WO2006133685A1 - Procede pour munir une chemise de cylindre d'un revetement - Google Patents

Procede pour munir une chemise de cylindre d'un revetement Download PDF

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Publication number
WO2006133685A1
WO2006133685A1 PCT/DE2006/001023 DE2006001023W WO2006133685A1 WO 2006133685 A1 WO2006133685 A1 WO 2006133685A1 DE 2006001023 W DE2006001023 W DE 2006001023W WO 2006133685 A1 WO2006133685 A1 WO 2006133685A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
alloy
sprayed
cylinder
cylinder liner
Prior art date
Application number
PCT/DE2006/001023
Other languages
German (de)
English (en)
Inventor
Gerhard Bucher
Original Assignee
Mahle International Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mahle International Gmbh filed Critical Mahle International Gmbh
Priority to EP06761655A priority Critical patent/EP1896626B1/fr
Priority to JP2008516123A priority patent/JP5199868B2/ja
Priority to DE502006004802T priority patent/DE502006004802D1/de
Priority to US11/921,692 priority patent/US20090110841A1/en
Priority to BRPI0612058-0A priority patent/BRPI0612058A2/pt
Priority to CN200680021287XA priority patent/CN101198712B/zh
Priority to KR1020077025418A priority patent/KR101319165B1/ko
Publication of WO2006133685A1 publication Critical patent/WO2006133685A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying

Definitions

  • the invention relates to a method for coating a cylinder liner according to the preamble of claim 1.
  • Cylinder crankcases are usually made of light metal, especially aluminum, cast, due to the poor tribological properties of light metals, the necessity exists to pour cylinder liners made of an iron-based material, such as gray cast iron, in the cylinder crankcase with. This results in the problems of anchoring the cylinder liners sufficiently firmly in the cylinder crankcase, and to ensure sufficient heat transfer between the cylinder liners and the cylinder crankcase. These problems can be solved by giving the outer surfaces of the cylinder liners a roughcast structure with undercuts. However, this entails that the webs between the cast-in cylinder liners in the cylinder liners are very wide, and therefore that the space requirement of the cylinder liners is very large.
  • an oxidation protection layer is applied, which consists of a zinc alloy, and whose task is to prevent the oxidation of the AlSi layer, whereby the metallic bonding of the cover layer is prevented with the Umgussmaterial the cylinder crankcase.
  • the disadvantage here is that the AISi alloy is already oxidized during the spraying of the cover layer.
  • the resulting oxide skin adheres very firmly to the AlSi layer.
  • their melting temperature is higher than the achievable temperatures during encapsulation.
  • the oxide skin is indeed removable, but it forms after removal very quickly again, so that even an additional applied protective layer of zinc or a zinc alloy does not ensure a metallic bond between the AlSi layer and the Umgussmaterial the cylinder crankcase can.
  • the coefficient of thermal expansion of the AISi cover layer is approximately 1.7 times the coefficient of thermal expansion of gray cast iron, so that, in the case of temperature changes, stresses arise in the known layer system which impair the bond between the cylinder liner and the cylinder crankcase.
  • the gradation of the melting temperatures, starting from the cylinder liner, through the layer system of the invention to the Umgussmaterial the cylinder crankcase causes a dissolution or a diffusion-based alloying of the outer layer with the Umgussmaterial, which causes a stable metallic bond between the cylinder liner and the Umgussmaterial the cylinder crankcase.
  • the coating consisting of the alloys according to the invention has the advantage that its alloy constituents participate in the precipitation hardening in the bonding zone.
  • a cylinder liner which consists of an iron-based material that may be alloyed or unalloyed.
  • the cylinder liner is made of gray cast iron, which may contain either lamellar graphite, vermicular graphite or nodular graphite.
  • the gray cast iron can in this case have a ferritic-pearlitic, a pearlitic, a bainitic or an austenitic basic structure.
  • the outer surface of the cylinder liner may be smooth. But it can also have all other surface finishes to a flat Raugussober Structure.
  • the cylinder liner may have a machined outer surface.
  • the cylinder crankcase is made of one of the common light metal casting material, with both aluminum-based and magnesium-based castings in question.
  • the outer surface of the cylinder liner is coated by thermal spraying. In preparation for this, it is necessary to clean the outer surface of dirt and oxides and then roughen. Suitable methods for this are brushing and / or blasting. In particular, blasting with coarse corundum, ie with crystallized Al 2 O 3 , is suitable for this purpose.
  • a first layer is applied to the outer surface of the cylinder liner by thermal spraying.
  • This first layer consists either of 99.9% copper, a CuAl8 alloy, a CuAl8Ni2 alloy, a CuP8 alloy, a CuSi3 alloy or a CuZn37 alloy (brass).
  • the aim here is a low-pore and low-oxide layer with a thickness between 60 ⁇ m and 130 ⁇ m.
  • a further layer of one of the aforementioned copper alloys whose melting temperature is lower than that of copper but whose melting temperature is higher than that of the material constituting the outer coating hereinafter referred to as the second layer.
  • wires of the alloys mentioned in the trade is available, is preferably applied as a thermal spraying method, the wire flame spraying, wherein the melted wire-shaped spray additive in the center of an acetylene-oxygen flame and is sprayed by means of a nebulizer gas, such as compressed air or nitrogen, on the outer surface of the cylinder liner.
  • a nebulizer gas such as compressed air or nitrogen
  • arc wire spraying wherein two wire-shaped spray additives are melted in an arc and thrown by means of a Zerstäubergases on the outer surface of the cylinder liner.
  • two wire-shaped spray additives are melted in an arc and thrown by means of a Zerstäubergases on the outer surface of the cylinder liner.
  • the composition of the layer produced thereby can be varied within wide ranges.
  • copper and zinc wire it is possible to apply a CuZn alloy with up to 45% zinc to the outer surface of the cylinder liner.
  • nitrogen or argon as a sputtering gas oxidation of the materials is largely prevented.
  • One way to further reduce the oxidation of the sprayed material and the oxide content of the sprayed layer is to use the Ka Itgassp scribe method, wherein unmelted and heated only to a few hundred degrees powder particles to a speed between 300m / sec. and 1200 m / sec. accelerated and sprayed onto the outer surface of the cylinder liner. Due to micro-friction due to the impact of the powder particles, the temperature at the contact surface increases and leads to micro-welding of the powder particles with the outer surface of the cylinder liner.
  • Applicable is also the high-speed flame spraying (HVOF spraying), wherein a continuous gas combustion takes place with high pressures within a combustion chamber, in the central axis of the powdery spray additive is supplied.
  • the high pressure generated in the combustion chamber of the fuel gas-oxygen mixture produces a high particle velocity, which leads to very dense spray coatings with good adhesion properties.
  • the functions of the first layer are to ensure good adhesion of the first layer to the gray cast iron of the cylinder liner, to provide good bond requirements for a second layer, and a gradation of melt temperatures, ie, a gradual transition of melt temperatures of the gray cast iron of the cylinder liner over the To realize first layer and the second layer up to the Umgussmetall the cylinder crankcase. In addition, this causes a gradation of the thermal expansion coefficients starting from the cylinder liner over the first and the second layer up to the light metal of the cylinder crankcase.
  • the second layer is applied to the first layer using one of the above-mentioned thermal spraying methods.
  • a Zn85Al15 alloy with 85% zinc and 15% aluminum is preferably used.
  • the aluminum content may vary between 3% and 20%.
  • the aim is a pore and low-oxide layer with a thickness between 60 .mu.m and 130 .mu.m.
  • the function of the second layer is to adhere well to the first layer.
  • the 15 wt.% Aluminum AlZn alloy has a melting point of 450 ° C, causing the second layer to melt from its casting material as the cylinder crankcase is cast, thereby ensuring metallic bonding between the cylinder liner and the cylinder crankcase surround material becomes.
  • the AlZn alloy forms a very thin oxide layer, this does not hinder the bond between cylinder liner and crankcase. Nevertheless, it is advantageous for the AlZn alloy to be a few wt%. Adding copper, because this the formation of the oxide layer is completely prevented, which brings a further improvement in the bond between the cylinder liner and the crankcase with it.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

L'invention concerne un procédé permettant de munir une chemise de cylindre consistant en un matériau à base de fer, d'un revêtement. Une première couche et une seconde couche d'un alliage de zinc sont pulvérisées sur la surface extérieure de la chemise de cylindre, au moyen d'un procédé de pulvérisation thermique. Une bonne liaison métallique s'opère entre la chemise de cylindre et le carter de vilebrequin, dans laquelle la chemise de cylindre est coulée, par utilisation de cuivre allié ou non allié pour la première couche et par utilisation d'un alliage zinc-aluminium pour la seconde couche.
PCT/DE2006/001023 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement WO2006133685A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP06761655A EP1896626B1 (fr) 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement
JP2008516123A JP5199868B2 (ja) 2005-06-15 2006-06-16 シリンダースリーブを被覆する方法
DE502006004802T DE502006004802D1 (de) 2005-06-15 2006-06-16 Verfahren zum beschichten einer zylinderlaufbuchse
US11/921,692 US20090110841A1 (en) 2005-06-15 2006-06-16 Method for coating a cylinder sleeve
BRPI0612058-0A BRPI0612058A2 (pt) 2005-06-15 2006-06-16 processo para o revestimento de uma camisa de cilindro
CN200680021287XA CN101198712B (zh) 2005-06-15 2006-06-16 气缸衬套涂敷涂层的方法
KR1020077025418A KR101319165B1 (ko) 2005-06-15 2006-06-16 실린더 슬리브 코팅 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005027828A DE102005027828A1 (de) 2005-06-15 2005-06-15 Verfahren zum Beschichten einer Zylinderlaufbuchse
DE102005027828.0 2005-06-15

Publications (1)

Publication Number Publication Date
WO2006133685A1 true WO2006133685A1 (fr) 2006-12-21

Family

ID=36972883

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2006/001023 WO2006133685A1 (fr) 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement

Country Status (9)

Country Link
US (1) US20090110841A1 (fr)
EP (1) EP1896626B1 (fr)
JP (1) JP5199868B2 (fr)
KR (1) KR101319165B1 (fr)
CN (1) CN101198712B (fr)
BR (1) BRPI0612058A2 (fr)
DE (2) DE102005027828A1 (fr)
RU (1) RU2414526C2 (fr)
WO (1) WO2006133685A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014053033A3 (fr) * 2012-10-05 2014-06-05 Mahle Metal Leve S/A Chemise de cylindre pour montage dans un bloc moteur et bloc moteur

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CN102160300B (zh) * 2008-09-19 2014-06-18 诺基亚西门子通信公司 网络元件以及操作网络元件的方法
CN102371351A (zh) * 2010-08-20 2012-03-14 宝馨实业股份有限公司 一种含高硅铝合金衬套及其制法
DE102010055162A1 (de) 2010-12-18 2012-06-21 Mahle International Gmbh Beschichtung sowie beschichtetes Eingussbauteil
DE102011085324A1 (de) * 2011-10-27 2013-05-02 Ford Global Technologies, Llc Plasmaspritzverfahren
DE102012015405B4 (de) * 2012-08-03 2014-07-03 Federal-Mogul Burscheid Gmbh Zylinderlaufbuchse und Verfahren zu deren Herstellung
CN105925928A (zh) * 2016-06-22 2016-09-07 成都成发科能动力工程有限公司 一种大型透平机械叶片的表面处理方法
US10780491B2 (en) 2018-01-11 2020-09-22 Ford Global Technologies, Llc Aluminum casting design with alloy set cores for improved intermetallic bond strength

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EP0900326A1 (fr) * 1996-12-05 1999-03-10 MAN B & W Diesel A/S Element de cylindre, tel que chemise de cylindre, piston, jupe de piston ou segment de piston, pour moteur a combustion interne de type diesel et segment des pistons pour un tel moteur
DE19729017A1 (de) * 1997-07-08 1999-02-04 Ae Goetze Gmbh Zylinderlaufbuchse
EP1230413A1 (fr) * 1999-10-29 2002-08-14 MAN B & W Diesel A/S Procede et dispositif pour produire des pieces de machine pourvues d'au moins une surface de glissement
US20010037786A1 (en) * 2000-04-20 2001-11-08 Manfred Fischer Cylinder liner for combustion engines and manufacturing method
US20020073982A1 (en) * 2000-12-16 2002-06-20 Shaikh Furqan Zafar Gas-dynamic cold spray lining for aluminum engine block cylinders
WO2004106721A1 (fr) * 2003-05-28 2004-12-09 Daimlerchrysler Ag Boite de glissement de cylindre, procede de fabrication et element composite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014053033A3 (fr) * 2012-10-05 2014-06-05 Mahle Metal Leve S/A Chemise de cylindre pour montage dans un bloc moteur et bloc moteur

Also Published As

Publication number Publication date
US20090110841A1 (en) 2009-04-30
EP1896626A1 (fr) 2008-03-12
JP5199868B2 (ja) 2013-05-15
RU2007147933A (ru) 2009-07-20
EP1896626B1 (fr) 2009-09-09
DE102005027828A1 (de) 2006-12-21
JP2008544175A (ja) 2008-12-04
DE502006004802D1 (de) 2009-10-22
RU2414526C2 (ru) 2011-03-20
CN101198712A (zh) 2008-06-11
CN101198712B (zh) 2010-12-15
KR20080019202A (ko) 2008-03-03
BRPI0612058A2 (pt) 2010-10-13
KR101319165B1 (ko) 2013-10-16

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