GB2447856A - Iron-nickel-cobalt alloy - Google Patents
Iron-nickel-cobalt alloy Download PDFInfo
- Publication number
- GB2447856A GB2447856A GB0813844A GB0813844A GB2447856A GB 2447856 A GB2447856 A GB 2447856A GB 0813844 A GB0813844 A GB 0813844A GB 0813844 A GB0813844 A GB 0813844A GB 2447856 A GB2447856 A GB 2447856A
- Authority
- GB
- United Kingdom
- Prior art keywords
- max
- accordance
- alloy
- weight
- remainder
- 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
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 8
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910018663 Mn O Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
- C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Use of an iron-nickel-cobalt alloy in CFC mould construction comprising (in % by mass) Ni from 30 to 35%, Co from 3 to 6%, Al from 0.001 to 0.1%, Mn from 0.005 to 0.5%, Si from 0.005 to 0.5%, C max. 0.1%, balance Fe and constituents resulting from production, with the alloy having a mean coefficient of thermal expansion in the temperature range from 20 to 200{C of < 2.0 <EMI ID=1.1 HE=4 WI=4 LX=366 LY=2469 TI=UI> <PC>10<-6>/K.
Description
Iron-Nickel-Cobalt Alloy The invention relates to the use of an
iron-nickel-cobalt alloy.
Increasingly, components are being produced from carbon fiber-reinforced composites (CFC), even those for products with safety consideratious, such as in aircraft manufacture. For producing such components, implements (molds) are needed in which the viscous resin-carbon fiber layer is cured at a temperature of approx. 180 C. In the so-called RIM (resin transfer molding) process, carbon fiber textiles are added to the mold, the mold is evacuated, and then the resin is injected into the mold. After curing at approx. 180 C, the component is removed from the implement. Materials used for these molds are either C steels or an alloy with a low coefficient of expansion (iron with 36% nickel, Ni36) that typically has a mean thermal expansion coefficient between 1.6 and 2.5 x l0 K'.
The use of these RTM molds is associated with difficulties and significant complexity because after it is cured the component is difficult to release from the mold and in addition the component must undergo complex subsequent processing so that it can satisfy its functional demands.
The underlying object of the invention is therefore to provide an alloy for these molds, with which alloy the aforesaid difficulties can be overcome simply.
This object is attained by using an iron-nickel-cobalt alloy in the CFC mold having (in % by weight): Ni 30 to 35% Co 3to6% Al O.OOltoO. l% Mn O.OOStoO.5% Si 0.005 to 0.5% C Max.0.1% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of< 2.0 x 10/K in the temperature range from 20 to 200 C.
Advantageous refinements of the inventive subject-matter can be found in the subordinate claims.
Depending on the application area, the Ni content can be adjusted ranging from 32 to 34.5%, where needed even 32.5 to 33.5%.
One preferred alloy is distinguished by the following composition (in % by weight): Ni 32.5 to 34.5% Co >3.Oto5.5% Al 0.001 to 0.5% Mn 0.005toO.I% Si O.OOStoO.l% C 0.005 to 0.05% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of< 1.5 x 1 0/K in the temperature range from 20 to 200 C.
The following elements with the given maximum contents can advantageously be provided for accompanymg elements in the alloy to be used: Cr max.0.l% Mo max.0.1% Cu max.0.1% Ti max.0.1% Mg max. 0.005% B max. 0.005% N max. 0.006% 0 max. 0.003% S max. 0.005% P max. 0.008% Ca max. 0.005% Zr max.0.05% Another alloy that can be used advantageously is distinguished by the following chemical composition (in % by weight): Ni 32.5 to 34.5% Co >3.Sto<4,5% Mo max. 0.05% Cr max. 0.05% C max. 0.009% Mn max. 0.04% Si max. 0.03% S max. 0.003% N max. 0.004% Ti max.0.0I% Cu max. 0.05% P max. 0.005% Al 0.001 to 0.05% Mg max. 0.0008% Ca max. 0.0001% Zr max. 0.03% 0 max. 0.006% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of< 1.3 x I 0fK in the temperature range from 20 to 200 C.
Advantageously, the molds are made as milled parts from heat-formed (forged or rolled) or cast mass material and then annealed. The alloy can also be used in the form of wire material, in particular as an added welding substance when producing the mold.
One preferred application for the alloy is found in aircraft manufacture, wherein it is possible to use the alloy as a molded component, in particular for producing CFC fittings using the RIM technology. Other aircraft components that are also embodied using the light-weight CFC construction can also be produced with components made of the suggested alloy.
Compared to alloys based on Ni 36 that have been used in the past, components can easily be removed from molds of this alloy, because the thermal shrinkage of the mold is lower after the curing process. Given a suitable design for the mold, the component can be removed such that it can perform its function without subsequent processing.
The simpler removal of the component from the mold will also increase the service life of the mold, because no sharp-edged tools have to be used in order to release the component from the mold.
Table I provides examples of chemical compositions for inventive iron-nickel-cobalt alloys (El, E2, E3, E4, E5, E6) compared to other iron-nickel-cobalt alloys (TI, Ui) that were investigated.
Element (%) El E2 3 E4 ES E6 C 0.002 0.47 0.002 0.008 0.002 0.036 S 0.0023 0.0009 0.0006 0.0015 0.0004 0.0011 0.001 _________ 0.001 0.001 0.001 _________ Cr 0.02 -0.01 <0.01 -<0.01 <0.01 0.01 Ni 34.20 34.25 32.75 32.80 32.80 32.55 Mn <0.01 <0.01 <0.01 <0. 01 <0.01 <0.01 0.07 <0.01 <0.01 <0.01 <0.01 <0.01 Mo __________ 0.01 0.02 -0.01 0.01 -0.05 f <0.01 -<0.01 <0.01 <0.01 <0.01 <0.01 Cu 0.01 <0.01 <0.01 <0.01 <0.01 -<0.01 P 0.002 0.002 -0.002 0.002 0.002 0.002 A 0.004 0007 0.001 0.005 0.005 0.014 Mj 0.0004 0.0003 0.0003 0.0003 0.0002 0.0003 Ca 0.0004 <0.001 0.0006 0.0006 0.0007 <0.001 3.1 -3.1 3.38 3.9 4.45 4.9 Fe Remainder Remajnd Remainder Remainder Remainder Remainder Element (%) TI UI C 0.004 002 S 0.0008 0.0025.
N ______ 0.001 Cr 0.01 0.02 Ni 35.50 34.20 Mn 0.03 -<0.01 Si 0.04 0.11 M0.09 ____ Ti <0.01 <0.01 Cu 0.05 0.01 P 0.002 -0.003 A1 0.011 0.010 Mg 0.0006 0.0005 Ca 0.0002 0.0003 Co 1.44 -2.3 Fe Remainder Remainder Inventive alloys El -E3 and E6 attain thermal expansion coefficients ranging from 1.5 -< 2.0 x I 0IK in the 20-200 C temperature range.
The inventive alloys E4 and ES attain an even lower expansion coefficient of about 1.3 x lO/K in the 20 to 200 C temperature range so that with the alloys E4 and E5 a combination of increased strength with simultaneously lower thermal expansion is attained.
Claims (12)
- Patent claims 1. Use of an iron-nickel-cobalt alloy in the CFC moldhaving (in % by weight): Ni 30 to 35% Co 3to6% Al 0.001 to 0.1% Mn O.OO5toO.5% Si 0.005 to 0.5% C max.0.1% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of< 2.0 x 10fK in the temperature range from 20 to 200 C.
- 2. Use in accordance with claim 1 having a Ni content of 32.0 to 34. 5% (in % by weight).
- 3. Use in accordance with claim 1, having a Ni content of 32.5 to 33.5% (in % by weight).
- 4. Use in accordance with any of claims I through 3, characterized by the following composition (in % by weight): Ni 32.5 to 34.5% Co >3.OtoS.5% Al 0.OOltoO.5% Mn 0.OO5toO.I% Si 0.OOStoO.1% C 0.005 to 0.05% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of < 1. 5 x I 0/K in the temperature range from 20 to 200 C.
- 5. Use in accordance with any of claims 1 through 4, having the following maximum contents of accompanying elements: Cr max.0.I% Mo max.O.I% Cu max.0.l% Ti max.O.1% Mg max. 0.005% B max. 0.005% N max. 0.006% 0 max. 0.003% S max. 0.005% P max. 0.008% Ca max. 0.005% Zr max. 0.05%
- 6. Use in accordance with any of claims 1 through 5 having the following composition (in % by weight): Ni 32.5 to 34.5% Co >3.Sto<4.5% Mo max. 0.05% Cr max. 0.05% C max. 0.009% Mn max. 0.04% Si max. 0.03% S max.0.003% N max.O.004% Ti max.O.O1% Cu max. 0.05% P max. 0.005% Al 0.OOItoO.05% Mg max. 0.0008% Ca max. 0.0003% Zr max. 0.05% o max. 0.006% remainder Fe and constituents resulting from the production process, the alloy having a mean thermal expansion coefficient of < 1. 3 x I 01K in the temperature range from 20 to 200 C.
- 7. Use in accordance with any of claims I through 6, as needed also containing Nb in contents of 0.001 to 0.1% (in % by weight).
- 8. Use in accordance with any of claims 1 through 7, wherein large-format semi-finished products are used in sheet material, strip material, or tube material.
- 9. Use in accordance with any of claims 1 through 7, wherein wire is used, especially in the form of an added welding substance.
- 10. Use in accordance with any of claims I through 8 as a molded component for producing aircraft parts from carbon fiber- reinforced composites.
- 11. Use in accordance with any of claims I through 7 as forged parts.
- 12. Use in accordance with any of claims I through 7 as cast components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006005252A DE102006005252B4 (en) | 2006-02-02 | 2006-02-02 | Molded part made of an iron-nickel-cobalt alloy |
| PCT/DE2007/000142 WO2007087786A1 (en) | 2006-02-02 | 2007-01-26 | Iron-nickel-cobalt alloy |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0813844D0 GB0813844D0 (en) | 2008-09-03 |
| GB2447856A true GB2447856A (en) | 2008-10-01 |
| GB2447856B GB2447856B (en) | 2011-09-07 |
Family
ID=38001632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0813844A Active GB2447856B (en) | 2006-02-02 | 2007-01-26 | Iron-nickel-cobalt alloy |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20100175847A1 (en) |
| EP (1) | EP1979502B1 (en) |
| JP (1) | JP2009525400A (en) |
| CN (1) | CN101379210B (en) |
| AT (1) | AT508430B1 (en) |
| CA (1) | CA2637499C (en) |
| DE (1) | DE102006005252B4 (en) |
| ES (1) | ES2330186B2 (en) |
| GB (1) | GB2447856B (en) |
| WO (1) | WO2007087786A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474839A (en) * | 2008-12-24 | 2009-07-08 | 西安飞机工业（集团）有限责任公司 | Mold structure for molding composite material |
| EP2440681B1 (en) * | 2009-06-11 | 2020-07-29 | Genius Solutions Engineering Company | Low cte slush molds with textured surface, and method of making and using the same |
| CN103924153B (en) * | 2014-04-22 | 2016-04-27 | 钢铁研究总院 | A kind of low bulk magnetic shielding Alloy And Preparation Method |
| JP6188643B2 (en) * | 2014-06-30 | 2017-08-30 | 新報国製鉄株式会社 | Extremely low thermal expansion alloy and manufacturing method thereof |
| US10351459B2 (en) * | 2015-08-14 | 2019-07-16 | Corning Incorporated | Molds and methods to control mold surface quality |
| WO2023227929A1 (en) * | 2022-05-27 | 2023-11-30 | Aperam | Alloy for manufacturing tools intended for manufacturing aeronautical parts made of composite material |
| KR20240098517A (en) * | 2022-12-21 | 2024-06-28 | 주식회사 포스코 | Non-coated austenitic steel sheet with improved corrosion resistance in an alkaline environment and method for manufacturing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049395A (en) * | 1999-08-11 | 2001-02-20 | Hitachi Metals Ltd | Iron-nickel-cobalt alloy excellent in etching characteristic and low thermal expansion characteristic, and shadow mask excellent in smoothness of inside peripheral shape of etch pit |
| JP2001181796A (en) * | 1999-12-28 | 2001-07-03 | Hitachi Metals Ltd | Fe-Ni-Co ALLOY EXCELLENT IN ETCHING CHARACTERISTIC AND LOW THERMAL EXPANSION CHARACTERISTIC, AND SHADOW MASK EXCELLENT IN ETCHING PIT SHAPE CHARACTERISTIC |
| JP2001262278A (en) * | 2000-03-17 | 2001-09-26 | Hitachi Metals Ltd | HIGH-STRENGTH AND LOW-EXPANSION Fe-Ni ALLOY, SHADOW MASK, AND LEAD FRAME |
| DE10258356B3 (en) * | 2002-12-12 | 2004-05-27 | Thyssenkrupp Vdm Gmbh | Use of an iron-nickel-cobalt alloy for shadow masks and their frames in flat monitors and TV screens |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1929909A (en) * | 1930-10-04 | 1933-10-10 | Lebanon Steel Foundry | Manufacture of die blocks and the like |
| GB912826A (en) * | 1960-03-23 | 1962-12-12 | British Petroleum Co | Improvements in or relating to the production of isoprene-containing material |
| US4853298A (en) * | 1986-04-08 | 1989-08-01 | Carpenter Technology Corporation | Thermally stable super invar and its named article |
| JPH01306540A (en) * | 1988-05-31 | 1989-12-11 | Shinichi Enomoto | Low thermal expansion alloy iron |
| JPH02298236A (en) * | 1989-05-12 | 1990-12-10 | Shinichi Enomoto | Low thermal expansion alloy |
| EP1134053B1 (en) * | 1998-10-02 | 2004-09-29 | Sumitomo Metal Industries, Ltd. | Welded structure made of low thermal expansion coefficient alloy and weld material |
| US6510601B1 (en) * | 2000-03-20 | 2003-01-28 | The Boeing Company | Invar forming method for making tooling |
| FR2819825B1 (en) * | 2001-01-24 | 2003-10-31 | Imphy Ugine Precision | PROCESS FOR MANUFACTURING A FE-NI ALLOY STRIP |
| ES2205961B2 (en) * | 2001-02-13 | 2005-03-01 | Eads Construcciones Aeronauticas, S.A. | PROCEDURE FOR THE MANUFACTURE OF COMPOSITE MATERIAL ELEMENTS THROUGH THE COENCOLATE TECHNOLOGY. |
| JP2004183000A (en) * | 2002-11-29 | 2004-07-02 | Jfe Steel Kk | Low thermal expansion alloy thin sheet excellent in formability and impact resistance, its production method, and shadow mask using the alloy thin sheet |
| DE102005008479B4 (en) * | 2005-02-24 | 2011-07-07 | Airbus Operations GmbH, 21129 | Arrangement and method for producing a component |
-
2006
- 2006-02-02 DE DE102006005252A patent/DE102006005252B4/en not_active Expired - Fee Related
-
2007
- 2007-01-26 CN CN2007800041283A patent/CN101379210B/en active Active
- 2007-01-26 GB GB0813844A patent/GB2447856B/en active Active
- 2007-01-26 WO PCT/DE2007/000142 patent/WO2007087786A1/en active IP Right Grant
- 2007-01-26 JP JP2008552672A patent/JP2009525400A/en active Pending
- 2007-01-26 US US12/223,131 patent/US20100175847A1/en not_active Abandoned
- 2007-01-26 EP EP07721865.9A patent/EP1979502B1/en active Active
- 2007-01-26 CA CA2637499A patent/CA2637499C/en active Active
- 2007-01-26 AT AT0900107A patent/AT508430B1/en active
- 2007-01-26 ES ES200850067A patent/ES2330186B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049395A (en) * | 1999-08-11 | 2001-02-20 | Hitachi Metals Ltd | Iron-nickel-cobalt alloy excellent in etching characteristic and low thermal expansion characteristic, and shadow mask excellent in smoothness of inside peripheral shape of etch pit |
| JP2001181796A (en) * | 1999-12-28 | 2001-07-03 | Hitachi Metals Ltd | Fe-Ni-Co ALLOY EXCELLENT IN ETCHING CHARACTERISTIC AND LOW THERMAL EXPANSION CHARACTERISTIC, AND SHADOW MASK EXCELLENT IN ETCHING PIT SHAPE CHARACTERISTIC |
| JP2001262278A (en) * | 2000-03-17 | 2001-09-26 | Hitachi Metals Ltd | HIGH-STRENGTH AND LOW-EXPANSION Fe-Ni ALLOY, SHADOW MASK, AND LEAD FRAME |
| DE10258356B3 (en) * | 2002-12-12 | 2004-05-27 | Thyssenkrupp Vdm Gmbh | Use of an iron-nickel-cobalt alloy for shadow masks and their frames in flat monitors and TV screens |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009525400A (en) | 2009-07-09 |
| AT508430A5 (en) | 2011-01-15 |
| ES2330186B2 (en) | 2010-04-19 |
| WO2007087786A8 (en) | 2007-10-11 |
| DE102006005252B4 (en) | 2010-10-28 |
| EP1979502B1 (en) | 2014-01-22 |
| EP1979502A1 (en) | 2008-10-15 |
| ES2330186A1 (en) | 2009-12-04 |
| CA2637499C (en) | 2012-04-17 |
| WO2007087786A1 (en) | 2007-08-09 |
| DE102006005252A1 (en) | 2007-08-16 |
| GB0813844D0 (en) | 2008-09-03 |
| CA2637499A1 (en) | 2007-08-09 |
| CN101379210B (en) | 2012-07-04 |
| GB2447856B (en) | 2011-09-07 |
| AT508430B1 (en) | 2011-01-15 |
| CN101379210A (en) | 2009-03-04 |
| US20100175847A1 (en) | 2010-07-15 |
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