EP2111475A1 - Composants en acier à ultra haute teneur en carbone, de densité réduite et à haute résistance à la calamine - Google Patents
Composants en acier à ultra haute teneur en carbone, de densité réduite et à haute résistance à la calamineInfo
- Publication number
- EP2111475A1 EP2111475A1 EP07801785A EP07801785A EP2111475A1 EP 2111475 A1 EP2111475 A1 EP 2111475A1 EP 07801785 A EP07801785 A EP 07801785A EP 07801785 A EP07801785 A EP 07801785A EP 2111475 A1 EP2111475 A1 EP 2111475A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- uhc
- steel
- hot
- uhc lightweight
- forming
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 79
- 239000010959 steel Substances 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 24
- 238000005275 alloying Methods 0.000 claims description 11
- 150000001247 metal acetylides Chemical class 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 229910000746 Structural steel Inorganic materials 0.000 abstract description 4
- 229910000621 Ultra-high-carbon steel Inorganic materials 0.000 description 52
- 229910052710 silicon Inorganic materials 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000005242 forging Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000007792 addition Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000641 cold extrusion Methods 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000368 lamellar mixture Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
- B21D22/208—Deep-drawing by heating the blank or deep-drawing associated with heat treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
-
- 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
Definitions
- the invention relates to ultra high carbon steels or Ultra High Carbon Steel (UHC) with reduced density and high scale resistance according to claim 1, as well as the production of components by hot forging according to claim 8.
- UHC Ultra High Carbon Steel
- UHC steels have been known for some time. They have been developed especially with regard to their superplastic properties. The superplastic deformation takes place in a narrow process window of temperature and
- Forming speed (strain rate ( ⁇ ')). In the superplastic forming strain values of some 100 to 1000% can be achieved. Typically, a forming temperature above about 50% of the melting temperature (ideally in the range of ⁇ -> Y conversion) and a very low deformation rate of about 10 "2 to 10 " 5 s "1. Be the optimum temperature and / or forming speed The ideal speed for superplastic forming is thus well below the limit of industrial acceptability for series products, which is around 0.1 / s.
- Unalloyed UHC steels such as known from US 3,951,697, have only a slight superplastic effect, since the grain growth structure is unstable.
- US Pat. No. 4,448,613 describes production processes of the superplastic structure for UHC steels. It also describes the setting of superplastic structures for UHC steels with low alloying additions of Cr, Mn and Si.
- a good formability includes a high achievable without component damage degree of deformation, a low yield stress during forming and the lowest possible forming temperature. Only then are complex components made available in a few cost-effective forming steps. In cold forging (cold extrusion), high dimensional accuracy, high surface quality and high component strength (by work hardening) are possible; but are the disadvantages of some very high required forming forces contrary.
- the object is achieved by an ultra-high carbon or UHC lightweight steel with improved formability and scale resistance with the features of claim 1 and by a method for the production of hot-formed components made of UHC lightweight steels by hot forming at a temperature of 800 to 980 0 C in air the features of claim 8, or by a method for the production of hot-formed components from UHC lightweight steels by hot forming at a temperature of 880 to 1050 0 C in air with the features of claim 9.
- the forming processes at a temperature in the range from 800 to 1050 ° C. are referred to below as hot forming.
- the following alloy composition is provided for the UHC lightweight steel having improved scale resistance (compositions below in% by weight unless otherwise specified).
- the density for a UHC lightweight steel with 0.4% Si and 6.7% Al is 7 g / ccm compared to the conventional 25MoCr4 steel with a density of 7.8 g / ccm.
- the Si is the Al transformation temperature in the given
- Alloy composition can greatly influence.
- the high content of Al significantly increases the Si sensitivity of the alloy.
- Even a small increase in Si alloy additions leads to a significant increase in the Al transformation temperature. This means that the alloying of the Si achieves an increase in the optimum forming temperature.
- the optimum forming temperature is to be understood in particular as meaning the temperature which permits the highest possible forming speeds without damaging the microstructure.
- the Al transformation temperature of about 82O 0 C for a 6.5% A1, 1.5% Cr, 1.35% C, 0.04% Si UHC- Lightweight steel already increased to 865 ° C by increasing the Si content to just 0.4%.
- the Al content in addition to reducing the density, also has the very significant effect of greatly reducing the scale formation at the hot working temperatures. Since only thin scale layers form, in which only a small surface finish is required, the UHC lightweight steels according to the invention are also particularly suitable for near-net-shape processes. In the case of the UHC lightweight steels according to the invention, it was possible to achieve a reduction in the corrosion rate of 92 to 99% compared to the conventional steels 25MoCr4.
- the Si content also has a significant influence on the decrease in scaling.
- the superplastic properties are retained, whereby in some cases a slight increase in the formability at high speed could be measured.
- the mechanical properties at room temperature are not adversely affected by the usually strongly embrittling Si.
- the UHC lightweight steels according to the invention show only slightly reduced elongation at break compared to Si-free UHC steels.
- Si is usually added to the alloy melt without special precautions from the furnace lining during alloy melting.
- this behavior is problematic and must be prevented by complex measures.
- this Si absorption no longer poses a problem because of their already high Si content. Cost-effective metallurgical production processes are therefore applicable.
- the alloying elements Al and Si influence each other favorably. Therefore, the Al / Si ratio is of particular interest.
- an Al / Si ratio between 10 and 20 is selected. More preferably, the Al / Si ratio is 14 to 16 at an Al content of 6 to 7%.
- the preferred Si content is a compromise between
- Increase of optimum forming temperature and deterioration the mechanical properties and is preferably in the range of 0.3 to 1.2 wt.%, Particularly preferably 0.4 to 0.8.
- composition in% by weight is given by:
- the steel-accompanying impurities may likewise be the typical steel alloy companion Ni, Mo, Nb and / or V. As a rule, fractions of these elements in an amount below 1% are not critical.
- the Ni, Mo and / or V content is preferably below 0.15% by weight. Particular preference is given to setting at least Ni and / or V to less than 0.05%.
- the UHC lightweight structural steel contains further stabilizing alloying elements selected from the group Nb, Ti, Mg and / or N.
- the content of these alloying elements is preferably limited to values below 0.8, preferably below 0.5%. Particularly preferably, the sum of these elements in the range of 0.02 to 0.5 wt.%. It should be regarded as a further advantage of the invention that can be dispensed with in the UHC lightweight steel according to the invention on the alloying of the very expensive alloying elements Ni, Mo and / or V.
- the UHC steels are generally not in a structural state that allows a high deformation rate of the hot forming.
- An ideal structure for this purpose typically corresponds to a structure with superplastic properties.
- the superplastic forming instead of the superplastic forming, can be deviated from this optimum superplastic structure, however, within wide limits. It is important that there is a homogeneous, fine-grained, spheroidal carbide distribution stable against grain growth and graphite formation in a likewise fine-grained and grain-growth-stable ferrite matrix.
- the grain size of the microstructure is preferably below 10 ⁇ m.
- the average particle size is particularly preferably below 1.5 ⁇ m.
- Most of the grains are preferably sphoid, with small amounts of lamellar carbide being tolerable for the properties of the UHC steel.
- thermo-mechanical treatment Only by a special thermo-mechanical treatment is a structure formed which contains the required fine crystallites or grains. At least two phases must be formed which prevent grain growth.
- the corresponding phases in the compositions according to the invention are composed essentially of the main phase ⁇ -ferrite and secondary phases of ⁇ -carbides.
- Al and Si stabilize the structure against grain growth.
- a relatively homogeneous material of pearlite is first prepared, which is a lamellar mixture of ferrite and cementite.
- this perlite structure is converted into a microstructure in which the carbides are predominantly spheroidal and the ferrite ultrafine-grained.
- the structure of the UHC lightweight steels preferably has fine spheroid carbides.
- the average cross-sectional area of the spheroid carbides is preferably below 8 ⁇ m 2 , more preferably below 3 ⁇ m 2 .
- the volume fraction of the fine spheroid carbides is 25 to 30%.
- the frequency of carbide particles or particles above 500 nm per surface element to be determined by light microscopy should be above 50,000 carbide particles / mm 2 , preferably above 150,000 carbide particles / mm 2 .
- a spheroidal shape is much cheaper than a lamellar form of the carbide particles.
- the average elongation of the carbide particles is preferably below 1.8. Particularly preferably, very roundish particles are formed, with an average elongation between 1 and 1.5.
- step B typically, strain levels above 1.5 are used. Preferably, degrees of deformation at 1.7 to 4 are used.
- the UHC lightweight steels according to the invention are preferably used for the production of suspension components, transmission parts, or gears for motor vehicles.
- a particularly demanding application are connecting rods, which have not been satisfactorily available as a lightweight component.
- Another aspect of the invention relates to methods of making thermoformed components from UHC lightweight steels.
- the invention provides a UHC lightweight steel the composition (% by weight)
- hot forming in principle, the various methods known in mechanical engineering can be used for the production of complex-shaped components made of metals. If necessary, make an appropriate adaptation of the cold process to hot forming. Suitable processes include, but are not limited to, hot extrusion, cross rolling, hot bore pressing, hot swaging, hot splining, hot swaging or hydroforming, and forging.
- the temperatures of the hot working used according to the invention are significantly below the forging temperature of the respective alloy. These comparatively lower temperatures have a further significant advantage for the forming tools. Frequently, conventional steel tools can be used instead of the otherwise required high-temperature tools.
- UHC lightweight steels is preferred in hot forming at a process pressure below 150 to 180 MPa and a forming speed or
- Length change / initial length per unit of time worked above 0.1 / s.
- the design of the process can be optimized to low process pressure or to high forming speeds, depending on the selected forming process or forming tool. Particularly preferred transformation rates are above 0.5 / s.
- the method according to the invention is preferably carried out as a near-net-shape method, so that the component is obtained in the most ready-to-use state after the forming and only has to be subsequently reworked on special functional surfaces. Cleaning and polishing the surfaces are considerably easier than with the known steels.
- the UHC lightweight steels according to the invention likewise have good hardenability (up to> 60 HRC without case hardening).
- a hardening process takes place. This is in particular conducted directly from the process heat of the forming process and under Luftabschreckung. Thereafter, it can be started in a known manner.
- tensile strengths of 1500 MPa at an elongation of 8% were measured at room temperature.
- Fig. 1 the results of the high-temperature corrosion resistance of the two UHC lightweight steels are shown. It shows the scale formation at 860 0 C and 910 0 C of UHC steel with 0.04% Si against the UHC steel with 0.4% Si (UHC steel SiO, 04 versus UHC steel SiO, 4).
- the Si content has a significant influence on the decrease in scaling.
- 91O 0 C there is a 70% decrease in scaling at the transition from 0.04 to 0.4% Si.
- the particularly relevant temperature of 860 ° C. for hot forming the relative decrease in scaling is even 98%.
- FIG. 25MoCr4 shows a 92 to 99% higher scaling at both temperatures compared to ÜHC0, 4Si.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Forging (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006041902A DE102006041902A1 (de) | 2006-09-07 | 2006-09-07 | Bauteile aus Ultrahochkohlenstoffhaltigen Stählen mit reduzierter Dichte und hoher Zunderbeständigkeit |
PCT/EP2007/007349 WO2008028561A1 (fr) | 2006-09-07 | 2007-08-21 | composants en acier à ultra haute teneur en carbone, de densité réduite et à haute résistance À la calamine |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2111475A1 true EP2111475A1 (fr) | 2009-10-28 |
EP2111475B1 EP2111475B1 (fr) | 2018-03-14 |
Family
ID=38648331
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07801785.2A Active EP2111475B1 (fr) | 2006-09-07 | 2007-08-21 | Composants en acier à ultra haute teneur en carbone, de densité réduite et à haute résistance à la calamine |
Country Status (4)
Country | Link |
---|---|
US (1) | US8257646B2 (fr) |
EP (1) | EP2111475B1 (fr) |
DE (1) | DE102006041902A1 (fr) |
WO (1) | WO2008028561A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007019980B4 (de) * | 2007-04-27 | 2018-04-12 | Daimler Ag | Herstellung von superplastischen UHC-Leichtbaustählen und deren Verarbeitung durch Warmumformung |
DE102008032024B4 (de) | 2008-07-07 | 2012-11-08 | Daimler Ag | Dichtereduzierte UHC-Stähle |
DE102010051682B4 (de) | 2010-11-17 | 2012-07-12 | Daimler Ag | Leichtbau-Kurbeltrieb und Herstellungsverfahren desselben |
DE102011112244B4 (de) | 2011-09-01 | 2013-09-05 | Daimler Ag | Leichtbau-Kolben für Verbrennungsmotoren und Halbzeug sowie Verfahren zu dessen Herstellung |
DE102011118298A1 (de) | 2011-11-10 | 2013-05-16 | Daimler Ag | Leichtbau-Kolben für Verbrennungsmotoren und Halbzeug sowie Verfahren zu dessen Herstellung |
DE102011118297A1 (de) | 2011-11-10 | 2013-05-16 | Daimler Ag | Kolben für Verbrennungsmotoren und Halbzeug sowie Verfahren zu dessen Herstellung |
CN104377281B (zh) * | 2014-11-24 | 2017-04-26 | 武汉钢铁江北集团精密带钢有限公司 | 一种led贴片支架用冷轧钢及生产方法 |
CN108220807B (zh) * | 2017-12-21 | 2020-07-24 | 钢铁研究总院 | 一种低密度高铝超高碳轴承钢及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1850953A (en) * | 1925-06-19 | 1932-03-22 | Percy A E Armstrong | Heat, rust, and acid resisting ferrous alloy |
DE678324C (de) * | 1931-10-16 | 1939-07-15 | Kohle Und Eisenforschung G M B | Verwendung einer an sich bekannten Stahllegierung zur Herstellung von elektrischen Heizdraehten |
FR831996A (fr) | 1937-01-30 | 1938-09-16 | British & Dominions Feralloy L | Perfectionnements à la fabrication de la fonte |
US4769214A (en) * | 1985-09-19 | 1988-09-06 | Sptek | Ultrahigh carbon steels containing aluminum |
US5445685A (en) * | 1993-05-17 | 1995-08-29 | The Regents Of The University Of California | Transformation process for production of ultrahigh carbon steels and new alloys |
DE102005027258B4 (de) | 2005-06-13 | 2013-01-31 | Daimler Ag | Hochkohlenstoffhaltiger Stahl mit Superplastizität |
-
2006
- 2006-09-07 DE DE102006041902A patent/DE102006041902A1/de not_active Withdrawn
-
2007
- 2007-08-21 WO PCT/EP2007/007349 patent/WO2008028561A1/fr active Application Filing
- 2007-08-21 US US12/439,548 patent/US8257646B2/en active Active
- 2007-08-21 EP EP07801785.2A patent/EP2111475B1/fr active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2008028561A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP2111475B1 (fr) | 2018-03-14 |
WO2008028561A1 (fr) | 2008-03-13 |
DE102006041902A1 (de) | 2008-03-27 |
US20100021339A1 (en) | 2010-01-28 |
US8257646B2 (en) | 2012-09-04 |
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Legal Events
Date | Code | Title | Description |
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