US20140086755A1 - Turbocharger and component therefor - Google Patents

Turbocharger and component therefor Download PDF

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Publication number
US20140086755A1
US20140086755A1 US14/119,242 US201214119242A US2014086755A1 US 20140086755 A1 US20140086755 A1 US 20140086755A1 US 201214119242 A US201214119242 A US 201214119242A US 2014086755 A1 US2014086755 A1 US 2014086755A1
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Prior art keywords
weight
component
turbocharger
iron
based alloy
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Abandoned
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US14/119,242
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English (en)
Inventor
Gerald Schall
Munevera Kulin
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BorgWarner Inc
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BorgWarner Inc
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Assigned to BORGWARNER INC. reassignment BORGWARNER INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHALL, GERALD, KULIN, Munevera
Publication of US20140086755A1 publication Critical patent/US20140086755A1/en
Abandoned legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/24—Casings; Casing parts, e.g. diaphragms, casing fastenings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B37/00—Engines characterised by provision of pumps driven at least for part of the time by exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C6/00—Plural gas-turbine plants; Combinations of gas-turbine plants with other apparatus; Adaptations of gas-turbine plants for special use
    • F02C6/04—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output
    • F02C6/10—Gas-turbine plants providing heated or pressurised working fluid for other apparatus, e.g. without mechanical power output supplying working fluid to a user, e.g. a chemical process, which returns working fluid to a turbine of the plant
    • F02C6/12—Turbochargers, i.e. plants for augmenting mechanical power output of internal-combustion piston engines by increase of charge pressure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W

Definitions

  • the invention relates to a component for turbocharger applications, in particular in a diesel engine, as per the preamble of claim 1 , and also to an exhaust-gas turbocharger comprising a component as per the preamble of claim 7 .
  • Exhaust-gas turbochargers are systems intended to increase the power of piston engines.
  • an exhaust-gas turbocharger the energy of the exhaust gases is used to increase the power.
  • the increase in power is a result of the increase in the throughput of mixture per working stroke.
  • a turbocharger consists essentially of an exhaust-gas turbine with a shaft and a compressor, wherein the compressor arranged in the intake tract of the engine is connected to the shaft and the blade wheels located in the casing of the exhaust-gas turbine and the compressor rotate.
  • adjusting blades are additionally mounted rotatably in a blade bearing ring and are moved by means of an adjusting ring arranged in the turbine casing of the turbocharger.
  • the material of the components of a turbocharger and in particular of the kinematics components or of the wastegate components thereof, or, in the case of a VTG turbocharger, also of the VTG components thereof.
  • the material of these components has to be heat-resistant, i.e. it still has to afford sufficient strength and therefore dimensional stability even at very high temperatures of up to about 900° C.
  • the material has to have a high resistance to wear and also appropriate oxidation resistance, so that the corrosion or wear on the material is reduced even at the high operating temperatures of several hundred ° C., and therefore the resistance of the material remains ensured under the extreme operating conditions.
  • turbocharger applications as per the preamble of claim 1 and also a turbocharger as per the preamble of claim 7 , which have an improved temperature and oxidation resistance and therefore also a very good dimensional stability and high-temperature strength, and also corrosion resistance, are distinguished by optimum tribological properties and additionally show a reduced susceptibility to wear.
  • an improved temperature resistance of the material and in particular improved sliding wear properties and a reduced tendency toward oxidation are achieved by the embodiment according to the invention, in the form of a component for turbocharger applications or of an exhaust-gas turbocharger comprising such a component, consisting of an iron-based alloy having a ferritic base structure which comprises a carbide and nitride structure.
  • a carbide structure or nitride structure is understood to mean in this case a microstructural carbide precipitation phase or nitride precipitation phase which is formed in the grain and at the grain boundaries of the iron-based alloy.
  • the carbide structure is, in particular, a dendritic microstructure, as a result of which a very good resistance of the material and therefore of the component to deformation and wear is also obtained.
  • the component according to the invention and therefore the exhaust-gas turbocharger according to the invention are also dimensionally stable in long-term operation.
  • the iron-based alloy according to the invention i.e. the ferritic iron-based material having a carbide and nitride structure which forms the component, is distinguished by a maximum sliding wear rate of 0.08 mm in diameter given a contact pressure of 20 MPa, a sliding speed of 0.0025 m/s, a component temperature of about 850° C. and 2 000 000 cycles, i.e. an extraordinary resistance to friction wear.
  • the high-temperature strength, the dimensional stability and also the high-temperature performance are also improved.
  • the wear properties of the component i.e. specifically the resistance thereof to friction wear
  • the elements W, Ti and Nb substantially form the carbide formations in the iron-based alloy, which, in addition to the very good wear performance, also increases the corrosion resistance of the material and therefore of the component according to the invention.
  • the component according to the invention for turbocharger applications is distinguished by the fact that it comprises at least one of the elements selected from: C, W, Cr, Mn, Ti, V, Nb and Si.
  • the presence of at least one of these elements is to be understood as meaning that such an element or a combination of these elements is used to produce the iron-based alloy, which is then processed to form the component according to the invention.
  • the elements added to the iron-based alloy can be present here in their original form, i.e. in elemental form, for example in the form of inclusions or precipitation phases, or else in the form of derivatives thereof, i.e. in the form of a compound of the corresponding element, e.g.
  • the component according to the invention as a metal carbide or metal nitride, which form either during the production of the iron-based alloy or else when forming the component according to the invention which is produced therefrom.
  • the presence of the elements can be detected directly in this case in the component according to the invention by conventional analytical methods.
  • the element carbon serves here primarily for forming the carbide structure according to the invention, i.e. the carbidic precipitation phases, and therefore improves the strength of the material and also the high-temperature strength thereof, and therefore of the component according to the invention for turbocharger applications.
  • the element tungsten too, mostly as a result of the formation of carbidic structures, increases the high-temperature strength and wear resistance of the material and contributes to the toughness thereof.
  • a combination of tungsten with chromium and/or molybdenum makes it possible to considerably improve the corrosion resistance of the material in acid media, and also the hot corrosion performance.
  • the use of chromium here increases the high-temperature tensile strength and the scaling resistance of the material.
  • Chromium is additionally a strong carbide former, and therefore the wear properties of the material, and therefore of the component according to the invention, are also optimized thereby.
  • the use of the element chromium in the iron-based alloy from which the component according to the invention for turbocharger applications is formed has yet another advantage: under the action of high exhaust-gas temperatures on the component, the chromium forms a Cr 2 O 3 surface layer, i.e. an oxidic surface layer on the component, which efficiently promotes the resistance of the component to sliding friction and friction wear under thermal loading.
  • the use of manganese has a deoxidizing effect. It expands the gamma region of the iron-based alloy and increases the yield strength and tensile strength of the material.
  • manganese promotes the wear resistance of the component, in particular at high operating temperatures.
  • Vanadium refines the primary grain of the iron-based alloy during the production thereof and therefore refines the cast structure thereof. This achieves a high degree of grain refinement, which promotes the homogeneity of the iron-based alloy and permits a higher dynamic contact pressure of the material.
  • the element niobium acts as a carbide former and therefore promotes the carbide structure in the grain and at the grain boundaries of the iron-based alloy.
  • Niobium also increases the high-temperature strength and the fatigue strength of the material, and therefore also of the component according to the invention for turbocharger applications.
  • Niobium furthermore promotes the ferrite formation and reduces the gamma region of the iron-based alloy, and can therefore be used in a regulative capacity.
  • Silicon promotes the casting properties of the iron-based alloy by reducing the viscosity of the melt during casting.
  • silicon in the material according to the invention promotes deoxidation, and therefore the addition of this element to the alloy decisively improves the resistance to hot corrosion.
  • the properties of the iron-based alloy can therefore be controlled in a targeted manner, such that the component according to the invention for turbocharger applications and therefore also the exhaust-gas turbocharger according to the invention have a particularly balanced profile of properties. Further elements, and also compounds, can be introduced into the iron-based alloy.
  • the component according to the invention for turbocharger applications is distinguished by the fact that it comprises substantially the elements carbon (C) with 0.1 to 0.5% by weight, in particular with 0.25 to 0.4% by weight, chromium (Cr) with 15 to 22% by weight, in particular with 18 to 20% by weight, manganese (Mn) with at most 1.3% by weight, in particular with at most 1% by weight, silicon (Si) with 0.8 to 2.1% by weight, in particular with 1 to 1.8% by weight, niobium (Nb) with 0.4 to 1.3% by weight, in particular with 0.6 to 1.1% by weight, titanium (Ti) with 0.2 to 0.6% by weight, in particular with 0.3 to 0.5% by weight, tungsten (W) with 1.8 to 3.0% by weight, in particular with 2 to 2.7% by weight, vanadium (V) with 0.3 to 1.0% by weight, in particular with 0.5 to 0.8% by weight, nitrogen (N) with at most 3% by weight, in particular with at most 2% by weight, and
  • the indications of quantity in each case relate here to the overall weight of the iron-based alloy from which the component according to the invention is formed.
  • the presence of said elements is to be understood as meaning that they can be present both in elemental form and also in the form of one of the compounds thereof in the iron-based alloy, and therefore in the component according to the invention for turbocharger applications.
  • substantially the aforementioned elements are present in the component according to the invention in the quantities indicated. This means that unavoidable impurities may be present, although these preferably make up less than 2% by weight and in particular less than 1% by weight, based on the overall weight of the iron-based alloy.
  • the unavoidable residues or impurities in this case comprise, for example, aluminum (Al), nickel (Ni), zirconium (Zr), cerium (Ce), boron (B), phosphorus (P) and sulfur (S).
  • Al aluminum
  • Ni nickel
  • Zr zirconium
  • Ce cerium
  • B boron
  • P phosphorus
  • S sulfur
  • the quantities of the individual elements can in this case be detected directly in the component according to the invention by means of conventional elemental analysis methods.
  • This composition according to the invention provides a component which has a particularly high high-temperature strength, a temperature resistance up to 900° C. and therefore dimensional stability at a high temperature, and which is distinguished by outstanding sliding properties and therefore particularly low sliding wear.
  • the corrosion resistance and oxidation resistance are maximized, in particular at high operating temperatures, as act during operation of a turbocharger on the corresponding component.
  • a material which is produced in this way and from which the component according to the invention is formed thus has the following properties:
  • the component for turbocharger applications is substantially free of sigma phases.
  • Sigma phases are brittle, intermetallic phases of high hardness. They arise when a body-centered cubic metal and a face-centered cubic metal, whose atomic radii match with only a slight discrepancy, strike one another. Sigma phases of this type are undesirable since they have an embrittling effect and also because of the property of the iron matrix to withdraw chromium.
  • the iron-based alloy according to the invention and therefore also the component according to the invention are substantially free of sigma phases, such that the undesirable effects described here fail to appear.
  • the reduction in or prevention of the formation of sigma phases is controlled, in particular, by a targeted selection of the elements of the iron-based alloy, and in particular is achieved in that the silicon content in the alloy material is at most 2.1% by weight and preferably at most 1.8% by weight, based in each case on the overall weight of the iron-based alloy.
  • a component for turbocharger applications which is distinguished by an outstanding wear performance, i.e. a high sliding wear resistance even at high temperatures of up to 900° C., a high high-temperature strength and also dimensional stability and furthermore by an excellent oxidation resistance and corrosion resistance.
  • the component according to the invention is suitable in particular for those components for turbocharger applications which are exposed to high temperatures of up to 900° C. and/or high levels of friction.
  • Exemplary components comprise kinematics components, wastegate components and VTG components, and in particular VTG components and flap mount parts.
  • the iron-based alloy can be produced and processed to form the component according to the invention for turbocharger applications by means of conventional processes. To ensure dimensional stability, age-annealing can be carried out at 900° C. for about 2 hours, with subsequent air cooling, in order to generate secondary precipitations.
  • the material can be welded by means of TIG, plasma and EB welding processes.
  • claim 7 defines an exhaust-gas turbocharger comprising at least one component, as already described, which consists of an iron-based alloy having a ferritic base structure and comprises a carbide and nitride structure.
  • FIG. 1 shows a perspective view, shown partially in section, of an exhaust-gas turbocharger according to the invention.
  • FIG. 1 shows a turbocharger 1 according to the invention, which has a turbine casing 2 and a compressor casing 3 which is connected to the latter via a bearing casing 28 .
  • the casings 2 , 3 and 28 are arranged along an axis of rotation R.
  • the turbine casing is shown partially in section in order to illustrate the arrangement of a blade bearing ring 6 and a radially outer guide grate 18 , which is formed by said ring and has a plurality of adjusting blades 7 which are distributed over the circumference and have rotary axles 8 .
  • nozzle cross sections are formed which, depending on the position of the adjusting blades 7 , are larger or smaller and act to a greater or lesser extent upon the turbine rotor 4 , positioned in the center on the axis of rotation R, with the exhaust gas from an engine, said exhaust gas being supplied via a supply duct 9 and discharged via a central connection piece 10 , in order to drive a compressor rotor 17 seated on the same shaft using the turbine rotor 4 .
  • an actuating device 11 is provided in order to control the movement or the position of the adjusting blades 7 .
  • This may be designed in any desired way, but a preferred embodiment has a control casing 12 which controls the control movement of a tappet member 14 fastened to it, in order to convert the movement of said tappet member on an adjusting ring 5 , located behind the blade bearing ring 6 , into a slight rotational movement of the latter.
  • a free space 13 for the adjusting blades 7 is formed between the blade bearing ring 6 and an annular part 15 of the turbine casing 2 . So that this free space 13 can be ensured, the blade bearing ring 6 has spacers 16 .
  • the indications of quantity of the individual elements relate in each case to the overall weight of the iron-based alloy.
  • An iron-based alloy from which a plurality of components according to the invention for turbocharger applications, specifically flap shaft, flap plate and bush, were formed was produced from the following elements by a common process.
  • the chemical analysis yielded the following values for the elements: C: 0.25 to 0.4% by weight, Cr: 18 to 20% by weight, Mn: less than 1% by weight, Si: 1 to 1.8% by weight, Nb: 0.6 to 1.1% by weight, Ti: 0.3 to 0.5% by weight, W: 2 to 2.7% by weight, V: 0.5 to 0.8% by weight, N: ⁇ 3% by weight, and Fe as the remainder.
  • unavoidable residues of Al, Ni, Zr, Ce, B, P and S were found in traces with a proportion of less than 1% by weight.
  • Measured value Property Tensile strength R m at 20° C. 655 MPa (ASTM E 8M/EN 10002-1) Yield strength R p 0.2 at 20° C. 277 MPa (standard process) Elongation at break 13.5% (standard process) Hardness 248 HB (ASTM E 92/ISO 6507-1) Coefficient of linear expansion at 20° C. 12.6 K ⁇ 1 (standard process) High-temperature strength R m at 900° C. 123 MPa (EN 10002-5) High-temperature strength R m at 800° C. 188 MPa (EN 10002-5) High-temperature strength R m at 700° C. 257 MPa (EN 10002-5) High-temperature strength R m at 600° C.
  • the material was subjected to a validation test series which comprised the following tests:
  • the respective component was distinguished in all tests by an outstanding resistance to the acting forces.
  • the material therefore had an extremely high wear resistance and outstanding oxidation resistance, such that corrosion and wear/friction wear to the material were reduced considerably under the indicated conditions, and therefore the resistance of the material and therefore also of the component formed therefrom also remained ensured over a long time.
  • the respective component (shaft/bush) according to the invention was distinguished by a low high-temperature oxidation, i.e. an oxidation rate of at most 40 ⁇ m, in particular of at most 35 ⁇ m, at a component temperature of 900° C.:
  • Parameter Result Bearing load 10-18 N/mm 2 Sliding speed 0.0025 m/s Component temperature 500-900° C.
  • Surface roughness Rz 6.3 Test medium Diesel exhaust gas Test duration 500 h Clock frequency 0.2 Hz Adjustment angle 45° Friction value ⁇ 0.18 Journal diameter 4.7 mm Pressure pulsation >200 bar Exhaust-gas pressure 1.5 bar Wear rate ⁇ 0.08 mm

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Supercharger (AREA)
  • Ceramic Products (AREA)
US14/119,242 2011-06-07 2012-05-24 Turbocharger and component therefor Abandoned US20140086755A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102011103535.8 2011-06-07
DE102011103535 2011-06-07
PCT/US2012/039278 WO2012170210A2 (fr) 2011-06-07 2012-05-24 Turbocompresseur et composant s'y rapportant

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US (1) US20140086755A1 (fr)
JP (1) JP2014523501A (fr)
KR (2) KR20140038472A (fr)
CN (1) CN103534458A (fr)
DE (1) DE112012001811T5 (fr)
WO (1) WO2012170210A2 (fr)

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WO2018022950A1 (fr) * 2016-07-28 2018-02-01 Borgwarner Inc. Acier ferritique pour turbocompresseurs
US20190048441A1 (en) * 2017-08-09 2019-02-14 Honeywell International Inc. Stainless steel alloys and turbocharger kinematic components formed from stainless steel alloys

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DE102013216473A1 (de) 2013-08-20 2015-02-26 Bosch Mahle Turbo Systems Gmbh & Co. Kg Buchsenelement zur Lagerung einer Stellwelle einer Wastegate-Einrichtung oder einer variablen Turbinen-Geometrie
US20150226110A1 (en) * 2014-02-07 2015-08-13 GM Global Technology Operations LLC Turbocharger waste-gate valve assembly wear reduction
US9499889B2 (en) 2014-02-24 2016-11-22 Honeywell International Inc. Stainless steel alloys, turbocharger turbine housings formed from the stainless steel alloys, and methods for manufacturing the same
US11492690B2 (en) 2020-07-01 2022-11-08 Garrett Transportation I Inc Ferritic stainless steel alloys and turbocharger kinematic components formed from stainless steel alloys
CN113088829A (zh) * 2021-04-07 2021-07-09 天津达祥精密工业有限公司 汽车涡轮壳及排气管用铁素体系耐热钢及其制备方法

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WO2012170210A2 (fr) 2012-12-13
KR20140038472A (ko) 2014-03-28
WO2012170210A3 (fr) 2013-01-31
DE112012001811T5 (de) 2014-02-06
KR20180108881A (ko) 2018-10-04
JP2014523501A (ja) 2014-09-11

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