the same metal or different metals.
- the metal joins described in the patent are Al-Al, Cu-Cu and Al-Cu, and also described are joins in which an intermediate agent is introduced between the pieces to be joined, such as an insert of silicon, aluminium-silicon alloy or silver. Bonding takes place by means of pressure at raised oxygen pressure, exploiting the eutectic reaction occurring between the metals.
- the temperature required by the eutectic reaction depends on the materials to be bonded and the temperature used is in the region of the eutectic temperature - +5O 0 C.
- the description of the method reveals that when an oxygen- enriched atmosphere is used for heating the pieces, the oxide layers formed on the contact points of the pieces are squeezed out with the liquefied eutectic alloy. Pure oxygen is used in the examples and the pressure used was in the region of 150 - 710 bar.
- the bonding of the pieces to each other described in the EP publication takes place at very high pressure, which squeezes the impurities and the layer that was oxidized during heating out of the joining point.
- the use of an oxygen atmosphere in heating and the high pressure make this a very expensive bonding method.
- JP application 57195592 relates to a method to join silver and aluminium to each other, in which the oxidation of the surfaces is prevented by making a join by hot pressing and in a vacuum or inert atmosphere.
- the purpose of the invention is to eliminate the drawbacks that arise in the methods described above.
- the purpose of the invention is to put forward a simple and cheap method for forming a highly conductive silver coating on a piece of aluminium.
- the aim is to put forward a method in which the silver coating is formed on the surface of the aluminium piece in a normal or slightly reductive environment and where the loading used in the join is only a fraction of that used in the prior art.
- the purpose of the invention is to put forward a method in which the aluminium piece is heated in stages, so that the silver piece is placed on the surface of the aluminium between heating periods. Before the silver piece is applied, the oxide layer may also be removed from the surface of the aluminium piece.
- the invention relates to a method for forming a highly electroconductive silver coating on the surface of an aluminium piece, whereby the aluminium piece, cleaned of the oxide layer, is heated in stages. After the first heating stage the silver piece is applied to the surface of the aluminium. The second heating stage is carried out at least at the temperature required by the eutectic reaction between aluminium and silver, where a metallurgical join is formed from the diffusion and molten layer between the metals. Heating takes place in atmospheric or slightly reductive conditions. Loading of around
- the loading is spot-like and repeated cyclically.
- the oxide layer is removed from the join surface of the aluminium piece as necessary after the first heating stage before the silver piece is applied to the join surface.
- the minimum eutectic melting point is at 567 0 C.
- the solubility of silver into aluminium rises steeply from 400 0 C up to the eutectic temperature, where the maximum solubility is around 56 per cent by weight.
- the solubility of aluminium into silver at the eutectic point is around 5 per cent by weight.
- the aim was to form a metallurgical join between aluminium and silver as easily and straightforwardly as possible.
- the join area of an aluminium piece is cleaned of its oxide layer and heated to 270 - 33O 0 C, preferably to 300 0 C.
- the removal of the oxide layer may be performed mechanically for instance by grinding, since the join area in question is generally not extensive. If necessary the removal of the oxide layer is also carried out after the first heating stage.
- the removal of an oxide layer at high temperatures can easily be avoided, and treatment can be done in its entirety before commencing heating.
- grinding can be carried out between heating stages too.
- the silver piece or silver foil to be attached is applied to the surface of the aluminium piece and the heating of the pieces is continued in the second stage towards the eutectic point of Al-Ag.
- the silver piece is pressed lightly so that the loading is around 0.2 - 3 bar.
- the pressure does not necessarily have to be continuous and over the entire area of the silver piece, instead it is preferably spot-like and repeated cyclically.
- the join area reaches the eutectic point, eutectics begin to bubble out under the silver piece. Heating is continued until there is a eutectic melt in the entire join area.
- the eutectic alloy that is formed solidifies and the silver is fastened to the aluminium by a metallurgical bond.
- Heating of the aluminium piece takes place depending on the piece either using a preheating torch, a heat-controlled heating tool adapted for the object (e.g. resistance-operated) or in a furnace. Heating may be done in either a normal air atmosphere or in slightly reductive conditions. Reductive conditions are achieved when for instance the preheating torch is adjusted to work with a reductive flame. If heating is performed in a furnace, either an inert shielding gas (e.g. argon) or a reductive gas (e.g. hydrogen) can be fed into the furnace.
- an inert shielding gas e.g. argon
- a reductive gas e.g. hydrogen
- finishing machining reduces the efficiency of a coating material made with hot spraying for instance in exactly the same way.
- a silver join was made on aluminium test rods with the method according to the invention. Heating was carried out with an acetylene torch and the temperature of the pieces was monitored during heating with a thermocouple-based digital surface thermometer. When the surface temperature of the test rod reached 300 0 C, the oxide layer was removed from the surface by grinding and the silver piece was placed on the cleaned surface. Heating was resumed up to the eutectic temperature of 567 0 C. Spot-like and intermittent loading of the order of 0.3 - 0.6 bar was directed on some test rods during heating, and others were not subjected to any loading at all. In practice heating could be continued to 25 0 C, even 4O 0 C above the eutectic point.
- Diffusion reactions proceed so quickly at said temperatures in the metals in question, that the formation of the join takes only a few seconds.
- controlling the temperature can be done visually by monitoring the behaviour of the melt / the melt bubbling out of the join edge.
- a reductive flame is achieved by ordinary torch adjustment (reductive part in the flame).
- Microsections were taken from the cooled test rods, and were examined by microscope.
- the microscope pictures showed that the eutectic in the test rods fabricated without loading had spread with a fragmentary and undulating topography, in fairly thick zones towards both the aluminium and the silver.
- the pictures also show a sigma phase, which is generated in the high temperatures of the eutectic point.
- the thickness of the join edge was several hundreds of micrometres.
- the microscope pictures of the test rods where loading had been used during joining showed that during mechanical compression the eutectic melt had bubbled out of the join edge and as a result there was an even join edge that was only tens of micrometres in thickness.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Manufacture Of Switches (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Chemically Coating (AREA)
- Insulators (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008508242A JP4937249B2 (en) | 2005-04-29 | 2006-04-25 | Method for forming an adherent silver surface on an aluminum material |
EA200702076A EA011380B1 (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
AU2006243159A AU2006243159B2 (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
EP06725893A EP1880040B1 (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
BRPI0610839-3A BRPI0610839A2 (en) | 2005-04-29 | 2006-04-25 | method for forming a silver surface firmly mounted on an aluminum part |
AT06725893T ATE518020T1 (en) | 2005-04-29 | 2006-04-25 | METHOD FOR FORMING A CLOSE-FITTING SILVER SURFACE ON AN ALUMINUM PART |
CA2605007A CA2605007C (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
US11/912,532 US8006892B2 (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
MX2007013181A MX2007013181A (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20050449A FI119647B (en) | 2005-04-29 | 2005-04-29 | A method for forming a dense silver surface on an aluminum piece |
FI20050449 | 2005-04-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006117425A1 true WO2006117425A1 (en) | 2006-11-09 |
Family
ID=34508134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI2006/000132 WO2006117425A1 (en) | 2005-04-29 | 2006-04-25 | Method for forming a tight-fitting silver surface on an aluminium piece |
Country Status (15)
Country | Link |
---|---|
US (1) | US8006892B2 (en) |
EP (1) | EP1880040B1 (en) |
JP (1) | JP4937249B2 (en) |
KR (1) | KR101261078B1 (en) |
CN (1) | CN100562604C (en) |
AT (1) | ATE518020T1 (en) |
AU (1) | AU2006243159B2 (en) |
BR (1) | BRPI0610839A2 (en) |
CA (1) | CA2605007C (en) |
EA (1) | EA011380B1 (en) |
ES (1) | ES2370604T3 (en) |
FI (1) | FI119647B (en) |
MX (1) | MX2007013181A (en) |
WO (1) | WO2006117425A1 (en) |
ZA (1) | ZA200708557B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2457131A (en) * | 2007-12-12 | 2009-08-12 | Innovation Patents Ltd | Silver article and method of cleaning a silver article |
WO2010000930A1 (en) | 2008-07-02 | 2010-01-07 | Valvas Oy | Method of providing electric current taker for support bar, and support bar |
WO2010149849A1 (en) * | 2009-06-25 | 2010-12-29 | Valvas Oy | Method for producing conductor rail used in electrolysis, and conductor rail |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8727203B2 (en) | 2010-09-16 | 2014-05-20 | Howmedica Osteonics Corp. | Methods for manufacturing porous orthopaedic implants |
CN106283123A (en) * | 2016-09-30 | 2017-01-04 | 天津宝兴威科技有限公司 | A kind of preparation method of nanometer silver coating |
CN109396588B (en) * | 2018-09-12 | 2022-03-15 | 云南科威液态金属谷研发有限公司 | Application of liquid metal in removing oxide film on surface of aluminum or aluminum alloy and method thereof |
DE102021213241A1 (en) | 2021-11-24 | 2023-05-25 | Hugo Kern Und Liebers Gmbh & Co. Kg Platinen- Und Federnfabrik | Process and device for welding dissimilar metallic joining partners |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2612682A (en) | 1946-04-05 | 1952-10-07 | Reynolds Metals Co | Method of cladding a copper-base metal to an aluminum core |
US3180022A (en) * | 1960-09-02 | 1965-04-27 | North American Aviation Inc | Method of bonding aluminum members |
EP0028763A2 (en) | 1979-10-29 | 1981-05-20 | Hitachi, Ltd. | Method for pressure bonding metal members by utilizing eutectic reaction |
GB1604976A (en) * | 1977-06-16 | 1981-12-16 | Chugai Electric Ind Co Ltd | Ag-sno alloy composite electrical contact |
JPS57195592A (en) | 1981-05-29 | 1982-12-01 | Nec Corp | Joining method for silver and aluminum |
EP0091222A2 (en) * | 1982-04-06 | 1983-10-12 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | Process for the diffusion bonding of aluminium based materials |
WO2004042121A1 (en) | 2002-11-07 | 2004-05-21 | Outokumpu Oyj | Method for the formation of a good contact surface on an aluminium support bar and a support bar |
EP1514634A1 (en) * | 2003-09-10 | 2005-03-16 | Fortum OYJ | Method for coating a contact surface of an electric conductor |
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US3063145A (en) * | 1957-08-15 | 1962-11-13 | Bell Telephone Labor Inc | Soldering of aluminum |
US3180222A (en) * | 1962-09-24 | 1965-04-27 | Tsoy K Moy | Simplified system to control postlaunch flooding |
US3381366A (en) * | 1965-10-01 | 1968-05-07 | Olin Mathieson | Process for obtaining a composite article |
GB1166465A (en) * | 1966-01-13 | 1969-10-08 | Olin Mathieson | Process for Obtaining a Composite Metal Article |
US3551998A (en) * | 1967-11-08 | 1971-01-05 | Gen Electric | Metallurgical bonding of dissimilar metals |
US3667110A (en) * | 1969-11-03 | 1972-06-06 | Contacts Inc | Bonding metals without brazing alloys |
CA961760A (en) * | 1971-12-30 | 1975-01-28 | Nicholas T. E. Dillon | Oxy-acetylene torches |
CN1016799B (en) * | 1988-02-04 | 1992-05-27 | 东南大学 | Controlled aluminium-powder calorization |
DE4118004A1 (en) * | 1991-06-01 | 1992-12-03 | Kabelmetal Electro Gmbh | METHOD FOR PRODUCING STRAND-SHAPED GOODS PLATED WITH A LAYER OF ALUMINUM |
JPH10148106A (en) * | 1996-11-19 | 1998-06-02 | Fuji Oozx Inc | Tappet for aluminum made internal combustion engine and manufacture thereof |
JP3850257B2 (en) * | 2000-10-19 | 2006-11-29 | 独立行政法人産業技術総合研究所 | Low temperature forming method for brittle material structures |
GB0118348D0 (en) * | 2001-07-27 | 2001-09-19 | Ghoshouni Amir A S | Surface treatment of aluminium-based materials |
-
2005
- 2005-04-29 FI FI20050449A patent/FI119647B/en not_active IP Right Cessation
-
2006
- 2006-04-25 MX MX2007013181A patent/MX2007013181A/en active IP Right Grant
- 2006-04-25 EA EA200702076A patent/EA011380B1/en not_active IP Right Cessation
- 2006-04-25 JP JP2008508242A patent/JP4937249B2/en not_active Expired - Fee Related
- 2006-04-25 CA CA2605007A patent/CA2605007C/en not_active Expired - Fee Related
- 2006-04-25 BR BRPI0610839-3A patent/BRPI0610839A2/en not_active IP Right Cessation
- 2006-04-25 EP EP06725893A patent/EP1880040B1/en not_active Not-in-force
- 2006-04-25 WO PCT/FI2006/000132 patent/WO2006117425A1/en active Application Filing
- 2006-04-25 CN CNB2006800146651A patent/CN100562604C/en not_active Expired - Fee Related
- 2006-04-25 US US11/912,532 patent/US8006892B2/en not_active Expired - Fee Related
- 2006-04-25 KR KR1020077024962A patent/KR101261078B1/en not_active IP Right Cessation
- 2006-04-25 ES ES06725893T patent/ES2370604T3/en active Active
- 2006-04-25 AU AU2006243159A patent/AU2006243159B2/en not_active Ceased
- 2006-04-25 AT AT06725893T patent/ATE518020T1/en not_active IP Right Cessation
-
2007
- 2007-10-08 ZA ZA200708557A patent/ZA200708557B/en unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US2612682A (en) | 1946-04-05 | 1952-10-07 | Reynolds Metals Co | Method of cladding a copper-base metal to an aluminum core |
US3180022A (en) * | 1960-09-02 | 1965-04-27 | North American Aviation Inc | Method of bonding aluminum members |
GB1604976A (en) * | 1977-06-16 | 1981-12-16 | Chugai Electric Ind Co Ltd | Ag-sno alloy composite electrical contact |
EP0028763A2 (en) | 1979-10-29 | 1981-05-20 | Hitachi, Ltd. | Method for pressure bonding metal members by utilizing eutectic reaction |
JPS57195592A (en) | 1981-05-29 | 1982-12-01 | Nec Corp | Joining method for silver and aluminum |
EP0091222A2 (en) * | 1982-04-06 | 1983-10-12 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | Process for the diffusion bonding of aluminium based materials |
WO2004042121A1 (en) | 2002-11-07 | 2004-05-21 | Outokumpu Oyj | Method for the formation of a good contact surface on an aluminium support bar and a support bar |
EP1514634A1 (en) * | 2003-09-10 | 2005-03-16 | Fortum OYJ | Method for coating a contact surface of an electric conductor |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2457131A (en) * | 2007-12-12 | 2009-08-12 | Innovation Patents Ltd | Silver article and method of cleaning a silver article |
WO2010000930A1 (en) | 2008-07-02 | 2010-01-07 | Valvas Oy | Method of providing electric current taker for support bar, and support bar |
KR20110036926A (en) * | 2008-07-02 | 2011-04-12 | 발바스 오와이 | Method of providing electric current taker for support bar, and support bar |
US8303793B2 (en) | 2008-07-02 | 2012-11-06 | Valvas Oy | Method of providing electric current taker for support bar, and support bar |
AU2009265569B2 (en) * | 2008-07-02 | 2013-10-24 | Valvas Oy | Method of providing electric current taker for support bar, and support bar |
EA020970B1 (en) * | 2008-07-02 | 2015-03-31 | Валвас Оу | Method of providing electric current taker for support bar, and support bar |
KR101638031B1 (en) | 2008-07-02 | 2016-07-11 | 발바스 오와이 | Method of providing electric current taker for support bar, and support bar |
WO2010149849A1 (en) * | 2009-06-25 | 2010-12-29 | Valvas Oy | Method for producing conductor rail used in electrolysis, and conductor rail |
EA021594B1 (en) * | 2009-06-25 | 2015-07-30 | Валвас Ой | Method for producing conductor rail used in electrolysis, and conductor rail |
Also Published As
Publication number | Publication date |
---|---|
CN100562604C (en) | 2009-11-25 |
ZA200708557B (en) | 2008-10-29 |
FI20050449A0 (en) | 2005-04-29 |
KR20080005935A (en) | 2008-01-15 |
EA011380B1 (en) | 2009-02-27 |
EP1880040A1 (en) | 2008-01-23 |
EA200702076A1 (en) | 2008-04-28 |
EP1880040A4 (en) | 2010-03-10 |
ATE518020T1 (en) | 2011-08-15 |
CA2605007A1 (en) | 2006-11-09 |
US20080190994A1 (en) | 2008-08-14 |
BRPI0610839A2 (en) | 2010-07-27 |
FI119647B (en) | 2009-01-30 |
JP2008539330A (en) | 2008-11-13 |
CN101166849A (en) | 2008-04-23 |
CA2605007C (en) | 2014-01-28 |
ES2370604T3 (en) | 2011-12-20 |
AU2006243159B2 (en) | 2011-03-10 |
JP4937249B2 (en) | 2012-05-23 |
US8006892B2 (en) | 2011-08-30 |
EP1880040B1 (en) | 2011-07-27 |
FI20050449A (en) | 2006-10-30 |
MX2007013181A (en) | 2008-01-16 |
KR101261078B1 (en) | 2013-05-06 |
AU2006243159A1 (en) | 2006-11-09 |
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