EP3029162A1 - Procédé de traitement à chaud d'un produit en manganèse-acier et produit en manganèse-acier - Google Patents

Procédé de traitement à chaud d'un produit en manganèse-acier et produit en manganèse-acier Download PDF

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Publication number
EP3029162A1
EP3029162A1 EP14195644.1A EP14195644A EP3029162A1 EP 3029162 A1 EP3029162 A1 EP 3029162A1 EP 14195644 A EP14195644 A EP 14195644A EP 3029162 A1 EP3029162 A1 EP 3029162A1
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Prior art keywords
steel product
holding
manganese
range
cooling
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EP14195644.1A
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German (de)
English (en)
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EP3029162B1 (fr
Inventor
Ludovic Samek
Friedrich FÜREDER-KITZMÜLLER
Enno Arenholz
Philipp Kürnsteiner
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Voestalpine Stahl GmbH
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Voestalpine Stahl GmbH
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Application filed by Voestalpine Stahl GmbH filed Critical Voestalpine Stahl GmbH
Priority to EP14195644.1A priority Critical patent/EP3029162B1/fr
Priority to ES14195644.1T priority patent/ES2674133T3/es
Priority to KR1020177017190A priority patent/KR102029561B1/ko
Priority to US15/528,928 priority patent/US11124850B2/en
Priority to JP2017528998A priority patent/JP2018502986A/ja
Priority to EP15802096.6A priority patent/EP3227465A1/fr
Priority to CN201580065026.7A priority patent/CN107109506B/zh
Priority to PCT/EP2015/078105 priority patent/WO2016087392A1/fr
Publication of EP3029162A1 publication Critical patent/EP3029162A1/fr
Publication of EP3029162B1 publication Critical patent/EP3029162B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/185—Hardening; Quenching with or without subsequent tempering from an intercritical temperature
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite

Definitions

  • the present invention relates to a method of heat treating a manganese steel product, also referred to herein as a mid-manganese steel product. It is also a special alloy of a manganese steel product that can be heat treated by a special process.
  • steel products may include ferrite, pearlite, retained austenite, annealed martensite phases, martensite phases and bainite microstructures form.
  • the properties of steel alloys depend, among other things, on the proportions of the different phases, microstructures and their structural arrangement in microscopic observation.
  • each of these phases and microstructures has different properties.
  • the steel alloys comprising several such phases and microstructures may therefore have significantly different mechanical properties.
  • IF steel deep-drawing steels
  • IF stands for "interstitial-free”
  • this IF steel has only a low content of alloying elements embedded in interstitial sites.
  • Mn manganese
  • the manganese content in% by weight is often in the range between 2.5 and 12%. Therefore, they are so-called medium-manganese steels, which are also referred to as medium-manganese steels.
  • Such medium-manganese steels are typically characterized by a microstructure consisting of a ferritic, martensite and austenite matrix. In this matrix, as the second or third phase, predominantly austenite is incorporated at the grain boundaries. Austenite has a strengthening effect.
  • the proportion of martensite in medium-manganese steels is usually at most 80-90 vol.%. Due to this ambivalent microstructure combination, the medium-manganese steel has a relatively low yield strength with a high tensile strength, which is favorable for the forming process.
  • Fig. 1 is a classical, highly schematic diagram shown in which the elongation at break (called elongation) in percent (also called ductility) is plotted on the tensile strength in MPa.
  • the tensile strength in MPa allows a statement about the lower yield strength of a material.
  • the diagram of Fig. 1 gives an overview of the strength classes of currently used steel materials. In general, the following statement applies: the higher the yield strength of a steel alloy, the lower the elongation at break of this alloy. In simple terms, it can be said that the elongation at break decreases with increasing tensile strength and vice versa. It must therefore be found for each application, an optimal compromise between the elongation at break and the tensile strength.
  • Fig. 1 statements can be made about the relationship between the strength and the forming capacity of different steel materials.
  • the range denoted by reference numeral 1 includes medium-manganese steels having an Mn content of between 3 and 7 wt.% And a carbon content of between 0.05 and 0.1 wt.%.
  • medium-manganese steels are expensive to produce because they undergo a 2-step heat treatment.
  • these steels are e.g. alloyed with manganese to get a martensitic phase.
  • a medium manganese steel with a high tensile strength of e.g. 1200 MPa typically has an elongation of only between 2 and 8%.
  • TRIP steels are designated by the reference numeral 2 and the so-called HD steels bear the reference numeral 3.
  • TRIP stands in English for "TRANSformation Induced Plasticity”.
  • HD stands for High Ductility.
  • AHSS HD Advanced High-Strength Steels High Ductility
  • AHSS HD steels have, for example, a medium manganese content in the range between 1.2 and 3.5 wt.% And a carbon content (C), which is between 0.05 and 0.25 wt.%.
  • the steel products of the invention should have a tensile strength R m (also called minimum strength) which is significantly greater than 1200 MPa.
  • R m also called minimum strength
  • the tensile strength should be even greater than 1400 MPa.
  • the minimum elongation at break (A 80 ) should be 10% - 20%.
  • the steel products of the invention should enable workability in the deep drawing process.
  • a combination of process and alloy concepts provides a multi-phase steel product having an ultrafine microstructure and good machinability.
  • the alloy of the steel products of the invention has an average manganese content, which means that the manganese content is in the range of 3.5% by weight ⁇ Mn ⁇ 6% by weight.
  • the manganese content in all embodiments is in the range of 4 wt% ⁇ Mn ⁇ 6 wt%.
  • the multiphase steel products of the invention form a heterogeneous system or a heterogeneous structure.
  • the steel products of the invention preferably have, according to the invention, a microstructure comprising austenite, bainite and martensite and a significantly reduced proportion of ferrite.
  • the ferrite phase is relatively soft compared to the bainite phase. Replacing the soft ferrite phase or matrix with a stronger and finer (nano-sized) bainite phase makes it possible to provide a steel product that has outstanding properties. Above all, the replacement of the ferrite phase or matrix by bainite leads to a significant increase in the hole expansion properties.
  • the steel products of the invention preferably have in all embodiments a proportion of a bainitic microstructure which is substantially greater than 5% by volume of the steel product. More preferably, the proportion of the bainitic microstructure is in the range of 10 to 80 vol.%. A proportion of the bainitic microstructure in the range from 20 to 40% by volume has proven to be particularly suitable.
  • the bainitic microstructure is characterized in that it has a very fine structure and that it comprises little or no carbide.
  • the retained austenite content is preferably significantly less than 30% by volume in all embodiments. Preferred embodiments are those in which the retained austenite content is less than 10% by volume.
  • the steel products of the invention preferably have at least proportionally microstructures or areas with an austenitic microstructure.
  • the proportion of the austenitic microstructure is preferably in the range of 5 to 20% by volume of the steel product in all embodiments.
  • the steel products of the invention preferably have proportionally austenite grains which are isotropic (ie independent of the direction) are distributed in the structure of the steel products.
  • the volume fraction of the austenite grains is preferably less than 5% in all embodiments.
  • the size of the austenite grains is preferably less than 1 ⁇ m in all embodiments.
  • the steel products of the invention preferably have in all embodiments a level of martensite that is lower than other steel alloys whose tensile strength is in the range above 1000 MPa.
  • the martensite content is usually 80-90% vol.% In prior art high tensile steel alloys. Although this low martensite content can be expected negative influences, the mechanical properties and the deep drawability of the steel product according to the invention are unexpectedly good.
  • the tensile strength R m of the steel products according to the invention in the region of 1400 MPa is significantly higher than the tensile strength which a steel alloy with conventionally large martensite content can offer.
  • the microstructure of the steel products according to the invention is characterized in that the comparatively low martensite content is in the form of lath-shaped martensite. It turns out that these fine martensitic battens have a positive effect on the tensile strength of the invention.
  • the steel products of the invention have proportionally microstructures or areas with ferrite.
  • the proportion of these microstructures or regions is preferably in the range below 50% by volume of the steel product in all embodiments.
  • the volume fraction of the ferrite phase is between 15 and 30%, wherein the ferrite phase forms a KRZ lattice (KRZ stands for cubic-body-centered) and has a low dislocation density.
  • the grains of the ferrite phase usually have a slightly anisotropic expansion.
  • the alloy of the steel products comprises Al and Si components.
  • the proportion of Al plus Si is preferably in the range ⁇ 4 wt.% In all embodiments.
  • the following condition holds: Al + Si ⁇ 3% by weight.
  • the addition of specifically Al and Si in said weight percent range unexpectedly leads to an improvement in the tensile strength and at the same time to an increased elongation at break.
  • the addition of Al and Si leads to the promotion of bainite formation.
  • the bainite microstructure has, as already mentioned, a significant influence on the positive properties of the alloy of the steel products.
  • Al and Si also serves to suppress carbide formation in bainite, which further improves the positive properties of the alloy.
  • the proportions of Al and Si can also be defined more precisely in all embodiments as follows: Si ⁇ 0.5% by weight and Al ⁇ 3% by weight.
  • the alloy of the steel products preferably comprises Al and Si fractions according to the following formula: Si + Al ⁇ 1% by weight.
  • the alloy of the steel products preferably comprises a phosphorus component.
  • the proportion of P is preferably ⁇ 0.03 wt% in all embodiments.
  • the alloy of the steel products preferably comprises a copper portion.
  • the proportion of Cu is preferably ⁇ 0.1% by weight in all embodiments.
  • the steel products of the invention preferably comprise, according to the invention, at least proportionally a small amount of Nb so as to reduce the Ms temperature.
  • Ms refers to the martensite start temperature.
  • the proportion of Nb is preferably less than 0.4 in all embodiments Wt.%.
  • the steel products of the invention preferably have at least proportionally a small amount of Ti according to the invention.
  • the proportion of Ti is preferably less than 0.2% by weight in all embodiments.
  • the steel products of the invention preferably have a small proportion of V according to the invention, at least proportionally.
  • the proportion of V in all embodiments is preferably less than 0.1% by weight.
  • the described structure of the steel products with the indicated weight percentages is achieved by a special temperature treatment, which leads to controlled transformations and microstructures in the multiphase steel product.
  • This temperature treatment is referred to herein as en-bloc temperature treatment because it involves only a single continuous treatment process. That is, the en-bloc thermal treatment of the invention has no break or break after which the steel product would have to be reheated.
  • ART stands for "austenite reverted transformation”.
  • the described alloys surprisingly lead to steel products having the desired properties, although they undergo only an en bloc thermal treatment with the process steps according to claim 1.
  • This special form of en-bloc temperature treatment has a significant influence on the formation of the specific ultrafine structure (s) of the steel product.
  • the microstructure or the microstructure of the steel product is specifically controlled and defined by a special and efficient form of en-bloc temperature treatment.
  • the en-bloc thermal treatment comprises a rapid heating phase up to a first holding temperature which is in the range of 820 ° C ⁇ 20 ° C.
  • a first holding temperature at about 810 ° C.
  • a rapid cooling phase occurs.
  • a second holding temperature is reached and there is an intermediate holding phase (second holding period) in the range of this second holding temperature.
  • the second holding temperature is in the range between 350 ° C and 450 ° C.
  • the second holding temperature is in all embodiments in the range between 380 ° C and 450 ° C.
  • the rapid cooling phase preferably has a cooling rate greater than -30 K / sec in all embodiments. Cooling rates which are greater than -50 K / sec are particularly preferred. These rapid cooling rates have a beneficial effect on the microstructure of the steel product of the invention.
  • the en-bloc temperature treatment of the invention serves to avoid the negative influences of the martensitic or ferritic matrix and at the same time to produce a new microstructure with the desired properties.
  • the first intermediate holding phase preferably has a maximum duration of 5 minutes in all embodiments.
  • the second intermediate holding phase preferably has a maximum duration of 10 minutes in all embodiments.
  • the first holding period is shorter than the second holding period.
  • the fine, batten-shaped bainite has been shown to improve the strength of the steel products of the invention.
  • the steel products of the invention have bainitic slats that have a width between 20 and 200 nm and a typical length in the range of 1 ⁇ m to 4 ⁇ m.
  • These bainitic laths also referred to here as nano-fine laths, form due to the special en-bloc temperature treatment.
  • the high dislocation density ferritic phases play an important role in improving the elongation and formability of the steel products of the invention.
  • the invention is used to provide cold rolled steel products in the form of cold rolled flat products (e.g., coils).
  • the invention can also be used to e.g. To produce thin sheets or wire and wire products.
  • the invention has, inter alia, the advantage that no ART heat treatment is needed.
  • ART stands for "Austenite Reverted Transformation”.
  • the invention relates to ultrafine multiphase medium-manganese steel products comprising martensite, ferrite and retained austenite regions or phases, and optionally also bainite microstructures.
  • the steel products of Invention are characterized by a special structure constellation, which is also referred to as a multi-phase structure.
  • steel (intermediate) products are sometimes referred to when it comes to emphasizing that it is not about the finished steel product but about a preliminary or intermediate product in a multi-stage production process.
  • the starting point for such production processes is usually a melt.
  • the following is an indication of the alloy composition of the melt, since on this side of the manufacturing process it is possible to influence the alloy composition relatively precisely (for example by attacking constituents such as silicon).
  • the alloy composition of the steel product usually deviates only insignificantly from the alloy composition of the melt.
  • phase is defined inter alia by its composition of proportions of the components, enthalpy content and volume. Different phases are separated in the steel product by phase boundaries.
  • the "constituents" or “constituents” of the phases can be either chemical elements (such as Mn, Ni, Al, Fe, C, etc.) or neutral, molecular aggregates (such as FeSi, Fe 3 C, SiO 2 , etc.). ) or charged, molecular aggregates (such as Fe 2+ , Fe 3+ , etc.).
  • Quantities or proportions are here largely in weight percent (short wt.%) Made, unless otherwise stated. If information is provided on the composition of the alloy, or the steel product, then the composition comprises in addition to the explicitly listed materials or materials as the basic iron (Fe) and so-called unavoidable impurities that always occur in the molten bath and also in the resulting steel product demonstrate. All% by weight must always be supplemented to 100% by weight and all% by volume must always be completed to 100% of the total volume.
  • the medium-manganese steel products of the invention all have a manganese content which is in the range of 3.5 and 6 wt.%, The stated limits being within the range thereof, i. the manganese content is in the range of 3.5% by weight ⁇ Mn ⁇ 6% by weight.
  • the manganese content in all embodiments is preferably in the range 4% by weight ⁇ Mn ⁇ 6% by weight.
  • the carbon content C in the following range is 0.02 ⁇ C ⁇ 0.35 wt%.
  • a starting amount of iron has a carbon content C in the range of 0.02 ⁇ C ⁇ 0.35 wt%, and a manganese content Mn in the range of 3.5 wt% ⁇ Mn ⁇ 6 wt. % added.
  • the corresponding procedure is well known.
  • en-bloc temperature treatment As part of the further processing of the alloy thus obtained, follows a particularly efficient annealing process (called en-bloc temperature treatment).
  • en-bloc is used here to emphasize that, unlike many alternative approaches, no two-fold annealing or tempering is required.
  • the first intermediate holding phase H1 preferably has a maximum duration of 5 minutes in all embodiments.
  • the second intermediate holding phase H2 preferably has a maximum duration of 10 minutes in all embodiments.
  • the first cooling A1 can be carried out in all embodiments in an air stream or using a cooling fluid.
  • the second cooling A2 can be carried out in all embodiments in an air stream.
  • the steel product of the invention may also be placed in a separate environment (e.g., an incandescent unit) to be held there for a while longer (e.g., at 300 to 450 ° C). In this case, the time 52 is extended accordingly.
  • the rapid cooling phase A1 preferably has a cooling rate greater than -30 K / sec in all embodiments. Cooling rates A1 which are greater than -50 K / sec are particularly preferred. These rapid cooling rates have a beneficial effect on the microstructure of the steel product of the invention.
  • the faster first cooling A1 occurs at a cooling rate higher than the cooling rate of the slower second cooling A2.
  • the second cooling takes place along an asymptotic curve A2 *, which is the asymptote Asy (see Fig. 2 ) approaches.
  • the steel product coils are left to self-cool so that they can continue to cool on their own.
  • steel products which comprise a proportion of a bainitic microstructure which is greater than 5% by weight of the steel product, the fraction of the bainitic microstructure preferably being in the range from 10 to 70% by volume of the steel product. Particularly preferably, the proportion of the microstructure is in the range from 20 to 40% by volume.
  • steel products which comprise a retained austenite content of less than 30% by volume of the steel product, the retained austenite content preferably being less than 10% by volume of the steel product.
  • steel products which comprise a volume fraction of austenite grains, which is preferably less than 5% of the total volume of the steel product.
  • These austenite grains preferably have a maximum size smaller than 1 ⁇ m.
EP14195644.1A 2014-12-01 2014-12-01 Procédé de traitement à chaud d'un produit en manganèse-acier Active EP3029162B1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP14195644.1A EP3029162B1 (fr) 2014-12-01 2014-12-01 Procédé de traitement à chaud d'un produit en manganèse-acier
ES14195644.1T ES2674133T3 (es) 2014-12-01 2014-12-01 Procedimiento para el tratamiento térmico de un producto de manganeso-acero
JP2017528998A JP2018502986A (ja) 2014-12-01 2015-11-30 マンガン鋼材の熱処理方法及び特定合金を含むマンガン鋼材
US15/528,928 US11124850B2 (en) 2014-12-01 2015-11-30 Method for the heat treatment of a manganese steel product, and manganese steel product having a special alloy
KR1020177017190A KR102029561B1 (ko) 2014-12-01 2015-11-30 망간강 제품의 열 처리 방법 및 특수 합금을 갖는 망간강 제품
EP15802096.6A EP3227465A1 (fr) 2014-12-01 2015-11-30 Procédé de traitement thermique d'un produit en acier au manganèse et produit en acier au manganèse comprenant un alliage spécial
CN201580065026.7A CN107109506B (zh) 2014-12-01 2015-11-30 锰钢产品的热处理方法和具有特定合金的锰钢产品
PCT/EP2015/078105 WO2016087392A1 (fr) 2014-12-01 2015-11-30 Procédé de traitement thermique d'un produit en acier au manganèse et produit en acier au manganèse comprenant un alliage spécial

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP14195644.1A EP3029162B1 (fr) 2014-12-01 2014-12-01 Procédé de traitement à chaud d'un produit en manganèse-acier

Publications (2)

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EP3029162A1 true EP3029162A1 (fr) 2016-06-08
EP3029162B1 EP3029162B1 (fr) 2018-04-25

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EP14195644.1A Active EP3029162B1 (fr) 2014-12-01 2014-12-01 Procédé de traitement à chaud d'un produit en manganèse-acier
EP15802096.6A Pending EP3227465A1 (fr) 2014-12-01 2015-11-30 Procédé de traitement thermique d'un produit en acier au manganèse et produit en acier au manganèse comprenant un alliage spécial

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US (1) US11124850B2 (fr)
EP (2) EP3029162B1 (fr)
JP (1) JP2018502986A (fr)
KR (1) KR102029561B1 (fr)
CN (1) CN107109506B (fr)
ES (1) ES2674133T3 (fr)
WO (1) WO2016087392A1 (fr)

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DE102016104800A1 (de) * 2016-03-15 2017-09-21 Salzgitter Flachstahl Gmbh Verfahren zur Herstellung eines warmumgeformten Stahlbauteils und ein warmumgeformtes Stahlbauteil
US10876184B2 (en) * 2016-03-30 2020-12-29 Tata Steel Limited Hot rolled high strength steel (HRHSS) product with tensile strength of 1000-1200 MPa and total elongation of 16%-17%
WO2018050387A1 (fr) * 2016-09-16 2018-03-22 Salzgitter Flachstahl Gmbh Procédé pour la fabrication d'une pièce façonnée en un produit plat en acier contenant du manganèse et pièce correspondante
KR101940912B1 (ko) * 2017-06-30 2019-01-22 주식회사 포스코 액상금속취화 균열 저항성이 우수한 강판 및 그 제조방법
EP3594368A1 (fr) * 2018-07-13 2020-01-15 voestalpine Stahl GmbH Produit intermédiaire d'acier milieu-manganèse-feuillard laminé à froid à teneur en carbone réduite et procédé de fourniture d'un tel produit intermédiaire d'acier
CN115323135B (zh) * 2022-08-12 2023-05-23 华北理工大学 一种强塑积不低于45GPa%的超高强塑积中锰钢的制备方法

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EP3029162B1 (fr) 2018-04-25
CN107109506B (zh) 2019-03-12
WO2016087392A1 (fr) 2016-06-09
US11124850B2 (en) 2021-09-21
KR102029561B1 (ko) 2019-11-08
CN107109506A (zh) 2017-08-29
EP3227465A1 (fr) 2017-10-11
KR20170090446A (ko) 2017-08-07
US20170306429A1 (en) 2017-10-26
JP2018502986A (ja) 2018-02-01

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