EP3134560B1 - Pièce structurale dotée d'un revêtement thermique - Google Patents

Pièce structurale dotée d'un revêtement thermique Download PDF

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Publication number
EP3134560B1
EP3134560B1 EP15711655.9A EP15711655A EP3134560B1 EP 3134560 B1 EP3134560 B1 EP 3134560B1 EP 15711655 A EP15711655 A EP 15711655A EP 3134560 B1 EP3134560 B1 EP 3134560B1
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EP
European Patent Office
Prior art keywords
pore
rounding
indentation
friction
pores
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15711655.9A
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German (de)
English (en)
Other versions
EP3134560A1 (fr
Inventor
Thomas Behr
Jens Böhm
Mareike Hahn
Martin Hartweg
Tobias Hercke
Thomas Kreisl
Manuel Michel
Günter RAU
Christoph Reckzügel
Stefan Schweickert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mercedes Benz Group AG
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Daimler AG
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Publication date
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Publication of EP3134560A1 publication Critical patent/EP3134560A1/fr
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    • 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
    • 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
    • C23C4/18—After-treatment
    • 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
    • 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
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/004—Cylinder liners
    • 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
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/18—Other cylinders
    • F02F1/20—Other cylinders characterised by constructional features providing for lubrication
    • 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 
    • F02F3/10—Pistons  having surface coverings
    • 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
    • F02F7/00—Casings, e.g. crankcases or frames
    • F02F7/0085—Materials for constructing engines or their parts

Definitions

  • the invention relates to a thermally coated component according to the type defined in more detail in the preamble of claim 1.
  • thermal coating which is made possible in particular by thermal spraying, for example the LDS (arc wire spraying) or PTWA (plasma transferred wire arc) process.
  • thermal spraying for example the LDS (arc wire spraying) or PTWA (plasma transferred wire arc) process.
  • Such surfaces have, in particular, open pores, which also help to keep oil in the area of the surface.
  • thermally applied coating can be combined with a subsequent machining process such as honing, for example.
  • Such a structure is from the generic DE 10 2012 002 766 A1 known.
  • the thermally coated component there is characterized by a certain so-called oil retention or oil retention volume, which ensures that a corresponding desired or theoretically predetermined amount of oil remains in the area of the friction-optimized surface during operation, i.e. when the friction partners slide on each other .
  • oil retention or oil retention volume which ensures that a corresponding desired or theoretically predetermined amount of oil remains in the area of the friction-optimized surface during operation, i.e. when the friction partners slide on each other .
  • optimal component pairings can be created with regard to friction, preferably for cylinder liners in internal combustion engines.
  • a coating which has good tribological properties. This is an iron-based coating that contains micropores. The coating can then be smoothed using a honing process.
  • the JP 0 198 764 H shows something similar when coating a piston ring.
  • a method for producing a sliding surface on a light metal alloy in which the layer is applied by thermal spraying, in particular plasma spraying.
  • a plain bearing and a method for its production are also known.
  • a filler material is applied by means of laser coating and then machined and / or etched.
  • the object of the present invention is now to optimize such a surface of a thermally coated component even further.
  • the thermally coated component according to the invention is realized in such a way that pores occurring in the thermally coated surface are optimized with regard to an indentation rounding in such a way that an increase in the indentation rounding, which results from a ratio of the depth of the indentation rounding to a length section of the surface or parallel to the
  • the surface in which the pore is located is calculated, in each case has a value of more than 2.5 ⁇ m / mm and up to 5.5 ⁇ m / mm.
  • Such an increase in the indentation rounding for example averaged over the entire surface for all pores of more than 2.5 ⁇ m / mm, allows a further significant increase in the oil holding volume through correspondingly smooth transitions of the pore flank into the actual surface.
  • Such surface features have a very beneficial effect on the wear of friction partners, e.g. in the case of a thermally coated cylinder liner, on the wear of piston rings.
  • Such high increase values of the indentation rounding can be achieved in particular by honing with ceramic honing stones, preferably if honing has been carried out beforehand with diamond honing stones.
  • Ceramic honing stones are honing stones with ceramic cutting materials, for example silicon carbide (SiC) or aluminum oxide (Al2O3), preferably with a ceramic bond. Grain sizes of the ceramic cutting materials of more than 400 mesh (approx. 40 ⁇ m) have proven to be well suited.
  • diamond honing stones have diamond cutting materials in a metallic bond.
  • the cutting materials can also be attached to the honing stones by means of synthetic resin or plastic bonds, but the aforementioned bonds are more advantageous for economic reasons (service life of the honing stones, tool costs, reprocessing of the tools).
  • Commonly used honing stones such as diamond honing stones, leave pores with an indentation rounding with a correspondingly flat transition between the pore flank and the actual indenting rounding and thus a rather small increase value, which is typically in the order of magnitude between 0.5 and 1.5. It is surprising that, by preferably subsequent honing with ceramic honing stones, the increase in the indentation rounding can be increased to values of more than 2.5 ⁇ m / mm, typically to values between 3 and 5.5 ⁇ m / mm. The surface then has a very smooth cover structure with a correspondingly open porosity without the individual pores being covered. Due to the high rise values and the correspondingly smooth transitions of the pore flanks into the indentation curves the oil holding volume can then be increased again significantly compared to the prior art, in particular by approx. 40-50%.
  • a boundary line can be detected, for example, which separates the area of the indenting rounding of the pore from the surrounding surface.
  • a mean height level of the surface surrounding the respective pore is first determined (e.g. by means of white light interferometry or other conventional measurement technology). Afterwards, points belonging to this pore are determined, which are lowered compared to this mean height level (by a predetermined value, e.g. the resolution limit of the respective measurement technology) and border on the surrounding surface. These points then form the boundary line of this pore.
  • a tangent to the boundary line is formed at least in some points of the boundary lines.
  • the mean slope of the fillet is recorded along a defined measuring section.
  • the mean slopes of all measurement sections of the pore are then averaged in order to obtain an average value for the rounding of the indentation of the respective pore, which is then formulated as a so-called increase in rounding of the indentation of the respective pore.
  • the method can then be continued at other pores in order to obtain an average value of all increases in all indentation fillets of all pores of the entire surface or of individual sections of the surface.
  • a first delimitation line is first recorded again, which separates the area of the rounding of the pore from the surrounding surface.
  • the first boundary line runs on a first defined height level.
  • a second boundary line is then formed within, which is shifted in the direction of the pore, ideally in the area in which the indentation rounding is separated from the pore itself and which also runs at a defined height level. If the height of the two boundary lines is known, a height difference can be determined. This difference in height can then be divided by the mean distance between the boundary lines in order to obtain a mean increase in the rounding of the indentation of the respective pore.
  • the measured values can be determined using a two-dimensional surface measurement method, in particular white light interferometry, and then converted with a three-dimensional data set on the basis of the measurement. This can then be used, for example, via image processing methods to detect the boundary lines, the inclines and the ascent.
  • the friction-optimized surface is machined, preferably machined.
  • This machining which can be implemented in particular as honing, takes place after the thermal coating has been applied, for example after a cylinder running surface or a cylinder liner has been coated on the surface by thermal spraying. The honing then improves the surface quality and the surface, e.g. B. brought the cylinder to the desired size.
  • the friction-optimized surface can be finished by a multi-stage honing, honing first with diamond honing stones and then with ceramic honing stones.
  • a pre-machining with diamond honing stones and a final post-processing with ceramic honing stones leads to very favorable indentation roundings, so that the advantageous increase values of the indentation roundings of more than 2.5 ⁇ m / mm, preferably more than 3 ⁇ m / mm, are achieved.
  • the tribological properties of the friction-optimized surface can be increased even further, in particular through a significantly increased oil holding volume compared to the prior art.
  • a pore 1 in a thermally sprayed, friction-optimized surface 2 is shown purely by way of example.
  • the representation of the Figure 1 comes from a white light interferometry and shows different colors or different shades of gray depending on the height of the material.
  • the representation in Figure 1 thus ultimately reproduces a three-dimensional topography of the measured surface 2 with the pore 1 and the surface 2 surrounding the pore 1.
  • This three-dimensional image of the topography of the surface 2 can then be processed further, in particular using image processing methods.
  • the pore 1 is analogous to the illustration in FIG Figure 1 on the left of the representation of the Figure 2 to recognize again.
  • a boundary line 3 is drawn and in the right illustration of the Figure 2 again shown separately.
  • This boundary line 3 which could also be referred to as the first boundary line, as will be shown later, separates the area of a so-called indentation rounding 4, which in the representations of FIG Figures 1 and 2 can be seen in corresponding shades of gray, of the surface 2 surrounding the pore 1.
  • a mean height level of the surface 2 surrounding the pore 1 is first determined by means of white light interferometry. Afterwards, points belonging to this pore 1 are determined which are lowered by twice the resolution limit compared to this mean height level and to the surrounding ones Adjacent surface. These points then form the delimitation line 3 of the pore 1 with respect to the surface 2.
  • FIG. 3 In the representation of the Figure 3 this is shown again in a basic sectional view of one side of the pore 1.
  • the scale is selected in the direction y in ⁇ m in the direction x in mm, which results in a distorted representation. However, this is necessary to visualize the indentation rounding.
  • the pore 1 can be seen as a partial depression in the surface 2 of the material denoted by 5, for example a thermally sprayed coating.
  • a connection of the actual pore 1 with the surface 2 can be seen with a solid line, which shows a comparatively flat transition from a flank 6 of the pore 1 into the area of the indentation rounding 4 and thus into the surface 2.
  • the solid line shows a comparatively smooth transition from the pore flank 6 to the indentation rounding 4.
  • the indentation rounding 4, 4 ′ can now, depending on how it turns out, definitely have an influence on the function of the component or the coating 5. It is therefore desirable to determine this indentation rounding 4, 4 ′ as one of the parameters of the surface 2 by measurement.
  • a so-called increase in the indentation rounding 4, 4 ′ can now be determined using appropriate image processing methods, for example, as shown in the illustration of FIG Figure 4 is indicated, at one - but in particular for each point - of the boundary line 3, a tangent designated by T is applied.
  • a measuring section M of defined length is formed perpendicular to this tangent T, the length of which is defined symmetrically to the boundary line 3 both in the direction of the pore and in the direction of the surroundings.
  • the total length of the measuring section M is 60 ⁇ m. Then, starting from the beginning of the measuring section M outside the boundary line 3 in the direction of the pore 1 inward, the mean slope along the measuring section M is recorded, for example using a linear regression method. If this determination of the slope is now carried out along the boundary line 3 in several, in particular in all points of this boundary line 3, a corresponding mean value can then be formed, so that a corresponding mean slope of the indentation rounding 4 of the pore 1 can be obtained.
  • This mean slope is then formulated as a so-called increase in the indentation rounding 4, 4 '.
  • the coordinates x and y drawn in are calculated by the ratio of the measured depth y of the indentation rounding 4, 4 'to the surrounding surface 2 in the ratio or normalized to a mean length x parallel to the surface 2 (corresponding to the mean value of all projections of all measuring sections M).
  • the value of the rise A is preferably given in ⁇ m / mm of the length segment x in the direction of the surface 2. The larger this value, the smoother the transition from the pore area 6 to the surface 2. A correspondingly smooth transition corresponds to FIG Figure 3 the indentation rounding marked 4. If the value of the rise becomes smaller, then the transition to the pore flank 6 becomes less smooth and could, for example, be that in the illustration of FIG Figure 3 correspond to transition marked 4 '.
  • the geometry of the indentation fillets 4, 4 ' can be compared accordingly , which facilitates the function-oriented measurement of the surface 2 and, based on the indentation rounding expressed in numbers and measured over the mean rise A in ⁇ m / mm, enables good comparability of the surface 2, for example after processing with different tools and / or different coatings 5 with one another.
  • a pore edge line 7 can be created in addition to the delimitation line 3, which separates the area of the indentation rounding 4, 4 'of the pore 1 from the pore 1 itself. This pore edge line 7 then forms the inner boundary of the measuring section M perpendicular to the tangent T. Zur Such a pore edge line 7 is illustrated in the illustration in FIG Figure 5 drawn.
  • the pore edge line 7, if, like in this case, like the first delimiting line 3, runs at a height level, can also be used for an alternative method for determining the slope of the indentation rounding 4, 4 ′.
  • the pore edge line 7 forms a second delimitation line 7, while the delimitation line 3 forms a first delimitation line 3.
  • both boundary lines 3, 7 run at the same (average) height level in relation to surface 2.
  • the method can be used as an alternative to the method mentioned above and, depending on the image processing, can possibly be faster than the method described above and accordingly require less computing power. Otherwise, it also applies here that a corresponding method can be carried out for each pore, and that accordingly the rounding of the respective pores 1 is available individually or as an average value for the entire surface 2 or for sections of the surface 2 in order to enable a function-oriented assessment of the surface 2 to be carried out.
  • the rise A can now be used in particular to assess the tribological properties of the friction-optimized surface 2.
  • the pores 1 are here in a thermal coating 5, which is applied to a cylinder liner or a cylinder housing for an internal combustion engine of a motor vehicle.
  • the mean slope A of pores 1 was determined using the method described above, after the pores 1 had been honed in a conventional manner with a diamond honing tool.
  • These mean increases A of the surface 2 honed with diamond tools are in the diagram of FIG Figure 7 rightmost. They have values between -1 and +1.5 for the slope.

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

Claims (7)

  1. Pièce structurale dotée d'un revêtement thermique, laquelle présente une surface optimisée en termes de frottements (2) d'une voie de roulement pour un partenaire de frottement, la surface (2) présentant des pores,
    caractérisée en ce que
    les pores (1) présentent un arrondi d'insertion (4, 4'),
    dont l'élévation (A) présente en tant que rapport entre la profondeur (y) de l'arrondi d'insertion (4, 4') et une section de longueur (x) de la surface (2) ou parallèle à la surface (2), une valeur supérieure à 2,5 µm/mm et jusqu'à 5, 5 µm/mm.
  2. Pièce structurale dotée d'un revêtement thermique selon la revendication 1, caractérisée en ce que l'élévation atteint au moyen de tous les pores de la surface (2) 3µm/mm.
  3. Pièce structurale dotée d'un revêtement thermique selon la revendication 1 ou la revendication 2, caractérisée en ce que la surface optimisée en termes de frottements (2) est usinée mécaniquement, de préférence usinée par enlèvement de copeaux.
  4. Pièce structurale dotée d'un revêtement thermique la revendication 1 ou la revendication 2 ou 3, caractérisée en ce que la surface optimisée en termes de frottement (2) est usinée par polissage.
  5. Pièce structurale dotée d'un revêtement thermique selon la revendication 4, caractérisée en ce que la surface optimisée en termes de frottement (2) est soumise à au moins deux passages de polissage de finition, d'abord à l'aide d'un outil doté de barres de polissage en diamant et ensuite à l'aide d'un outil doté de barres de polissage en céramique.
  6. Pièce structurale dotée d'un revêtement thermique selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le revêtement thermique est une couche appliquée selon le procédé de projection à chaud, de préférence une couche appliquée selon le procédé de projection à chaud de fil par arc électrique ou une couche PTWA.
  7. Pièce structurale dotée d'un revêtement thermique selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la pièce structurale est un bloc moteur ou un piston ou une chemise, de préférence une chemise de cylindre.
EP15711655.9A 2014-04-24 2015-03-13 Pièce structurale dotée d'un revêtement thermique Active EP3134560B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014005947 2014-04-24
PCT/EP2015/000563 WO2015161909A1 (fr) 2014-04-24 2015-03-13 Pièce structurale dotée d'un revêtement thermique

Publications (2)

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EP3134560A1 EP3134560A1 (fr) 2017-03-01
EP3134560B1 true EP3134560B1 (fr) 2021-04-21

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US (1) US20170044652A1 (fr)
EP (1) EP3134560B1 (fr)
JP (1) JP6495941B2 (fr)
CN (1) CN106232856A (fr)
WO (1) WO2015161909A1 (fr)

Citations (1)

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Publication number Priority date Publication date Assignee Title
JPH0198764A (ja) * 1987-10-08 1989-04-17 Teikoku Piston Ring Co Ltd シリンダとピストンリングとの組合わせ

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US2602709A (en) * 1950-03-24 1952-07-08 Norton Co Bearing combination
JPS6039747B2 (ja) * 1976-07-08 1985-09-07 トヨタ自動車株式会社 軽金属の表面処理方法
JPH02219851A (ja) * 1989-02-21 1990-09-03 Mitsuboshi Belting Ltd ポリアセタール樹脂組成物
DE4440713C2 (de) * 1993-11-23 1998-07-02 Volkswagen Ag Verfahren zum Herstellen von Gleitflächen an Gußeisenteilen, insbesondere von Zylinderlaufbahnen von Brennkraftmaschinen, sowie Honwerkzeug zur Durchführung des Verfahrens
US5663124A (en) * 1994-12-09 1997-09-02 Ford Global Technologies, Inc. Low alloy steel powder for plasma deposition having solid lubricant properties
ES2143239T3 (es) * 1995-10-31 2000-05-01 Volkswagen Ag Procedimiento para la realizacion de una superficie de deslizamiento sobre una aleacion de metal ligero.
US7265467B2 (en) * 2003-11-07 2007-09-04 Nidec Corporation Fluid dynamic pressure bearing and spindle motor
EP2157304B1 (fr) * 2008-08-18 2013-07-10 Wärtsilä Schweiz AG Procédé d'usinage destiné à produire une surface de roulement sur une paroi de cylindre d'une chemise de cylindre d'un moteur à combustion interne, et chemise de cylindre
KR101534864B1 (ko) * 2009-06-30 2015-07-08 현대자동차주식회사 차량용 실린더라이너의 제조방법
DE102010053326A1 (de) * 2010-12-03 2011-08-25 Daimler AG, 70327 Gleitlager und Verfahren zu dessen Herstellung
DE102012002766B4 (de) 2012-02-11 2014-05-22 Daimler Ag Thermisch beschichtetes Bauteil mit einer reibungsoptimierten Laufbahnoberfläche und Verfahren zur Bauteil-Beschichtungsoberflachensimulation eines thermisch beschichteten Bauteils

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198764A (ja) * 1987-10-08 1989-04-17 Teikoku Piston Ring Co Ltd シリンダとピストンリングとの組合わせ

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CN106232856A (zh) 2016-12-14
JP2017519947A (ja) 2017-07-20
WO2015161909A1 (fr) 2015-10-29
EP3134560A1 (fr) 2017-03-01
JP6495941B2 (ja) 2019-04-03
US20170044652A1 (en) 2017-02-16

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