EP2920334B1 - Procédé de fabrication d'un composant de moteur, composant de moteur et utilisation d'un alliage d'aluminium - Google Patents

Procédé de fabrication d'un composant de moteur, composant de moteur et utilisation d'un alliage d'aluminium Download PDF

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EP2920334B1
EP2920334B1 EP13798957.0A EP13798957A EP2920334B1 EP 2920334 B1 EP2920334 B1 EP 2920334B1 EP 13798957 A EP13798957 A EP 13798957A EP 2920334 B1 EP2920334 B1 EP 2920334B1
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Prior art keywords
aluminium alloy
weight
engine component
silicon
iron
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EP2920334A1 (fr
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Roman Morgenstern
Klaus Lades
Scott Kenningley
Philipp Koch
Robert Willard
Rainer Weiss
Isabella Sobota
Martin Popp
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Federal Mogul Nuernberg GmbH
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Federal Mogul Nuernberg GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/0084—Pistons  the pistons being constructed from specific materials

Definitions

  • the present invention relates to a method for producing and using an engine component, in particular a piston for an internal combustion engine, in which an aluminum alloy is gravity-cast, an engine component at least partially made of an aluminum alloy, and the use of an aluminum alloy for producing such an engine component ,
  • a piston for an internal combustion engine must have a high heat resistance and at the same time be as light and strong as possible. It is of particular importance how the microstructural distribution, morphology, composition and thermal stability of highly heat-resistant phases are formed. An optimization in this regard usually takes into account a minimum content of pores and oxide inclusions.
  • the sought-after material has to be optimized in terms of both isothermal fatigue strength (HCF) and thermo-mechanical fatigue strength (TMF) become.
  • HCF isothermal fatigue strength
  • TMF thermo-mechanical fatigue strength
  • a fine microstructure reduces the risk of microplasticity or microcracks on relatively large primary phases (especially primary silicon precipitates) and hence the risk of crack initiation and propagation.
  • the DE 44 04 420 A1 describes an alloy which can be used in particular for pistons and for components which are exposed to high temperatures and are stressed mechanically.
  • the described aluminum alloy comprises 8.0 to 10.0% by weight of silicon, 0.8 to 2.0% by weight of magnesium, 4.0 to 5.9% by weight of copper, 1.0 to 3.0 Wt .-% nickel, 0.2 to 0.4 wt .-% manganese, less than 0.5 wt .-% iron and at least one element selected from antimony, zirconium, titanium, strontium, cobalt, chromium, and vanadium wherein at least one of these elements is present in an amount of> 0.3% by weight, the sum of these elements being ⁇ 0.8% by weight.
  • the EP 0 924 310 B1 describes an aluminum-silicon alloy which has its application in the production of pistons, in particular for pistons in internal combustion engines.
  • the aluminum alloy has the following composition: 10.5 to 13.5% by weight of silicon, 2.0 to less than 4.0% by weight of copper 0.8 to 1.5% by weight of magnesium, 0, 5 to 2.0% by weight of nickel, 0.3 to 0.9% by weight of cobalt, at least 20 ppm of phosphorus and either 0.05 to 0.2% by weight of titanium or up to 0.2% by weight. % Zirconium and / or up to 0.2% by weight vanadium and balance aluminum and unavoidable impurities.
  • the WO 00/71767 A1 describes an aluminum alloy suitable for high temperature applications, such as heavy loaded pistons or other applications in internal combustion engines.
  • the aluminum alloy is composed of the following elements: 6.0 to 14.0% by weight of silicon, 3.0 to 8.0% by weight of copper, 0.01 to 0.8% by weight of iron, 0 , 5 to 1.5% by weight of magnesium, 0.05 to 1.2% by weight of nickel, 0.01 to 1.0% by weight of manganese, 0.05 to 1.2% by weight of titanium , 0.05 to 1.2 wt .-% zirconium, 0.05 to 1.2 wt .-% vanadium, 0.001 to 0.10 wt .-% strontium and balance aluminum.
  • the DE 103 33 103 B4 describes a piston made of a cast aluminum alloy, wherein the aluminum casting alloy contains: 0.2 or less wt .-% magnesium, 0.05 to 0.3 mass% titanium, 10 to 21 wt .-% silicon, 2 to 3, 5 wt.% Copper, 0.1 to 0.7 wt.% Iron, 1 to 3 wt.% Nickel, 0.001 to 0.02 wt.% Phosphorus, 0.02 to 0.3 wt. % Zirconium and balance aluminum and impurities. It is further described that the size of a non-metallic inclusion present within the bulb is less than 100 ⁇ m.
  • the EP 1 975 262 B1 describes an aluminum casting alloy consisting of: 6 to 9% silicon, 1.2 to 2.5% copper, 0.2 to 0.6% magnesium, 0.2 to 3% nickel, 0.1 to 0.7% iron, 0.1 to 0.3% titanium, 0.03 to 0.5% zirconium, 0.1 to 0.7% manganese, 0.01 to 0.5% vanadium and one or more of the following elements: strontium 0.003 to 0.05%, antimony 0.02-0.2% and sodium 0.001-0.03%, the total amount of titanium and zirconium being less than 0.5%, and aluminum and unavoidable impurities forming the balance when the total amount is 100 percent by mass is used.
  • the WO 2010/025919 A2 describes a method for producing a piston of an internal combustion engine, wherein a piston blank made of an aluminum-silicon alloy with the addition of copper portions is poured and then finished.
  • the invention provides that the copper content is at most 5.5% of the aluminum-silicon alloy and that the aluminum-silicon alloy portions of titanium (Ti), zirconium (Zr), chromium (Cr) or vanadium (V) are admixed and the sum of all ingredients is 100%.
  • the registration DE 102011083969 relates to a method for producing an engine component, in particular a piston for an internal combustion engine, in which an aluminum alloy is gravity-poured by casting, an engine component that consists at least partially of an aluminum alloy, and the use of an aluminum alloy for producing an engine component.
  • the aluminum alloy has the following alloying elements: 6 to 10 wt .-% silicon, 1.2 to 2 wt .-% nickel, 8 to 10 wt .-% copper, 0.5 to 1.5 wt .-% magnesium , 0.1 to 0.7% by weight of iron, 0.1 to 0.4% by weight of manganese, 0.2 to 0.4% by weight of zirconium, 0.1 to 0.3% by weight Vanadium, 0.1 to 0.5 wt .-% of titanium and aluminum and avoidable impurities as the remainder.
  • this alloy has a phosphorus content of less than 30 ppm.
  • JP 2004 256873 A discloses an alloy comprising in mass percent 9.5 to 11.5% Si, 5.0 to 7.7% Cu, 3.5 to 5.5% Ni, 0.55 to 1.5% Mg, 0.003 to 0 , 1% P and 0.15 to 0.7% Fe, and if necessary, at least one of the following metals 0.005 to 0.3% Ti, 0.02 to 0.3% Zr, 0.02 to 0.3 % V, 0.001 to 0.1% B and 0.1 to 0.7% Mn, and the remainder being essentially Al.
  • 0.01 to 0.3% of Ti, 0.0001 to 0.03% of B, 0.01 to 0.3% of Cr, 0.01 to 0.3% of Zr or the like may be contained.
  • JP H8-134577 A an aluminum alloy containing 1-7% Cu, 10-16% Si, 0.3-2% Mg, 0.5-2% Fe, 0.1-4% Mn, 0.01-0.3% Ti, 0.001-0.02% P, 0.0001-0.02% Ca and more, if necessary, containing 0.2-6% Ni.
  • An object of the present invention is to provide a method for producing an engine component, in particular a piston for an internal combustion engine, in which an aluminum alloy is poured by gravity die casting method, so that a highly heat resistant engine component can be produced by gravity die casting.
  • a further object of the invention is to provide an engine component, in particular a piston for an internal combustion engine, which is highly heat-resistant and at least partially consists of an aluminum alloy.
  • the aluminum alloy has the following alloying elements: Silicon: 9% by weight to ⁇ 10.5 wt%, Nickel: > 2.0% by weight to ⁇ 3.5% by weight, Copper: > 3.7% by weight to 5.2% by weight, Cobalt: to ⁇ 1% by weight Magnesium: 0.5% by weight to 1.5% by weight, Iron: 0.1% by weight to 0.7% by weight, Manganese: 0.1% by weight to 0.4% by weight, Zirconium: > 0.1% by weight to ⁇ 0.2% by weight, vanadium: > 0.1% by weight to ⁇ 0.2% by weight, Titanium: 0.05% by weight to ⁇ 0.2% by weight, Phosphorus: 0.004% by weight to 0.008% by weight, and the balance aluminum and unavoidable impurities.
  • the selected aluminum alloy it is possible to produce a motor component in the gravity die casting process, which has a high proportion of finely divided, highly heat-resistant, thermally stable phases and a fine microstructure. Susceptibility to crack initiation and crack propagation e.g. of oxides or primary phases and the TMF-HCF lifetime is reduced by the choice of the alloy according to the invention over the previously known production methods of pistons and similar engine components.
  • the alloy according to the invention in particular the comparatively low silicon content, also results in comparatively less and finer primary silicon being present in its thermally highly loaded bowl edge region, at least in the case of a piston produced according to the invention, so that the alloy leads to particularly good properties of a piston produced according to the invention.
  • a highly heat resistant engine component can be produced by the gravity die casting method.
  • the proportions of cobalt and nickel according to the invention are advantageous for increasing the heat resistance of the alloy. Nickel contributes to the formation of thermally stable intermetallic phases. Cobalt also increases the hardness and overall strength of the alloy. Phosphorus as a nucleating agent contributes to primary silicon precipitates are excreted as finely and homogeneously distributed.
  • the aluminum alloy preferably comprises 0.6% to 0.8% by weight of magnesium, which in particular contributes to the effective formation of secondary, strength-increasing phases in the preferred concentration range without excessive oxide formation occurring.
  • the alloy alternatively or additionally preferably has from 0.4% by weight to 0.6% by weight of iron, which advantageously reduces the tendency of the alloy to stick in the casting mold, wherein the formation of plate-shaped phases remains limited in said concentration range.
  • the weight ratio of iron to manganese in the aluminum alloy is at most about 5: 1, preferably about 2.5: 1.
  • the aluminum alloy contains at most five parts iron versus one part manganese, preferably about 2.5 parts iron versus one part manganese.
  • the sum of nickel and cobalt is> 2.0 wt% and ⁇ 3.8 wt%.
  • the lower limit ensures an advantageous strength of the alloy and the upper limit advantageously ensures a fine microstructure and avoids the formation of coarse, plate-shaped phases which would reduce the strength.
  • the aluminum alloy has a fine microstructure with a low content of pores and inclusions and / or little and small primary silicon, especially in the highly loaded bowl edge region.
  • a low content of pores is preferably to be understood as meaning a porosity of ⁇ 0.01% and less than a few primary silicon ⁇ 1%.
  • the fine microstructure advantageously characterized in that the average length of the primary silicon is about ⁇ 5 microns and its maximum length is about ⁇ 10 microns and the intermetallic phases and / or primary precipitates lengths of on average about ⁇ 30 microns and max ⁇ 50 ⁇ m have.
  • the aluminum alloy in particular in the trough edge region, has an average value of an area of silicon precipitates ⁇ about 100 ⁇ m 2 and / or an average value of an area of the intermetallic phases ⁇ about 200 ⁇ m 2 .
  • the characterization of the microstructure of the aluminum alloy is preferably carried out by means of quantitative microstructure analysis.
  • a metallographic cut is made and micrographically corresponding micrographs are recorded, in particular for the technologically particularly important bowl rim area.
  • an inverted reflected-light microscope can be used for this purpose.
  • individual images are taken, compiled by computer into a surface (for example 5.5 mm ⁇ 4.1 mm) and the areas and surface portions of specific phases determined by means of image processing software.
  • the fine microstructure contributes in particular to the improvement of the thermomechanical fatigue strength. Limiting the size of the primary phases can reduce the susceptibility to crack initiation and crack propagation, thus significantly increasing the TMF-HCF lifetime. Furthermore, it is particularly advantageous due to the notch effect of pores and inclusions to keep their content low.
  • An engine component according to the invention consists at least partially of one of the abovementioned aluminum alloys.
  • Another independent aspect of the invention resides in the use of the above-described aluminum alloy for the manufacture of an engine component, in particular a piston of an internal combustion engine.
  • the found Aluminum alloy processed by gravity die casting process.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)

Claims (15)

  1. Procédé servant à fabriquer un composant de moteur, en particulier un piston pour un moteur à combustion interne, dans lequel un alliage d'aluminium est coulé lors d'un procédé de coulée en coquille par gravité, dans lequel un alliage d'aluminium est constitué des éléments d'alliage qui suivent :
    silicium : 9 % en poids à ≤ 10,5 % en poids,
    nickel : > 2,0 % en poids à < 3,5 % en poids,
    cuivre : > 3,7 % en poids à 5,2 % en poids,
    cobalt : jusqu'à < 1 % en poids,
    magnésium : 0,5 % en poids à 1,5 % en poids,
    fer : 0,1 % en poids à 0,7 % en poids,
    manganèse : 0,1 % en poids à 0,4 % en poids,
    zirconium : > 0,1 % en poids à < 0,2 % en poids,
    vanadium : > 0,1 % en poids à < 0,2 % en poids,
    titane : 0,05 % en poids à < 0,2 % en poids
    phosphore : 0,004 % en poids à 0,008 % en poids,
    et est constitué, pour le reste, d'aluminium et des impuretés inévitables.
  2. Procédé selon la revendication 1, dans lequel l'alliage d'aluminium présente de manière préférée 0,6 % en poids à 0,8 % en poids de magnésium.
  3. Procédé selon l'une quelconque des revendications précédentes 1 à 2, dans lequel l'alliage d'aluminium présente de manière préférée 0,4 % en poids à 0,6 % en poids de fer.
  4. Procédé selon l'une quelconque des revendications précédentes 1 à 3, dans lequel un rapport de poids entre le fer et le manganèse est égal environ à 5:1, de manière préférée le rapport de poids entre le fer et le manganèse est égal environ à 2,5:1 dans l'alliage d'aluminium.
  5. Procédé selon l'une quelconque des revendications précédentes 1 à 4, dans lequel une somme du nickel et du cobalt est de manière préférée > 2,0 % en poids et < 3,8 % en poids.
  6. Procédé selon l'une quelconque des revendications précédentes 1 à 5, dans lequel l'alliage d'aluminium présente une microstructure fine comprenant une faible teneur de pores et d'inclusions et/ou du silicium primaire en petite quantité et de petite dimension, en particulier dans la zone de bord de cavité, dans lequel la porosité est < 0,01 % et/ou la teneur en silicium primaire est < 1 %, dans lequel le silicium primaire présente des longueurs < 5 µm en moyenne et/ou des longueurs maximales < 10 µm, et les phases intermétalliques et/ou les précipités primaires présentent des longueurs < 30 µm en moyenne et/ou des longueurs maximales < 50 µm.
  7. Procédé selon l'une quelconque des revendications précédentes 1 à 6, dans lequel l'alliage d'aluminium présente, en particulier dans la zone de bord de cavité, une valeur moyenne d'une surface de précipités de silicium < 100 µm2 environ et/ou une valeur moyenne d'une surface des phases intermétalliques < 200 µm2 environ.
  8. Composant moteur, en particulier piston pour un moteur à combustion interne, qui est constitué au moins en partie d'un alliage d'aluminium,
    dans lequel l'alliage d'aluminium est constitué des éléments d'alliage qui suivent :
    silicium : 9 % en poids à ≤ 10,5 % en poids,
    nickel : > 2,0 % en poids à < 3,5 % en poids,
    cuivre : > 3,7 % en poids à 5,2 % en poids,
    cobalt : jusqu'à < 1 % en poids,
    magnésium : 0,5 % en poids à 1,5 % en poids,
    fer : 0,1 % en poids à 0,7 % en poids,
    manganèse : 0,1 % en poids à 0,4 % en poids,
    zirconium : > 0,1 % en poids à < 0,2 % en poids,
    vanadium : > 0,1 % en poids à < 0,2 % en poids,
    titane : 0,05 % en poids à < 0,2 % en poids
    phosphore : 0,004 % en poids à 0,008 % en poids,
    et est constitué, pour le reste, d'aluminium et des impuretés inévitables.
  9. Composant de moteur selon la revendication 8, dans lequel l'alliage d'aluminium présente de manière préférée 0,6 % en poids à 0,8 % en poids de magnésium.
  10. Composant de moteur selon l'une quelconque des revendications précédentes 8 à 9, dans lequel l'alliage d'aluminium présente de manière préférée 0,4 % en poids à 0,6 % en poids.
  11. Composant de moteur selon l'une quelconque des revendications précédentes 8 à 10, dans lequel un rapport de poids entre le fer et le manganèse est égal, dans l'alliage d'aluminium à environ 5:1 au maximum, de manière préférée le rapport de poids entre le fer et le manganèse est égal à environ 2,5:1.
  12. Composant de moteur selon l'une quelconque des revendications précédentes 8 à 11, dans lequel une somme composée du nickel et du cobalt doit être de manière préférée > 2,0 % en poids et < 3,8 % en poids.
  13. Composant de moteur selon l'une quelconque des revendications précédentes 8 à 12, dans lequel l'alliage d'aluminium présente une microstructure fine présentant une faible teneur de pores et d'inclusions et/ou du silicium primaire en petite quantité et de petite dimension, en particulier dans la zone de bord de cavité, dans lequel la porosité est < 0,01 % et/ou la teneur en silicium primaire est < 1 %, dans lequel le silicium primaire présente des longueurs < 5 µm en moyenne et/ou des longueurs maximales < 10 µm, et les phases intermétalliques et/ou les précipités primaires présentent des longueurs < 30 µm en moyenne et/ou des longueurs maximales < 50 µm.
  14. Composant de moteur selon l'une quelconque des revendications précédentes 8 à 13, dans lequel l'alliage d'aluminium présente, en particulier dans la zone de bord de cavité, une valeur moyenne d'une surface de précipités de silicium < 100 µm2 environ et/ou une valeur moyenne d'une surface des phases intermétalliques < 200 µm2 environ.
  15. Utilisation d'un alliage d'aluminium servant à fabriquer un composant de moteur, en particulier un piston d'un moteur à combustion interne,
    dans laquelle l'alliage d'aluminium est constitué des éléments d'alliage qui suivent :
    silicium : 9 % en poids à ≤ 10,5 % en poids,
    nickel : > 2,0 % en poids à < 3,5 % en poids,
    cuivre : > 3,7 % en poids à 5,2 % en poids,
    cobalt : jusqu'à < 1 % en poids,
    magnésium : 0,5 % en poids à 1,5 % en poids,
    fer : 0,1 % en poids à 0,7 % en poids,
    manganèse : 0,1 % en poids à 0,4 % en poids,
    zirconium : > 0,1 % en poids à < 0,2 % en poids,
    vanadium : > 0,1 % en poids à < 0,2 % en poids,
    titane : 0,05 % en poids à < 0,2 % en poids
    phosphore : 0,004 % en poids à 0,008 % en poids,
    et est constitué, pour le reste, d'aluminium et des impuretés inévitables.
EP13798957.0A 2012-11-14 2013-11-14 Procédé de fabrication d'un composant de moteur, composant de moteur et utilisation d'un alliage d'aluminium Active EP2920334B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012220765.1A DE102012220765A1 (de) 2012-11-14 2012-11-14 Verfahren zur Herstellung eines Motorbauteils, Motorbauteil und Verwendung einer Aluminiumlegierung
PCT/EP2013/073812 WO2014076174A1 (fr) 2012-11-14 2013-11-14 Procédé de fabrication d'un composant de moteur, composant de moteur et utilisation d'un alliage d'aluminium

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EP2920334A1 EP2920334A1 (fr) 2015-09-23
EP2920334B1 true EP2920334B1 (fr) 2016-11-02

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US (2) US10022788B2 (fr)
EP (1) EP2920334B1 (fr)
JP (2) JP6526564B2 (fr)
KR (1) KR102138394B1 (fr)
CN (1) CN104812921B (fr)
BR (1) BR112015010798B1 (fr)
DE (1) DE102012220765A1 (fr)
ES (1) ES2611970T3 (fr)
HU (1) HUE032076T2 (fr)
MX (1) MX2015005896A (fr)
PL (1) PL2920334T3 (fr)
WO (1) WO2014076174A1 (fr)

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DE102014209102A1 (de) 2014-05-14 2015-11-19 Federal-Mogul Nürnberg GmbH Verfahren zur Herstellung eines Motorbauteils, Motorbauteil und Verwendung einer Aluminiumlegierung
DE102014224229A1 (de) * 2014-11-27 2016-06-02 Federal-Mogul Nürnberg GmbH Verfahren zur Herstellung eines Motorbauteils, Motorbauteil und Verwendung einer Aluminiumlegierung
DE102015205895A1 (de) * 2015-04-01 2016-10-06 Federal-Mogul Nürnberg GmbH Aluminium-Gusslegierung, Verfahren zur Herstellung eines Motorbauteils, Motorbauteil und Verwendung einer Aluminium-Gusslegierung zur Herstellung eines Motorbauteils
DE102020108585A1 (de) * 2019-04-09 2020-10-15 Ks Kolbenschmidt Gmbh Kolben für einen Verbrennungsmotor
DE102020205193A1 (de) 2019-05-16 2020-11-19 Mahle International Gmbh Verfahren zur Herstellung eines Motorbauteils, Motorbauteil und die Verwendung einer Aluminiumlegierung
CN113502417A (zh) * 2021-07-14 2021-10-15 无锡华星机电制造有限公司 一种高热强度铝硅合金材料及其制造方法
CN114959378B (zh) * 2022-06-15 2023-05-26 湖南江滨机器（集团）有限责任公司 一种铝硅合金和铝硅合金的铸件的制备方法

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EP2920334A1 (fr) 2015-09-23
WO2014076174A1 (fr) 2014-05-22
PL2920334T3 (pl) 2017-03-31
JP6526564B2 (ja) 2019-06-05
CN104812921A (zh) 2015-07-29
HUE032076T2 (en) 2017-08-28
US20160271687A1 (en) 2016-09-22
MX2015005896A (es) 2015-09-10
JP2016505382A (ja) 2016-02-25
CN104812921B (zh) 2018-01-19
ES2611970T3 (es) 2017-05-11
US20180093322A1 (en) 2018-04-05
KR102138394B1 (ko) 2020-07-28
JP2018114556A (ja) 2018-07-26
KR20150070449A (ko) 2015-06-24
BR112015010798B1 (pt) 2019-12-10
DE102012220765A1 (de) 2014-05-15
US10189080B2 (en) 2019-01-29
US10022788B2 (en) 2018-07-17

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