EP1888819B1 - Verfahren zur vorbereitung von metallischen werkstücken zum kaltumformen - Google Patents
Verfahren zur vorbereitung von metallischen werkstücken zum kaltumformen Download PDFInfo
- Publication number
- EP1888819B1 EP1888819B1 EP06742777.3A EP06742777A EP1888819B1 EP 1888819 B1 EP1888819 B1 EP 1888819B1 EP 06742777 A EP06742777 A EP 06742777A EP 1888819 B1 EP1888819 B1 EP 1888819B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- phosphate
- process according
- phosphating
- coating
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- 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]
- Y10T428/31678—Of metal
Definitions
- Phosphating processes have been used for decades to protect against corrosion, to increase the adhesion of subsequent coatings, such as e.g. a lacquer layer and / or to improve the Kaltumform s in use.
- aqueous zinc-rich phosphating solutions are used for this purpose.
- bodies are pretreated with very high quality zinc manganese nickel phosphating, which provide a very high corrosion protection and a very high paint adhesion before the paint system is applied.
- Lubricant carrier salts calcium hydroxide or phosphates, in particular based on zinc phosphate, can be applied as a first layer to the surfaces of the metallic workpieces to be formed.
- these coatings additionally require a lubricant layer so that the workpieces coated in this way can be used for cold forming.
- the content of an alkaline earth metal-containing phosphating solution of fluoride and complex fluoride is preferably zero, since these contents often lead to precipitation.
- the content of an alkaline earth metal-free phosphating solution of fluoride or / and complex fluoride is preferably in the range of 0.01 to 5 g / L, which content may cause pickling.
- the value of the total acid GS (TA) of a phosphating solution is preferably in the range from 20 to 200 points, more preferably in the range from 30 to 120 points, in particular from 70 to 100 points.
- the value of the total acid Fischer GSF (TAF) is preferably in the range from 6 to 100 points, more preferably in the range from 7 to 70 or from 8 to 60 points, in particular at 35 to 55 points.
- the value of the free acid FS (FA) is preferably 1 to 50 Points, more preferably 2 to 40 points, especially 4 to 20 points.
- the alternating current may preferably have an amplitude in the range from 0.5 to 30 A / dm 2 , particularly preferably in the range from 1 to 20 A / dm 2 , very particularly preferably in the range from 1.5 to 15 A / dm 2 , in particular in the range of 2 to 8 A / dm 2 .
- the contactable or contacted anode is used predominantly or wholly in the phosphating solution of the bath and preferably consists of a metallic, electrically conductive material, which - if it dissolves in the phosphating and optionally enriched, possibly as a mud - not the phosphating and not affects the electrolytic phosphating. Therefore, ferrous materials are basically possible, which slowly dissolve in the bath and form iron phosphate-rich sludge.
- the anode consists of a in the bath solution not or little dissolvable material such as titanium-based, in particular because of the conductivity and possibly low solubility in the bath solution still with a Precious metal of the 8th subgroup of the Periodic Table of the Chemical Elements may be coated.
- At least one lubricant layer is then applied to the at least one phosphate coating, preferably in a thickness in the range from 1 to 40 ⁇ m, more preferably in the range from 2 to 30 ⁇ m, usually with a coating weight in the range from 1 to 40 g / m 2 , often with a coating weight in the range of 3 to 30 g / m 2 , partly with a coating weight in the range of 5 to 18 g / m 2 .
- a reactive stearate-containing solution or suspension - as in many wires - results in a layer system that together with the phosphate coating substantially three layers and usually more or less inconsistent.
- this layer package preferably has a thickness in the range from 2 to 100 ⁇ m, particularly preferably in the range from 4 to 75 ⁇ m, very particularly preferably in the range from 6 to 50 ⁇ m, in particular in the range from 8 to 25 ⁇ m.
- the optionally at least partially chemically converted phosphate coating and the at least one, optionally partially chemically converted lubricant layer together often have a coating weight in the range of 2 to 100 g / m 2 . The thus coated metallic workpieces can then be cold formed.
- the metallic workpieces in particular also strips or sheets which are coated with at least one phosphate coating, can then be used in particular for cold forming and / or for the sliding friction insert.
- at least one substantially organic coating may be applied before and / or after at least one cold working.
- the wire was switched as a cathode, inserted vertically into the beaker with the phosphating solution and then immediately applied current. After the treatment time, which represents the time of the applied current, the power was turned off and immediately the wire was run, rinsed and dried with compressed air.
- the titanium anode was switched as the cathode and the wire as the anode, there was only one stain effect, but no well-recognizable coating.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005023023.7A DE102005023023B4 (de) | 2005-05-19 | 2005-05-19 | Verfahren zur Vorbereitung von metallischen Werkstücken zum Kaltumformen, mit dem Verfahren beschichtete Werkstücke und ihre Verwendung |
PCT/EP2006/004121 WO2006122651A1 (de) | 2005-05-19 | 2006-05-03 | Verfahren zur vorbereitung von metallischen werkstücken zum kaltumformen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1888819A1 EP1888819A1 (de) | 2008-02-20 |
EP1888819B1 true EP1888819B1 (de) | 2019-07-10 |
Family
ID=36791735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06742777.3A Active EP1888819B1 (de) | 2005-05-19 | 2006-05-03 | Verfahren zur vorbereitung von metallischen werkstücken zum kaltumformen |
Country Status (14)
Country | Link |
---|---|
US (1) | US20080166575A1 (zh) |
EP (1) | EP1888819B1 (zh) |
JP (1) | JP2008540845A (zh) |
CN (1) | CN101189366B (zh) |
AU (1) | AU2006246764B2 (zh) |
BR (1) | BRPI0610136B1 (zh) |
CA (1) | CA2608390C (zh) |
DE (1) | DE102005023023B4 (zh) |
EA (1) | EA012533B1 (zh) |
ES (1) | ES2749926T3 (zh) |
MX (1) | MX2007014320A (zh) |
UA (1) | UA93509C2 (zh) |
WO (1) | WO2006122651A1 (zh) |
ZA (1) | ZA200710308B (zh) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100792278B1 (ko) * | 2007-02-27 | 2008-01-07 | 고려상사주식회사 | 인산염 피막 냉간 압조용 스테인리스 강선 및 이를 이용한직결 나사 |
DE102007061109B4 (de) * | 2007-12-19 | 2013-01-17 | Henkel Ag & Co. Kgaa | Behandlungslösung zum Beschichten eines Stahlbandes, ein Verfahren zum Aufbringen derselben sowie ein Stahlband mit einer Beschichtung erhalten aus der Behandlungslösung zur Verbesserung des Umformverhaltens |
TWI457431B (zh) | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一種潤滑劑組成物的方法 |
TWI457433B (zh) | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一磷酸鹽層然後施以一潤滑劑層的方法 |
TWI457432B (zh) | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一含蠟的潤滑劑組成物的方法 |
DE102008000600B4 (de) * | 2008-03-11 | 2010-05-12 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel, die hiermit erzeugte Beschichtung und ihre Verwendung |
DE102009041248A1 (de) * | 2009-09-04 | 2011-05-05 | Innotere Gmbh | Bioaktiv beschichtete Metallimplantate und Verfahren zu deren Herstellung |
DE102011009012A1 (de) * | 2011-01-20 | 2012-07-26 | Profil Verbindungstechnik Gmbh & Co. Kg | Funktionselement in Form eines Einpresselements |
CN102719872B (zh) * | 2012-06-08 | 2018-04-27 | 南京派诺金属表面处理技术有限公司 | 一种无渣低温快速电解磷化液及其磷化工艺 |
CN102899702B (zh) * | 2012-08-31 | 2015-10-28 | 华南理工大学 | 镁合金表面复合处理方法 |
CA2902066C (en) * | 2013-03-06 | 2018-01-02 | Quaker Chemical Corporation | High temperature conversion coating on steel and iron substrates |
CN103643230B (zh) * | 2013-12-07 | 2015-07-15 | 山东建筑大学 | 一种适应温挤压的复合硫酸-磷酸钙盐表面处理方法 |
EP2883917A1 (de) * | 2013-12-13 | 2015-06-17 | Kronos International, Inc. | Calciumphosphat-haltige Kompositpigmente und Verfahren zu ihrer Herstellung |
CN104087919A (zh) * | 2014-06-30 | 2014-10-08 | 张家港市华尊宝特种材料科技有限公司 | 一种异型钢管的表面磷化工艺 |
CN104451097A (zh) * | 2014-09-26 | 2015-03-25 | 无锡市天力五金弹簧厂 | 一种弹簧渗碳淬火工艺 |
CN104962896B (zh) * | 2015-06-30 | 2017-12-05 | 大连碧城环保科技股份有限公司 | 一种锌系磷化液添加剂及其使用方法 |
DE102016100245A1 (de) * | 2016-01-08 | 2017-07-13 | Staku Anlagenbau Gmbh | Selbstschmierende elektrolytisch abgeschiedene Phosphatierungsbeschichtung |
DE102017124724B4 (de) | 2016-10-25 | 2022-01-05 | Koki Technik Transmission Systems Gmbh | Verfahren zur Herstellung einer Schaltgabel |
CN108949315B (zh) * | 2018-06-25 | 2021-11-12 | 杰锡工业技术(上海)有限公司 | 一种环保节能的新型金属冷成型加工方法 |
CN109097809A (zh) * | 2018-08-06 | 2018-12-28 | 佛山科学技术学院 | 一种高耐蚀厚磷化膜层的制备工艺 |
CN111575696A (zh) * | 2020-06-20 | 2020-08-25 | 烟台博昌汽车标准件有限公司 | 一种螺栓磷化后表面处理设备与工艺 |
DE102021004167A1 (de) | 2021-03-25 | 2022-09-29 | Wilhelm Brummer | Verfahren für Vorbehandlung von Stahl und Eisen in einem Behandlungsbad |
EP4063535A3 (de) * | 2021-03-25 | 2022-11-30 | Brummer, Wilhelm | Verfahren für vorbehandlung von stahl und eisen in einem behandlungsbad |
CN113652727A (zh) * | 2021-07-29 | 2021-11-16 | 天津正达科技有限责任公司 | 一种循环冷却水系统快速预膜方法 |
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US2132438A (en) * | 1933-12-11 | 1938-10-11 | American Chem Paint Co | Method of coating metal |
US3586612A (en) * | 1969-03-27 | 1971-06-22 | Council Scient Ind Res | Anodic phosphating of metallic articles |
JPS5429979B2 (zh) * | 1974-02-22 | 1979-09-27 | ||
SE406940B (sv) * | 1974-04-13 | 1979-03-05 | Collardin Gmbh Gerhard | Forfarande for framstellning av fosfatbeleggningar med sprutningsmetoden pa jern och stal |
JPS5456038A (en) * | 1977-10-12 | 1979-05-04 | Nippon Paint Co Ltd | Controlling method for acidic phosphate film forming liquid |
JPS6043491A (ja) * | 1983-08-19 | 1985-03-08 | Nippon Denso Co Ltd | 鉄鋼表面に燐酸塩化成被膜を形成する方法 |
JPS6148597A (ja) * | 1984-08-14 | 1986-03-10 | Nippon Paint Co Ltd | リン酸亜鉛化成処理法 |
JPS6250496A (ja) * | 1985-08-29 | 1987-03-05 | Nippon Kokan Kk <Nkk> | 金属材料の電解処理方法 |
JPH01100281A (ja) * | 1987-10-13 | 1989-04-18 | Nippon Parkerizing Co Ltd | 金属表面の皮膜化成処理液 |
DE3800835A1 (de) * | 1988-01-14 | 1989-07-27 | Henkel Kgaa | Verfahren zur phosphatierung von metalloberflaechen |
DE3808609A1 (de) * | 1988-03-15 | 1989-09-28 | Electro Chem Eng Gmbh | Verfahren zur erzeugung von korrosions- und verschleissbestaendigen schutzschichten auf magnesium und magnesiumlegierungen |
JPH0436498A (ja) * | 1990-06-01 | 1992-02-06 | Nippon Parkerizing Co Ltd | 鉄鋼線材の表面処理方法 |
DE4111186A1 (de) * | 1991-04-06 | 1992-10-08 | Henkel Kgaa | Verfahren zum phosphatieren von metalloberflaechen |
JPH0578881A (ja) * | 1991-07-22 | 1993-03-30 | Kawasaki Steel Corp | 表面処理厚鋼板 |
DE4232292A1 (de) * | 1992-09-28 | 1994-03-31 | Henkel Kgaa | Verfahren zum Phosphatieren von verzinkten Stahloberflächen |
DE4433946A1 (de) * | 1994-09-23 | 1996-03-28 | Henkel Kgaa | Phosphatierverfahren ohne Nachspülung |
JPH1046351A (ja) * | 1996-07-25 | 1998-02-17 | Nippon Parkerizing Co Ltd | 軸受用鋼線材の表面処理方法 |
DK173338B1 (da) * | 1996-08-29 | 2000-07-31 | Danfoss As | Fremgangsmåde til elektrokemisk phosphatering af metaloverflader, især af rustfrit stål, med CaZnPO4 ved koldflydning af me |
JPH116076A (ja) * | 1997-06-13 | 1999-01-12 | Nippon Parkerizing Co Ltd | 鉄鋼材料のりん酸塩処理方法 |
EP0972862A3 (en) * | 1998-07-01 | 2004-01-02 | Nihon Parkerizing Co., Ltd. | Method for forming a phosphate film on steel wires and apparatus used therefor |
KR20000023075A (ko) * | 1998-09-11 | 2000-04-25 | 사또미 유따까 | 금속 재료의 냉간 단조용으로 적당한 윤활 피막을형성하는 방법 |
JP2000144494A (ja) * | 1998-09-11 | 2000-05-26 | Nippon Parkerizing Co Ltd | 冷間圧造用の潤滑皮膜を形成する方法 |
BR9907916B1 (pt) * | 1998-12-17 | 2011-07-26 | processo de tratamento quÍmico por fosfato eletrolÍtico para formar uma pelÍcula, e, pelÍcula composta sobre uma superfÍcie de aÇo. | |
DE10010355A1 (de) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
JP2003535975A (ja) * | 2000-06-06 | 2003-12-02 | 日本パーカライジング株式会社 | 冷間加工金属用の被覆 |
CN1155736C (zh) * | 2000-08-02 | 2004-06-30 | 暨南大学 | 钢铁冷变形加工的磷化液及其磷化工艺 |
ATE399218T1 (de) * | 2002-07-10 | 2008-07-15 | Chemetall Gmbh | Verfahren zur beschichtung von metallischen oberflächen |
-
2005
- 2005-05-19 DE DE102005023023.7A patent/DE102005023023B4/de active Active
-
2006
- 2006-03-05 UA UAA200714348A patent/UA93509C2/uk unknown
- 2006-05-03 EA EA200702422A patent/EA012533B1/ru not_active IP Right Cessation
- 2006-05-03 AU AU2006246764A patent/AU2006246764B2/en not_active Ceased
- 2006-05-03 US US11/913,529 patent/US20080166575A1/en not_active Abandoned
- 2006-05-03 MX MX2007014320A patent/MX2007014320A/es active IP Right Grant
- 2006-05-03 WO PCT/EP2006/004121 patent/WO2006122651A1/de active Application Filing
- 2006-05-03 JP JP2008511586A patent/JP2008540845A/ja not_active Withdrawn
- 2006-05-03 EP EP06742777.3A patent/EP1888819B1/de active Active
- 2006-05-03 BR BRPI0610136-4A patent/BRPI0610136B1/pt active IP Right Grant
- 2006-05-03 CN CN200680017145.6A patent/CN101189366B/zh active Active
- 2006-05-03 CA CA 2608390 patent/CA2608390C/en active Active
- 2006-05-03 ZA ZA200710308A patent/ZA200710308B/xx unknown
- 2006-05-03 ES ES06742777T patent/ES2749926T3/es active Active
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
WO2006122651A1 (de) | 2006-11-23 |
CA2608390C (en) | 2013-01-08 |
CN101189366B (zh) | 2015-05-06 |
CA2608390A1 (en) | 2006-11-23 |
EP1888819A1 (de) | 2008-02-20 |
DE102005023023A1 (de) | 2006-11-23 |
UA93509C2 (uk) | 2011-02-25 |
ZA200710308B (en) | 2009-05-27 |
CN101189366A (zh) | 2008-05-28 |
BRPI0610136A2 (pt) | 2010-06-01 |
MX2007014320A (es) | 2008-02-11 |
AU2006246764B2 (en) | 2011-09-08 |
US20080166575A1 (en) | 2008-07-10 |
EA012533B1 (ru) | 2009-10-30 |
JP2008540845A (ja) | 2008-11-20 |
BRPI0610136B1 (pt) | 2018-02-06 |
DE102005023023B4 (de) | 2017-02-09 |
EA200702422A1 (ru) | 2008-06-30 |
AU2006246764A1 (en) | 2006-11-23 |
ES2749926T3 (es) | 2020-03-24 |
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