EP1514282A1 - Weichmagnetischer pulververbundwerkstoff, verfahren zu dessen hersellung und dessen verwendung - Google Patents
Weichmagnetischer pulververbundwerkstoff, verfahren zu dessen hersellung und dessen verwendungInfo
- Publication number
- EP1514282A1 EP1514282A1 EP03704253A EP03704253A EP1514282A1 EP 1514282 A1 EP1514282 A1 EP 1514282A1 EP 03704253 A EP03704253 A EP 03704253A EP 03704253 A EP03704253 A EP 03704253A EP 1514282 A1 EP1514282 A1 EP 1514282A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- composite material
- soft magnetic
- starting mixture
- soft
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000006247 magnetic powder Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001035 Soft ferrite Inorganic materials 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000004200 microcrystalline wax Substances 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 4
- 229910003962 NiZn Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 3
- 229910002546 FeCo Inorganic materials 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
- H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/33—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials mixtures of metallic and non-metallic particles; metallic particles having oxide skin
Definitions
- the invention relates to a soft magnetic powder composite material, a method for producing such a material and its use according to the type of the independent claims.
- DE 199 60 095 AI describes a sintered soft magnetic composite and a method for its production, in which a ferromagnetic starting component is used as the main component and a ferritic starting component as a secondary component in a starting mixture from which a soft magnetic composite is formed after heat treatment.
- the second starting component forms a grain boundary phase after the heat treatment of the starting mixture to form the composite material.
- the first starting component is, for example, a pure iron powder or a phosphated iron powder
- the second starting component is, for example, a ferrite powder, in particular a soft ferritic powder such as MnZn ferrite or NiZn ferrite.
- the proportion of iron powder in the starting mixture is 95 to 99 percent by weight, the proportion of ferrite powder 1 to 25 percent by weight.
- the object of the present invention was to provide a soft magnetic powder composite material which has the highest possible magnetic saturation polarization and magnetic permeability in combination with the highest possible specific electrical resistance and which in particular improves the properties of the composite material according to DE 199 60 095 AI.
- the soft-magnetic powder composite material according to the invention has the advantage over the prior art that it has a magnetic saturation polarization of more than 1.85 Tesla, in particular 1.90 Tesla to 2.05 Tesla, and that it has one over the prior art has significantly increased specific electrical resistance of more than 1 ⁇ m, in particular from 5 ⁇ m to 15 ⁇ . As a rule, the specific electrical resistance is approx. 10 ⁇ m.
- the soft magnetic powder composite material according to the invention has a bending strength of more than 120 MPa, measured on cylindrical samples.
- the edge breaking strength of components made from this material in the form of magnetic pots for injection valves is over 45 kN, and the soft magnetic powder composite obtained is also temperature-resistant and fuel-resistant up to at least 400 ° C. In this respect, it is very well suited for the production of fast-switching solenoid valves, as are required for diesel injection in motor vehicle engines.
- the pressing can be facilitated by adding a pressing aid to the starting mixture, for example a micro wax, and that the properties of the powder composite material obtained are very simple via the gas atmosphere and the temperature program during debinding or the heat treatment can be adjusted.
- a pressing aid for example a micro wax
- the soft ferrite powder used is a MnZn ferrite powder, a NiZn ferrite powder or a mixture of both powders.
- the pure iron powder, iron alloy powder or the preferred phosphated iron powder used further advantageously have an average grain size of the powder particles between 30 ⁇ m and 150 ⁇ m, while the grain size of the one used In contrast, soft ferrite powder is advantageously significantly smaller and is less than 20 ⁇ m on average.
- the average grain size of the soft ferrite powder particles used is preferably less than 5 ⁇ m, in particular less than 1 ⁇ m.
- the soft magnetic powder composite material To produce the soft magnetic powder composite material, one starts with a starting mixture consisting of a pure iron powder or a phosphated iron powder and a soft ferrite powder.
- iron alloy powders such as FeCr powder or FeCo powder can also be used.
- Phosphated iron powder is preferably used, since it achieves the best electrical properties of the powder composite.
- a pressing aid such as a micro wax
- the proportion of the pressing aid in the starting mixture is 0% by mass to a maximum of 0.8% by mass.
- the starting mixture consists of at least 99.4 pounds of pure iron powder or a phosphated iron powder and 0.1 mass% to 0.6 mass% of a soft ferrite powder.
- the proportion of pure iron powder or of the phosphated iron powder is preferably more than 99.5% by mass, in particular 99.7% by mass to 99.8% by mass.
- the proportion of the soft ferrite powder is preferably less than 0.5% by mass, in particular 0.1% by mass to 0.3% by mass.
- the soft ferrite powder used is preferably a manganese-zinc ferrite (MnZnOFe 2 0 3 ) or a nickel-zinc ferrite (NiZnO-Fe 2 0 3 ) or a mixture of both powders. Phosphated iron powder or phosphated pure iron powder and one of these two soft ferritic powders are preferably used.
- the pure iron powder or the phosphated iron powder has an average particle size of the powder particles of 50 ⁇ m to 100 ⁇ m.
- the grain size of the soft ferritic powder used is preferably well below 20 ⁇ m, preferably below 5 ⁇ m. For example, it is in the range between 0.5 ⁇ m to 2 ⁇ m, in particular 1 ⁇ m.
- the composition of the starting mixture which essentially consists of pure iron powder or the phosphated iron powder and the soft ferrite powder, depending on the intended use of the material obtained, on the one hand, by varying the composition of the material, adding more weight to the highest possible magnetic Saturation polarization and the highest possible magnetic permeability, ie f a -> - greater than 800, or on the other hand more weight can be placed on the highest possible specific electrical resistance.
- the powders explained above are first prepared as explained in the form of a starting mixture, this is mixed and then compressed with the aid of a press under increased pressure and shaped into the desired shape. introduced.
- the green bodies produced in this way are then debindered in an oven in an inert gas atmosphere, for example a nitrogen atmosphere, or in an oxygen-containing gas atmosphere.
- the compressed starting mixture is heated in the oven to a temperature of 400 ° C to 500 ° C and held there for a period of 10 minutes to 1 hour.
- the temperature during debinding depends primarily on the pressing aid used, ie the micro wax used. In this respect, it can also be below the 400 ° C. explained, for example in the range from 220 ° C. to 300 ° C.
- the debindered, compressed starting mixture is subjected to a further heat treatment in an oxidizing gas atmosphere at a temperature of 410 ° C. to 500 ° C. in an oven.
- the pressure in the oven is heated to this temperature and held there for a period of 20 minutes to 400 minutes, for example 200 minutes.
- the gas atmosphere in the furnace is, for example, air.
- a soft magnetic powder composite material is obtained in which the soft ferrite powder used is at least largely present as a grain boundary phase, i.e. the soft ferritic powder particles surround the iron powder particles used in the powder composite.
- the pressing aid used in the course of the manufacturing process facilitates the compression and shaping of the starting mixture during pressing.
- the pressing aid should be completely removed or evaporated again during debinding, so that it has no direct influence on the achievable material characteristics of the soft magnetic powder composite material obtained. This is especially lem achieved by using micro wax as a pressing aid.
- the starting mixture is compacted in the die under increased pressure, preferably by uniaxial pressing at a pressure of preferably 500 MPa to 1000 MPa.
- solenoid valves produced with the soft magnetic powder composite material according to the invention are unrestrictedly resistant to fuel and temperature under typical operating conditions in the diesel injection of motor vehicles. They also have a very good mechanical strength, both in terms of bending strength and edge breaking strength.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Soft Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10225154A DE10225154B4 (de) | 2002-06-06 | 2002-06-06 | Weichmagnetischer Pulververbundwerkstoff, Verfahren zu dessen Herstellung und dessen Verwendung |
| DE10225154 | 2002-06-06 | ||
| PCT/DE2003/000211 WO2003105161A1 (de) | 2002-06-06 | 2003-01-27 | Weichmagnetischer pulververbundwerkstoff, verfahren zu dessen hersellung und dessen verwendung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1514282A1 true EP1514282A1 (de) | 2005-03-16 |
| EP1514282B1 EP1514282B1 (de) | 2009-04-15 |
Family
ID=29723091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03704253A Expired - Lifetime EP1514282B1 (de) | 2002-06-06 | 2003-01-27 | Weichmagnetischer pulververbundwerkstoff; verfahren zu dessen hersellung und dessen verwendung |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7686894B2 (de) |
| EP (1) | EP1514282B1 (de) |
| JP (1) | JP2005536036A (de) |
| CN (1) | CN1331169C (de) |
| AT (1) | ATE429020T1 (de) |
| AU (1) | AU2003206641A1 (de) |
| DE (2) | DE10225154B4 (de) |
| WO (1) | WO2003105161A1 (de) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100380537C (zh) * | 2005-05-27 | 2008-04-09 | 罗计添 | 一种软磁复合材料及由其制造导磁构件的方法 |
| CN100594565C (zh) * | 2008-01-25 | 2010-03-17 | 华中科技大学 | 一种铁氧体纳米颗粒嵌入反铁磁氧化物母体的复合材料及制备方法 |
| CN101777407B (zh) * | 2010-03-26 | 2012-12-26 | 北京科源科金属材料有限公司 | 一种改进非晶粉芯导磁率及损耗的方法及依据此方法制备的复合粉芯 |
| CN102528024B (zh) * | 2012-01-20 | 2013-06-26 | 钢铁研究总院 | 一种软磁复合材料用绝缘铁粉的制备方法 |
| CN103664159A (zh) * | 2012-09-26 | 2014-03-26 | 比亚迪股份有限公司 | 一种镍锌铁氧体软磁材料及其制备方法 |
| TWI518713B (zh) * | 2012-12-06 | 2016-01-21 | China Steel Corp | Soft magnetic powder and its making method and composite material sheet body which can suppress electromagnetic interference |
| DE102013200229B4 (de) | 2013-01-10 | 2024-06-06 | Robert Bosch Gmbh | Verfahren zum Herstellen eines weichmagnetischen Verbundwerkstoffs |
| DE102013215520A1 (de) | 2013-08-07 | 2015-02-12 | Robert Bosch Gmbh | Weichmagnetischer Metallpulver-Verbundwerkstoff und Verfahren zur Herstellung eines solchen |
| CN103426584B (zh) * | 2013-09-11 | 2016-04-13 | 中国计量学院 | 一种铁氧体复合磁粉芯及其制备方法 |
| US20160307679A1 (en) * | 2013-12-26 | 2016-10-20 | Drexel University | Soft Magnetic Composites for Electric Motors |
| CN104332266A (zh) * | 2014-10-30 | 2015-02-04 | 安徽首文高新材料有限公司 | 一种耐高温铁粉芯的制备方法 |
| DE102015209970A1 (de) | 2015-05-29 | 2016-12-01 | Robert Bosch Gmbh | Weichmagnetischer Pulververbundwerkstoff und Verfahren zu seiner Herstellung |
| CN105565392B (zh) * | 2015-12-23 | 2017-07-14 | 苏州冠达磁业有限公司 | 一种高磁导率镍锌铁软磁体及其制备方法 |
| JP6459986B2 (ja) * | 2016-01-08 | 2019-01-30 | 株式会社村田製作所 | 金属磁性粉含有シート、インダクタの製造方法及びインダクタ |
| EP3354437A1 (de) * | 2017-01-25 | 2018-08-01 | Continental Automotive GmbH | Elektromagnetisches schaltventil sowie kraftstoffhochdruckpumpe |
| KR102311667B1 (ko) | 2017-07-26 | 2021-10-13 | 현대자동차주식회사 | Fe-Si 연자성 분말을 이용한 연자성체 제조방법 |
| CN107818855A (zh) * | 2017-10-31 | 2018-03-20 | 桂林市漓江机电制造有限公司 | 一种细晶粒软磁体复合材料及其制造方法 |
| CN107799261A (zh) * | 2017-10-31 | 2018-03-13 | 桂林市漓江机电制造有限公司 | 一种软磁体复合材料及其制造方法 |
| CN107818856A (zh) * | 2017-10-31 | 2018-03-20 | 桂林市漓江机电制造有限公司 | 一种软磁粉末冶金材料及其制造方法 |
| CN111243813B (zh) * | 2020-03-12 | 2021-10-15 | 钢铁研究总院 | 高电阻率钕铁硼永磁合金及其制备方法 |
| EP3937347A1 (de) * | 2020-07-08 | 2022-01-12 | Siemens Aktiengesellschaft | Materiallage für ein blechpaket einer elektrischen maschine |
| KR20220167986A (ko) | 2021-06-15 | 2022-12-22 | 현대자동차주식회사 | 철계 혼합분말 제조장치 및 제조방법 |
| CN113658768A (zh) * | 2021-08-27 | 2021-11-16 | 西安交通大学 | 稳定磁导率低损耗FeSiAl/MnZn铁氧体软磁复合磁粉芯及其制备方法 |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR984544A (fr) * | 1949-02-11 | 1951-07-06 | Telecommunications Sa | Noyau en poudre magnétique comprimée |
| GB805710A (en) | 1955-05-31 | 1958-12-10 | Siemens Ag | Improvements in or relating to magnetically soft sintered bodies |
| GB805110A (en) * | 1956-05-22 | 1958-11-26 | Distillers Co Yeast Ltd | Process for the oxidation of paraffins |
| JPS5391397A (en) * | 1977-01-21 | 1978-08-11 | Hitachi Ltd | Material with high permeability |
| JPS6413705A (en) * | 1987-07-08 | 1989-01-18 | Matsushita Electric Industrial Co Ltd | Compound magnetic material of high flux density |
| DE69028360T2 (de) * | 1989-06-09 | 1997-01-23 | Matsushita Electric Ind Co Ltd | Verbundmaterial sowie Verfahren zu seiner Herstellung |
| JPH03180434A (ja) | 1989-12-09 | 1991-08-06 | Fuji Elelctrochem Co Ltd | サーメット型フェライトの製造方法 |
| JPH04352403A (ja) | 1991-05-30 | 1992-12-07 | Tokin Corp | 複合型圧粉磁芯 |
| JPH05251224A (ja) * | 1992-03-09 | 1993-09-28 | Sony Corp | 複合磁性材料 |
| JPH05267036A (ja) * | 1992-03-23 | 1993-10-15 | Sony Corp | 複合磁性材料 |
| JP3180434B2 (ja) | 1992-04-28 | 2001-06-25 | ダイキン工業株式会社 | フィン・チューブ型熱交換器 |
| JPH06236808A (ja) * | 1993-02-10 | 1994-08-23 | Kawasaki Steel Corp | 複合磁性材料およびその製造方法 |
| JPH09134522A (ja) * | 1995-11-08 | 1997-05-20 | Kao Corp | 磁気記録媒体 |
| US5796018A (en) * | 1997-01-29 | 1998-08-18 | Procedyne Corp. | Process for coating iron particles with phosphorus and forming compacted articles |
| JPH111702A (ja) * | 1997-06-11 | 1999-01-06 | Kawasaki Steel Corp | 鉄基金属−フェライト酸化物複合粉末の製造方法 |
| CN1324783C (zh) | 1997-10-17 | 2007-07-04 | 精工爱普生株式会社 | 电机叠片铁心、其制造方法、电机以及喷墨记录装置 |
| US5982073A (en) * | 1997-12-16 | 1999-11-09 | Materials Innovation, Inc. | Low core loss, well-bonded soft magnetic parts |
| DE19960095A1 (de) | 1999-12-14 | 2001-07-05 | Bosch Gmbh Robert | Gesinterter weichmagnetischer Verbundwerkstoff und Verfahren zu dessen Herstellung |
| DE10031923A1 (de) * | 2000-06-30 | 2002-01-17 | Bosch Gmbh Robert | Weichmagnetischer Werkstoff mit heterogenem Gefügebau und Verfahren zu dessen Herstellung |
| JP4352403B2 (ja) | 2004-09-14 | 2009-10-28 | 横河電機株式会社 | Xyステージ |
-
2002
- 2002-06-06 DE DE10225154A patent/DE10225154B4/de not_active Expired - Fee Related
-
2003
- 2003-01-27 WO PCT/DE2003/000211 patent/WO2003105161A1/de not_active Ceased
- 2003-01-27 CN CNB038119706A patent/CN1331169C/zh not_active Expired - Fee Related
- 2003-01-27 AT AT03704253T patent/ATE429020T1/de not_active IP Right Cessation
- 2003-01-27 AU AU2003206641A patent/AU2003206641A1/en not_active Abandoned
- 2003-01-27 US US10/515,738 patent/US7686894B2/en not_active Expired - Fee Related
- 2003-01-27 JP JP2004512146A patent/JP2005536036A/ja active Pending
- 2003-01-27 DE DE50311421T patent/DE50311421D1/de not_active Expired - Lifetime
- 2003-01-27 EP EP03704253A patent/EP1514282B1/de not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03105161A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1514282B1 (de) | 2009-04-15 |
| DE50311421D1 (de) | 2009-05-28 |
| US20050217759A1 (en) | 2005-10-06 |
| AU2003206641A1 (en) | 2003-12-22 |
| JP2005536036A (ja) | 2005-11-24 |
| WO2003105161A1 (de) | 2003-12-18 |
| ATE429020T1 (de) | 2009-05-15 |
| DE10225154B4 (de) | 2012-06-06 |
| CN1331169C (zh) | 2007-08-08 |
| DE10225154A1 (de) | 2004-01-15 |
| CN1656575A (zh) | 2005-08-17 |
| US7686894B2 (en) | 2010-03-30 |
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