JP2009544855A - Nickel base alloy - Google Patents
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- JP2009544855A JP2009544855A JP2009522080A JP2009522080A JP2009544855A JP 2009544855 A JP2009544855 A JP 2009544855A JP 2009522080 A JP2009522080 A JP 2009522080A JP 2009522080 A JP2009522080 A JP 2009522080A JP 2009544855 A JP2009544855 A JP 2009544855A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims 3
- 239000000356 contaminant Substances 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 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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- 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
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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)
- Manufacture And Refinement Of Metals (AREA)
- Contacts (AREA)
Abstract
Description
本発明は、合金成分としてケイ素、アルミニウム及び反応性元素を有するニッケルベース合金に関する。 The present invention relates to nickel-based alloys having silicon, aluminum and reactive elements as alloy components.
ニッケルベース合金は、特に、内燃機関の着火要素の電極を製造するために使用される。この種の電極の消耗では、２つの損傷機構が観察され、即ち高温腐食及びスパークエロージョンである。 Nickel-based alloys are used in particular for producing the electrodes of ignition elements of internal combustion engines. In this type of electrode wear, two damage mechanisms are observed: hot corrosion and spark erosion.
高温腐食による消耗は、材料損失測定により並びにメタログラフ試験により、取り出し（Anlagerung）の後に設定した試験温度で測定される。 The wear due to hot corrosion is measured at the test temperature set after the removal by means of material loss measurements and by metallographic tests.
スパークエロージョンは、材料燃焼であり、これは火花（Zuendfunke）により引き起こされる。それぞれの火花のフラッシュオーバーの際には、限定された材料容積が電極から溶融して排出され、かつ、部分的に蒸発される。 Spark erosion is material combustion, which is caused by sparks (Zuendfunke). During each spark flashover, a limited volume of material is melted out of the electrode and partially evaporated.
両方の損傷機構のためには、酸化物層形成の種類は特別な意味を有する。 For both damage mechanisms, the type of oxide layer formation has a special meaning.
具体的な適用の場合のための最適な酸化物層形成を達成するために、ニッケルベース合金では様々な合金要素が公知である。従って、例えばアルミニウムが、酸化物層形成に対して有利に作用する。反応性元素が、形成される酸化物層の付着を改善することができ、かつ、次いで使用期間を向上できることも公知である。 Various alloy elements are known for nickel-based alloys in order to achieve optimal oxide layer formation for specific applications. Thus, for example, aluminum has an advantageous effect on oxide layer formation. It is also known that reactive elements can improve the adhesion of the oxide layer that is formed and can then improve the period of use.
GB-A 2031950によりニッケル合金が公知になり、この合金は（質量％で）約０．２〜３％のＳｉ、約０．５％以下のＭｎ、次の群：約０．２〜３％のＣｒ、約０．２〜３％のＡｌ及び約０．０１〜１％のＹからなる群から選択された少なくとも２種の金属、残分ニッケルからなる。 GB-A 2031950 makes nickel alloys known, which are (by weight) about 0.2-3% Si, about 0.5% or less Mn, the following group: about 0.2-3% And at least two metals selected from the group consisting of about 0.2-3% Al and about 0.01-1% Y, the balance being nickel.
DE-A 102 24 891中には、ニッケルベース合金が提案され、これは（質量％で）１．８〜２．２％のケイ素、０．０５〜０．１％のイットリウム及び／又はハフニウム及び／又はジルコニウム、２〜２．４％のアルミニウム、残分のニッケルを有する。この種の合金は、この高いアルミニウム−及びケイ素含有量に関して、困難な条件下でのみ加工され、かつ従って、大工業的な使用（technischen Grosseinsatz）にあまり適さない。 In DE-A 102 24 891, a nickel-based alloy is proposed, which is (by weight) 1.8-2.2% silicon, 0.05-0.1% yttrium and / or hafnium and / Or zirconium, 2 to 2.4% aluminum, remaining nickel. This type of alloy is processed only under difficult conditions with regard to this high aluminum and silicon content and is therefore not very suitable for technischen Grosseinsatz.
本発明による主題の目的は、スパークエロージョン−及び酸化抵抗性の向上により、同時に良好な成形性及び溶接性をで、製造される部材の使用期間の向上をもたらすニッケルベース合金を提供することである。 The object of the subject-matter according to the invention is to provide a nickel-based alloy which, by improving spark erosion and oxidation resistance, at the same time gives good formability and weldability and improves the service life of the manufactured parts. .
この目的は、質量％で、
本発明の主題の有利な選択的な形態は、以下のとおり下位請求項から取り出すことができる。 Advantageous alternative forms of the inventive subject matter can be taken from the subclaims as follows.
反応性元素に関して、従って３つの変形が考慮可能であり、即ち、
Ｙ＋Ｈｆ、
Ｙ＋Ｌａ並びに
Ｙ＋Ｈｆ＋Ｌａである。
With respect to reactive elements, therefore, three variants can be considered:
Y + Hf,
Y + La and Y + Hf + La.
本発明によるニッケルベース合金は有利には、ガソリンエンジンのための点火プラグの電極のための原料として使用可能である。 The nickel-based alloy according to the invention can advantageously be used as a raw material for spark plug electrodes for gasoline engines.
一方では元素Ａｌ、Ｓｉ、Ｃｒ、Ｍｎ、Ｍｇの、そして他方では反応性元素Ｙ、Ｈｆ、Ｌａの狙いを定めた調整により、このそれぞれの組み合わせにおいて、電極材料の使用期間の改善を、同時に良好な成形性及び溶接性で、スパークエロージョン−及び酸化抵抗性の向上により引き起こすことができる。 With the targeted adjustment of the elements Al, Si, Cr, Mn, Mg on the one hand and the reactive elements Y, Hf, La on the other hand, it is possible to simultaneously improve the period of use of the electrode material in each of these combinations With good formability and weldability, it can be caused by improved spark erosion and oxidation resistance.
元素Ｍｇは、硫黄の結合に関して特別に重要であり、従ってここでは狙いを定めた少ない硫黄含有量が本発明によるニッケルベース合金中で調整されることができる。 The element Mg is of particular importance with regard to the binding of sulfur, so that a low sulfur content aimed here can be adjusted in the nickel-base alloy according to the invention.
有利なアルミニウム含有量（質量％で）は、１．２〜１．５％の範囲内が有利である。 An advantageous aluminum content (in mass%) is advantageously in the range from 1.2 to 1.5%.
有利なケイ素含有量（質量％で）は、１．２〜１．８％、１．２〜１．５％の範囲内が有利であり、この一方で、この有利なＭｇ含有量（質量％で）は０．００８〜０．０５％に調整される。 The advantageous silicon content (in% by weight) is advantageously in the range from 1.2 to 1.8%, 1.2 to 1.5%, while this advantageous Mg content (in% by weight) In) is adjusted to 0.008-0.05%.
第１表は、対比として、技術水準に属する大工業的なチャージ２つと比較した本発明による実験室チャージ５つを示す。 Table 1 shows, in contrast, five laboratory charges according to the present invention compared to two large industrial charges belonging to the state of the art.
実験室チャージ１１３２は、反応性元素Ｙ＋Ｈｆが本発明によるニッケルベース合金中に添加されている一実施例を示す。
実験室チャージ１１４０は、反応性元素Ｙ＋Ｌａが本発明によるニッケルベース合金中に存在する一実施例を示す。
実験室チャージ１１４１及び１１４２は、反応性元素としてＹ＋Ｌａ＋Ｈｆが本発明によるニッケルベース合金中で調整されている実施例を開示する。 Laboratory charges 1141 and 1142 disclose examples in which Y + La + Hf as a reactive element is adjusted in a nickel-based alloy according to the present invention.
図１及び２は、第１表に応じた合金のための一方で９００℃そして他方で１０００℃の温度での材料損失試験を示す。 1 and 2 show material loss tests at temperatures of 900 ° C. on the one hand and 1000 ° C. on the other for the alloys according to Table 1.
この両方の比較合金は、既に９００℃で、前もって構成された酸化物層の剥離を示す。これは確かに１０００℃で本発明による合金に対しても生じ、しかしながら比較例と同じ程度ではない。 Both of these comparative alloys already exhibit a pre-configured oxide layer delamination at 900 ° C. This certainly occurs for the alloys according to the invention at 1000 ° C., but not to the same extent as the comparative example.
Claims (11)
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 最大０．１％
Ｆｅ ０．０２〜０．２％
Ｍｇ ０．００５〜０．０６％
Ｐｂ 最大０．００５％
Ｙ ０．０５〜０．１５％及びＨｆ ０．０５〜０．１０％又は
Ｙ ０．０５〜０．１５％及びＬａ ０．０５〜０．１０％又は
Ｙ ０．０５〜０．１５％及びＨｆ ０．０５〜０．１０％及びＬａ ０．０５〜０．１０％（質量％で）
Ｎｉ残分及び製造に条件付けられた汚染物質
からなるニッケルベース合金。 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 up to 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb up to 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% (in mass%)
Nickel-based alloy consisting of Ni residue and contaminants conditioned to manufacture.
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 最大０．１％
Ｆｅ ０．０２〜０．２％
Ｍｇ ０．００５〜０．０６％
Ｐｂ 最大０．００５％
Ｙ ０．１０〜０．１５％及びＨｆ ０．０５〜０．１０％（質量％で）
Ｎｉ残分及び製造に条件付けられた汚染物質
を含有する請求項１記載のニッケルベース合金。 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 up to 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb up to 0.005%
Y 0.10 to 0.15% and Hf 0.05 to 0.10% (by mass)
The nickel-base alloy of claim 1 containing Ni residue and contaminants conditioned to manufacture.
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 最大０．１％
Ｆｅ ０．０２〜０．２％
Ｍｇ ０．００５〜０．０６％
Ｐｂ 最大０．００５％
Ｙ ０．１０〜０．１５％及びＬａ ０．０５〜０．１０％（質量％で）
Ｎｉ残分及び製造に条件付けられた汚染物質
を含有する請求項１記載のニッケルベース合金。 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 up to 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb up to 0.005%
Y 0.10 to 0.15% and La 0.05 to 0.10% (by mass)
The nickel-base alloy of claim 1 containing Ni residue and contaminants conditioned to manufacture.
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 最大０．１％
Ｆｅ ０．０２〜０．２％
Ｍｇ ０．００５〜０．０６％
Ｐｂ 最大０．００５％
Ｙ ０．１０〜０．１５％及びＨｆ ０．０５〜０．１０％及びＬａ ０．０５〜０．１０％
（質量％で）を含有する請求項１記載のニッケルベース合金。 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 up to 0.1%
Fe 0.02-0.2%
Mg 0.005-0.06%
Pb up to 0.005%
Y 0.10-0.15% and Hf 0.05-0.10% and La 0.05-0.10%
The nickel-base alloy according to claim 1, containing (in mass%).
Ｓｉ １．２〜１．５％
の含量（質量％で）を有する、請求項１から４までのいずれか１項記載のニッケルベース合金。 Al 1.2-1.5%
Si 1.2-1.5%
The nickel-based alloy according to claim 1, having a content (in mass%) of 5.
の含量（質量％で）を有する、請求項１から５までのいずれか１項記載のニッケルベース合金。 Mg 0.008-0.05%
The nickel-base alloy according to any one of claims 1 to 5, having a content of
の含量（質量％で）を有する、請求項１から６までのいずれか１項記載のニッケルベース合金。 Y + Hf 0.11-0.18%
The nickel-base alloy according to any one of claims 1 to 6, having a content of
の含量（質量％で）を有する、請求項１から６までのいずれか１項記載のニッケルベース合金。 Y + La 0.11-0.18%
The nickel-base alloy according to any one of claims 1 to 6, having a content of
の含量（質量％で）を有する、請求項１から６までのいずれか１項記載のニッケルベース合金。 Y + Hf + La 0.18-0.22%
The nickel-base alloy according to any one of claims 1 to 6, having a content of
の含量（質量％で）を有する、請求項１から９までのいずれか１項記載のニッケルベース合金。 Y + Mg 0.11-0.13%
Nickel-based alloy according to any one of claims 1 to 9, having a content of
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006035111A DE102006035111B4 (en) | 2006-07-29 | 2006-07-29 | Nickel-based alloy |
| DE102006035111.8 | 2006-07-29 | ||
| PCT/DE2007/001203 WO2008014741A1 (en) | 2006-07-29 | 2007-07-06 | Nickel-based alloy |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2009544855A true JP2009544855A (en) | 2009-12-17 |
| JP2009544855A5 JP2009544855A5 (en) | 2012-11-01 |
| JP5273620B2 JP5273620B2 (en) | 2013-08-28 |
Family
ID=38626548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009522080A Active JP5273620B2 (en) | 2006-07-29 | 2007-07-06 | Nickel base 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947474A (en) * | 2010-06-21 | 2013-02-27 | 蒂森克鲁普德国联合金属制造有限公司 | Nickel-based alloy |
| JP2014037630A (en) * | 2012-08-17 | 2014-02-27 | Alstom Technology Ltd | Oxidation resistant nickel alloy |
| US9932656B2 (en) | 2013-03-14 | 2018-04-03 | Vdm Metals International Gmbh | Nickel-based alloy with silicon, aluminum, and chromium |
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| 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 |
| 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 |
| 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 |
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| WO2000000652A1 (en) * | 1998-06-30 | 2000-01-06 | Federal-Mogul Corporation | Spark plug electrode alloy |
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- 2007-07-06 MX MX2009000987A patent/MX2009000987A/en active IP Right Grant
- 2007-07-06 AT AT07785601T patent/ATE510034T1/en active
- 2007-07-06 WO PCT/DE2007/001203 patent/WO2008014741A1/en active Application Filing
- 2007-07-06 RU RU2009107229/02A patent/RU2399690C1/en active
- 2007-07-06 PL PL07785601T patent/PL2047004T3/en unknown
- 2007-07-06 US US12/309,775 patent/US20100003163A1/en not_active Abandoned
- 2007-07-06 JP JP2009522080A patent/JP5273620B2/en active Active
- 2007-07-06 EP EP07785601A patent/EP2047004B1/en active Active
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| JPH0234736A (en) * | 1988-07-25 | 1990-02-05 | Mitsubishi Metal Corp | Ni-base alloy for spark plug electrode of internal combustion engine |
| JPH0445239A (en) * | 1990-06-08 | 1992-02-14 | Toshiba Corp | Alloy for spark plug |
| JP2004011024A (en) * | 2002-06-04 | 2004-01-15 | Robert Bosch Gmbh | Nickel based alloy and its usage |
| JP2006236977A (en) * | 2005-01-31 | 2006-09-07 | Ngk Spark Plug Co Ltd | Spark plug for internal combustion engine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102947474A (en) * | 2010-06-21 | 2013-02-27 | 蒂森克鲁普德国联合金属制造有限公司 | Nickel-based alloy |
| CN102947474B (en) * | 2010-06-21 | 2015-07-29 | 蒂森克鲁普德国联合金属制造有限公司 | Nickel-base alloy |
| JP2014037630A (en) * | 2012-08-17 | 2014-02-27 | Alstom Technology Ltd | Oxidation resistant nickel alloy |
| US9932656B2 (en) | 2013-03-14 | 2018-04-03 | Vdm Metals International Gmbh | Nickel-based alloy with silicon, aluminum, and chromium |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008014741A1 (en) | 2008-02-07 |
| DE102006035111B4 (en) | 2010-01-14 |
| JP5273620B2 (en) | 2013-08-28 |
| US20100003163A1 (en) | 2010-01-07 |
| PL2047004T3 (en) | 2011-10-31 |
| BRPI0715515A2 (en) | 2013-03-05 |
| MX2009000987A (en) | 2009-02-06 |
| BRPI0715515B1 (en) | 2015-08-04 |
| ATE510034T1 (en) | 2011-06-15 |
| DE102006035111A1 (en) | 2008-02-07 |
| EP2047004B1 (en) | 2011-05-18 |
| RU2399690C1 (en) | 2010-09-20 |
| EP2047004A1 (en) | 2009-04-15 |
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