EP2047004B1 - Nickel-based alloy - Google Patents
Nickel-based alloy Download PDFInfo
- Publication number
- EP2047004B1 EP2047004B1 EP07785601A EP07785601A EP2047004B1 EP 2047004 B1 EP2047004 B1 EP 2047004B1 EP 07785601 A EP07785601 A EP 07785601A EP 07785601 A EP07785601 A EP 07785601A EP 2047004 B1 EP2047004 B1 EP 2047004B1
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- European Patent Office
- Prior art keywords
- nickel
- mass
- max
- master alloy
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- 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.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract 5
- 229910052745 lead Inorganic materials 0.000 claims abstract 5
- 230000001419 dependent effect Effects 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000009760 electrical discharge machining Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement 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
- 230000008092 positive effect Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
Definitions
- the invention relates to a nickel-based alloy with silicon, aluminum and reactive elements as alloying constituents.
- Nickel-base alloys are used inter alia to produce electrodes of ignition elements for internal combustion engines. At wear of such electrodes are two damage mechanisms to consider, namely the high temperature corrosion and spark erosion.
- the wear caused by high-temperature corrosion can be determined by mass loss measurements as well as by metallographic investigations after aging at given test temperatures.
- Spark erosion is a material burn caused by the spark. At each flashover, a limited volume of material is melted out of the electrodes and partially evaporated.
- various alloying elements are known in nickel-based alloys.
- aluminum has a positive effect on the oxide layer formation.
- reactive elements can improve the adhesion of the forming oxide layer and then increase the lifetime.
- a nickel alloy has been disclosed consisting of (in mass%) about 0.2 to 3% Si, about 0.5% or less Mn, at least two metals selected from the group consisting of about 0.2 to 3% Cr , about 0.2 to 3% Al and about 0.01 to 1% Y, balance nickel.
- nickel-based alloy which contains (in mass%) 1.8 to 2.2% silicon, 0.05 to 0.1% yttrium and / or hafnium and / or zirconium, 2 to 2.4% aluminum, Rest has nickel.
- Such alloys can be processed only in difficult conditions with respect to the high aluminum and silicon contents and are therefore not very suitable for large-scale industrial use.
- the object of the subject invention is to provide a nickel-based alloy, by which an increase in the life of components made therefrom by increasing the spark erosion and oxidation resistance at the same time good formability and weldability can be brought about.
- This goal is achieved by a nickel-based alloy containing (in% by mass) al 1.2 - ⁇ 2.0% Si 1.2 - ⁇ 1.8% C 0.001 - 0.1% S 0.001 - 0.1% Cr 0.03 - 0.1% Mn 0.03 - 0.1% Cu Max. 0.1% Fe 0.02 - 0.2% mg 0.005 - 0.06% pb Max. 0.005% Y 0.05-0.15% and Hf 0.05-0.10% or Y 0.05-0.15% and La 0.05-0.10% or Y 0.05-0.15% and Hf 0.05-0.10% and La 0.05-0.10% Ni Remainder and production-related impurities.
- Nickel-based alloy with (in% by mass)
- Nickel-based alloy with (in% by mass)
- Nickel-based alloy with (in% by mass)
- the nickel-based alloy according to the invention is preferably usable as a material for electrodes of spark plugs for gasoline engines.
- an improvement in the lifetime of electrode materials can be achieved by increasing the resistance to spark erosion and oxidation while at the same time providing good formability and weldability become.
- the element Mg is of particular importance for the setting of sulfur, so that it is possible to selectively set low sulfur contents in the nickel-based alloy according to the invention.
- Preferred aluminum contents are (in% by mass) in the range of 1.2-1.5%.
- Preferred silicon contents are (in mass%) in the range between 1.2 and 1.8%, in particular between 1.2 and 1.5%, while the preferred Mg content (in% by mass) is between 0.008 and 0, 05% is set.
- Table 1 shows a comparison of four inventive laboratory batches in comparison with two related to the prior art large-scale batches.
- the laboratory batch 1132 represents an example in which the reactive elements Y + Hf are given in the nickel-based alloy according to the invention.
- Lab batch 1140 shows an example in which the reactive elements Y + La are present in the alloy of the invention.
- the two comparative alloys show flaking at 900 ° C of the pre-built oxide layer. Although this also applies to the alloys according to the invention at 1,000 ° C., it does not apply to the same extent as in the case of the comparative alloys.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Spark Plugs (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Continuous Casting (AREA)
- Fuel Cell (AREA)
- Contacts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Die Erfindung betrifft eine Nickelbasislegierung mit Silizium, Aluminium und reaktiven Elementen als Legierungsbestandteile.The invention relates to a nickel-based alloy with silicon, aluminum and reactive elements as alloying constituents.
Nickelbasislegierungen werden unter anderem dazu eingesetzt, Elektroden von Zündelementen für Verbrennungskraftmaschinen zu erzeugen. An Verschleiß derartiger Elektroden sind zwei Schadensmechanismen zu betrachten, nämlich die Hochtemperaturkorrosion und die Funkenerrosion.Nickel-base alloys are used inter alia to produce electrodes of ignition elements for internal combustion engines. At wear of such electrodes are two damage mechanisms to consider, namely the high temperature corrosion and spark erosion.
Der Verschleiß durch Hochtemperaturkorrosion lässt sich durch Masseverlustmessungen sowie durch metallographische Untersuchungen nach Auslagerung bei vorgegebenen Prüftemperaturen bestimmen.The wear caused by high-temperature corrosion can be determined by mass loss measurements as well as by metallographic investigations after aging at given test temperatures.
Funkenerrosion ist ein Materialabbrand, der durch den Zündfunken verursacht wird. Bei jedem Funkenüberschlag wird ein begrenztes Materialvolumen aus den Elektroden herausgeschmolzen und teilweise verdampft.Spark erosion is a material burn caused by the spark. At each flashover, a limited volume of material is melted out of the electrodes and partially evaporated.
Für beide Schadensmechanismen ist die Art der Oxidschichtausbildung von besonderer Bedeutung.For both damage mechanisms, the type of oxide layer formation is of particular importance.
Um eine optimale Oxidschichtausbildung für den konkreten Anwendungsfall zu erreichen, sind bei Nickelbasislegierungen verschiedene Legierungselemente bekannt. So wirkt sich zum Beispiel Aluminium positiv auf die Oxidschichtausbildung aus. Auch ist bekannt, dass reaktive Elemente die Haftung der sich ausbildenden Oxidschicht verbessern können und dann die Lebensdauer erhöhen.In order to achieve an optimum oxide layer formation for the specific application, various alloying elements are known in nickel-based alloys. For example, aluminum has a positive effect on the oxide layer formation. It is also known that reactive elements can improve the adhesion of the forming oxide layer and then increase the lifetime.
Durch die
In der
Ziel des Erfindungsgegenstandes ist es, eine Nickelbasislegierung bereitzustellen, durch welche eine Erhöhung der Lebensdauer von daraus hergestellten Bauteilen durch Erhöhung der Funkenerrosions- und Oxidationsbeständigkeit bei gleichzeitig guter Umformbarkeit und Schweißbarkeit herbeiführbar ist.The object of the subject invention is to provide a nickel-based alloy, by which an increase in the life of components made therefrom by increasing the spark erosion and oxidation resistance at the same time good formability and weldability can be brought about.
Dieses Ziel wird erreicht durch eine Nickelbasislegierung, beinhaltend (in Masse-%)
Bevorzugte alternative Ausgestaltungen des Erfindungsgegenstandes sind den Unteransprüchen wie folgt zu entnehmen.Preferred alternative embodiments of the subject invention are set forth in the dependent claims as follows.
Bezüglich der reaktiven Elemente sind somit drei Varianten denkbar, nämlich
Y + Hf,
Y + La sowie
Y + Hf + La.With regard to the reactive elements, three variants are thus conceivable, namely
Y + Hf,
Y + La as well
Y + Hf + La.
Die erfindungsgemäße Nickelbasislegierung ist bevorzugt einsetzbar als Werkstoff für Elektroden von Zündkerzen für Benzinmotoren.The nickel-based alloy according to the invention is preferably usable as a material for electrodes of spark plugs for gasoline engines.
Durch gezielte Einstellung einerseits der Elemente Al, Si, Cr, Mn, Mg und andererseits der reaktiven Elemente Y, Hf, La in ihren jeweiligen Kombinationen kann eine Verbesserung der Lebensdauer von Elektrodenwerkstoffen durch Erhöhung der Funkenerrosions- und Oxidationsbeständigkeit bei gleichzeitig guter Umformbarkeit und Schweißbarkeit herbeigeführt werden.By selective adjustment of the elements Al, Si, Cr, Mn, Mg on the one hand and the reactive elements Y, Hf, La in their respective combinations on the other hand, an improvement in the lifetime of electrode materials can be achieved by increasing the resistance to spark erosion and oxidation while at the same time providing good formability and weldability become.
Dem Element Mg kommt bezüglich der Abbindung von Schwefel eine besondere Bedeutung zu, so dass hier gezielt geringe Schwefelgehalte in der erfindungsgemäßen Nickelbasislegierung eingestellt werden können.The element Mg is of particular importance for the setting of sulfur, so that it is possible to selectively set low sulfur contents in the nickel-based alloy according to the invention.
Bevorzugte Aluminiumgehalte werden (in Masse-%) gesehen im Bereich von 1,2 - 1,5 %.Preferred aluminum contents are (in% by mass) in the range of 1.2-1.5%.
Bevorzugte Siliziumgehalte werden (in Masse-%) gesehen im Bereich zwischen 1,2 und 1,8 %, insbesondere zwischen 1,2 und 1,5 %, während der bevorzugte Mg-Gehalt (in Masse-%) zwischen 0,008 und 0,05 % eingestellt wird.Preferred silicon contents are (in mass%) in the range between 1.2 and 1.8%, in particular between 1.2 and 1.5%, while the preferred Mg content (in% by mass) is between 0.008 and 0, 05% is set.
Tabelle 1 zeigt als Gegenüberstellung vier erfindungsgemäße Laborchargen im Vergleich mit zwei dem Stand der Technik zugehörigen großtechnischen Chargen.Table 1 shows a comparison of four inventive laboratory batches in comparison with two related to the prior art large-scale batches.
Die Laborcharge 1132 stellt ein Beispiel dar, bei welchem die reaktiven Elemente Y + Hf in der erfindungsgemäßen Nickelbasislegierung gegeben sind.The
Die Laborcharge 1140 zeigt ein Beispiel, bei welchem die reaktiven Elemente Y + La in der erfindungsgemäßen Legierung vorhanden sind.
Die Laborchargen 1141 und 1142 offenbaren Beispiele, bei welchen als reaktive Elemente Y + La + Hf in der erfindungsgemäßen Nickelbasislegierung eingestellt wurden.
Die beiden Vergleichslegierungen zeigen bereits bei 900°C Abplatzungen der vorab aufgebauten Oxidschicht. Bei 1.000°C trifft dies zwar auch auf die erfindungsgemäßen Legierungen zu, nicht jedoch in gleichem Umfang, wie bei den Vergleichslegierungen.The two comparative alloys show flaking at 900 ° C of the pre-built oxide layer. Although this also applies to the alloys according to the invention at 1,000 ° C., it does not apply to the same extent as in the case of the comparative alloys.
Claims (11)
- A nickel master alloy composed of (in % by mass)
Al 1.2 - < 2.0% Si 1.2 - < 1.8% C 0.001 - 0.1 % S 0.001 - 0.1 % Cr 0.03-0.1% Mn 0.03-0.1% Cu max. 0.1 % Fe 0.02 - 0.2% Mg 0.005 - 0.06% Pb max.0.005% Y 0.05 - 0.15% and Hf 0.05 - 0.10% or Y 0.05 - 0.15% and La 0.05 - 0.10% or Y 0.05 - 0.15% and Hf 0.05 - 0.10% and La 0.05 - 0.10% Ni rest and elaboration dependent impurities. - A nickel master alloy according to claim 1 comprising (in % by mass)
Al 1.2 - < 2.0% Si 1.2 - < 1.8% C 0.001 - 0.05% S 0.001 - 0.05% Cr 0.03-0.1% Mn 0.03-0.1% Cu max. 0.1 % Fe 0.02 - 0.2% Mg 0.005 - 0.06% Pb max.0.005% Y 0.10 - 0.15% and Hf 0.05 - 0.10% Ni rest and elaboration dependent impurities. - A nickel master alloy according to claim 1 comprising (in % by mass)
Al 1.2 - < 2.0% Si 1.2 - < 1.8% C 0.001 - 0.05% S 0.001 - 0.05% Cr 0.03-0.1% Mn 0.03-0.1% Cu max. 0.1 % Fe 0.02 - 0.2% Mg 0.005 - 0.06% Pb max.0.005% Y 0.10 - 0.15% and La 0.05 - 0.10% Ni rest and elaboration dependent impurities. - A nickel master alloy according to claim 1 comprising (in % by mass)
Al 1.2 - < 2.0% Si 1.2 - < 1.8% C 0.001 - 0.05% S 0.001 - 0.05% Cr 0.03-0.1% Mn 0.03-0.1% Cu max. 0.1 % Fe 0.02 - 0.2% Mg 0.005 - 0.06% Pb max.0.005% Y 0.10 - 0.15% and Hf 0.05 - 0.10% and La 0.05 - 0.10%. - A nickel master alloy according to one of the claims 1 through 4 comprising a content of (in % by mass)
Al 1.2 - 1.5% Si 1.2 - 1.5%. - A nickel master alloy according to one of the claims 1 through 5 comprising a content of (in % by mass)
Mg 0.008 - 0.05%. - A nickel master alloy according to one of the claims 1 through 6 comprising a content of (in % by mass)
Y + Hf 0.11 - 0.18%. - A nickel master alloy according to one of the claims 1 through 6 comprising a content of (in % by mass)
Y + La 0.11 - 0.18%. - A nickel master alloy according to one of the claims 1 through 6 comprising a
content of (in % by mass)Y + Hf+La 0.18 - 0.22%. - A nickel master alloy according to one of the claims 1 through 9 comprising a content of (in % by mass)
Y + Mg 0.11 - 0.13%. - Use of the nickel master alloy according to one of the claims 1 through 10 as electrode material of ignition elements of combustion engines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL07785601T PL2047004T3 (en) | 2006-07-29 | 2007-07-06 | Nickel-based alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006035111A DE102006035111B4 (en) | 2006-07-29 | 2006-07-29 | Nickel-based alloy |
| PCT/DE2007/001203 WO2008014741A1 (en) | 2006-07-29 | 2007-07-06 | Nickel-based alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2047004A1 EP2047004A1 (en) | 2009-04-15 |
| EP2047004B1 true EP2047004B1 (en) | 2011-05-18 |
Family
ID=38626548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07785601A Active EP2047004B1 (en) | 2006-07-29 | 2007-07-06 | Nickel-based alloy |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20100003163A1 (en) |
| EP (1) | EP2047004B1 (en) |
| JP (1) | JP5273620B2 (en) |
| AT (1) | ATE510034T1 (en) |
| BR (1) | BRPI0715515B1 (en) |
| DE (1) | DE102006035111B4 (en) |
| MX (1) | MX2009000987A (en) |
| PL (1) | PL2047004T3 (en) |
| RU (1) | RU2399690C1 (en) |
| WO (1) | WO2008014741A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9137482B2 (en) * | 2010-03-31 | 2015-09-15 | Verizon Patent And Licensing Inc. | Methods and systems for resolution-based modification of recording instructions associated with a scheduled recording of a media content instance |
| DE102010024488B4 (en) * | 2010-06-21 | 2012-04-26 | Thyssenkrupp Vdm Gmbh | Nickel-based alloy |
| EP2634871B1 (en) * | 2010-10-26 | 2019-09-04 | NGK Spark Plug Co., Ltd. | Spark plug |
| JP5697484B2 (en) * | 2011-02-25 | 2015-04-08 | 株式会社デンソー | Spark plug electrode material |
| DE102011007532A1 (en) * | 2011-04-15 | 2012-10-18 | Robert Bosch Gmbh | A spark plug electrode material and spark plug, and a method of manufacturing the spark plug electrode material |
| EP2698439B1 (en) * | 2012-08-17 | 2014-10-01 | Alstom Technology Ltd | Oxidation resistant nickel alloy |
| DE102013004365B4 (en) * | 2013-03-14 | 2015-09-24 | VDM Metals GmbH | Nickel-based alloy with silicon, aluminum and chrome |
| DE102013005677B3 (en) | 2013-04-03 | 2014-07-17 | Geräte- und Pumpenbau GmbH Dr. Eugen Schmidt | Shaft bearing with shaft seal, especially for water pumps in motor vehicles |
| US20170009704A1 (en) * | 2015-07-06 | 2017-01-12 | Rohr, Inc. | Thrust reverser staggered translating sleeve |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB943141A (en) * | 1961-01-24 | 1963-11-27 | Rolls Royce | Method of heat treating nickel alloys |
| US4013459A (en) * | 1975-10-24 | 1977-03-22 | Olin Corporation | Oxidation resistant nickel base alloys |
| GB1542283A (en) * | 1975-12-19 | 1979-03-14 | Draftex Dev Ag | Channel-shaped sealing strips |
| JPS6043897B2 (en) * | 1978-09-07 | 1985-10-01 | 日本特殊陶業株式会社 | Nickel alloy for spark plug electrodes |
| US5204059A (en) * | 1988-07-25 | 1993-04-20 | Mitsubishi Metal Corporation | Ni base alloy for spark plug electrodes of internal combustion engines |
| JP2550158B2 (en) * | 1988-07-25 | 1996-11-06 | 三菱マテリアル株式会社 | Spark plug electrode material for internal combustion engines |
| JPH0445239A (en) * | 1990-06-08 | 1992-02-14 | Toshiba Corp | Alloy for spark plug |
| EP1090155A1 (en) * | 1998-06-30 | 2001-04-11 | Federal-Mogul Corporation | Spark plug electrode alloy |
| CA2348145C (en) * | 2001-05-22 | 2005-04-12 | Surface Engineered Products Corporation | Protective system for high temperature metal alloys |
| DE10224891A1 (en) * | 2002-06-04 | 2003-12-18 | Bosch Gmbh Robert | Nickel alloy suitable for internal combustion engine spark plug electrodes, contains silicon and aluminum with yttrium, hafnium or zirconium |
| JP4769070B2 (en) * | 2005-01-31 | 2011-09-07 | 日本特殊陶業株式会社 | Spark plug for internal combustion engine |
-
2006
- 2006-07-29 DE DE102006035111A patent/DE102006035111B4/en not_active Expired - Fee Related
-
2007
- 2007-07-06 JP JP2009522080A patent/JP5273620B2/en active Active
- 2007-07-06 WO PCT/DE2007/001203 patent/WO2008014741A1/en active Application Filing
- 2007-07-06 PL PL07785601T patent/PL2047004T3/en unknown
- 2007-07-06 EP EP07785601A patent/EP2047004B1/en active Active
- 2007-07-06 AT AT07785601T patent/ATE510034T1/en active
- 2007-07-06 US US12/309,775 patent/US20100003163A1/en not_active Abandoned
- 2007-07-06 BR BRPI0715515-8A patent/BRPI0715515B1/en active IP Right Grant
- 2007-07-06 RU RU2009107229/02A patent/RU2399690C1/en active
- 2007-07-06 MX MX2009000987A patent/MX2009000987A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| RU2399690C1 (en) | 2010-09-20 |
| EP2047004A1 (en) | 2009-04-15 |
| JP5273620B2 (en) | 2013-08-28 |
| DE102006035111B4 (en) | 2010-01-14 |
| DE102006035111A1 (en) | 2008-02-07 |
| JP2009544855A (en) | 2009-12-17 |
| PL2047004T3 (en) | 2011-10-31 |
| WO2008014741A1 (en) | 2008-02-07 |
| ATE510034T1 (en) | 2011-06-15 |
| US20100003163A1 (en) | 2010-01-07 |
| BRPI0715515A2 (en) | 2013-03-05 |
| BRPI0715515B1 (en) | 2015-08-04 |
| MX2009000987A (en) | 2009-02-06 |
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