EP3538676B1 - Procédé de traitement thermique d'une pièce à usiner constituée d'un acier fortement allié - Google Patents

Procédé de traitement thermique d'une pièce à usiner constituée d'un acier fortement allié Download PDF

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Publication number
EP3538676B1
EP3538676B1 EP17800725.8A EP17800725A EP3538676B1 EP 3538676 B1 EP3538676 B1 EP 3538676B1 EP 17800725 A EP17800725 A EP 17800725A EP 3538676 B1 EP3538676 B1 EP 3538676B1
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Prior art keywords
workpiece
temperature
process gas
treatment
holding phase
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EP17800725.8A
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German (de)
English (en)
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EP3538676A1 (fr
Inventor
Ralf Kuebler
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Robert Bosch GmbH
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Robert Bosch GmbH
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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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D1/06—Surface hardening
    • 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/773—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material under reduced pressure or vacuum
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces

Definitions

  • the present invention relates to a method for heat treatment of a workpiece made of a high-alloy steel.
  • Nitriding causes different nitrides to separate out within the metallic material in the surface area. This leads to the build-up of internal compressive stresses, which in some cases assume very high values in the edge area. Depending on the surface distance, the residual stresses decrease with increasing distance from the edge area. The presence of internal compressive stresses leads to improved fatigue strengths. Nitriding is also used for high-alloy steels, especially for components such as nozzle bodies, valve bodies or throttle plates.
  • high-alloy steels Due to the high oxygen affinity of their alloying elements, high-alloy steels form a natural oxide layer of a few nanometers.
  • This oxide layer is formed when it comes into contact with air and consists, for example, of chromium oxide, vanadium oxide, iron oxide and other oxides. Since the oxide layer is very compact and partially diffusion-tight, subsequent diffusion of nitrogen at elevated temperatures, in particular between 480 ° C. and 590 ° C., can be negatively influenced and even completely prevented. Inhomogeneous connecting layers as well as diffusion layers with different functional Properties are the result.
  • the naturally occurring oxide layer can be removed chemically, for example by pickling with an acid, before the actual nitriding process. Furthermore, the oxide layer can also be removed mechanically by brushing and / or grinding, or else electrically by applying a corresponding voltage.
  • a method for heat treatment of metallic workpieces in particular for nitriding or nitrocarburizing of alloyed iron materials, is known.
  • the workpieces are heated in a nitriding furnace to a temperature between 400 ° C and 500 ° C in an ammonia-containing gas atmosphere.
  • the workpieces are then heated to a temperature between 500 ° C. and 700 ° C. in a gas atmosphere containing ammonia and an added oxidizing agent.
  • the workpieces are exposed to this temperature and this gas atmosphere for a period of up to 5 hours.
  • the workpiece which consists of a high-alloy steel, is heated to a first temperature in a vacuum environment, the first temperature being kept constant during a first holding phase, the workpiece then being heated to a second temperature that is higher than the first temperature, the second temperature during is kept constant in a second holding phase, and wherein the workpiece is quenched after the second holding phase, preferably in gaseous or evaporating media.
  • a surface of the workpiece, in particular also the inner contours, are flowed around a surface of the workpiece during the first holding phase in a first treatment step with a process gas that emits hydrogen and / or a process gas mixture for cleaning and activation of the surface, the surface during the first holding phase in a second treatment step with a process gas that emits nitrogen and / or process gas mixture is flowed around to form a thin nitride-containing layer, and the nitride-containing layer is provided to optimize a downstream gas nitriding process.
  • the heat treatment according to the invention is subdivided into the manufacturing process of a workpiece consisting of a high-alloy steel behind the initial soft machining, in particular the production of the workpiece from a blank.
  • the tempering of the workpiece takes place, for example, in an evacuable, oxygen-free tempering furnace.
  • the tempering of the workpieces is a second heat treatment.
  • the third heat treatment step takes place by grinding, hard turning or similar processes, in which the properties required for the workpiece, in particular the workpiece surface, are set by means of gas nitriding at preferably 480-590 ° C by diffusing nitrogen into the workpiece.
  • the vacuum furnace is hermetically sealed and a pump connected to the interior of the vacuum furnace creates the vacuum ambient conditions in the vacuum furnace.
  • the naturally formed oxide layer or passive layer is broken up by the hardening process according to the invention and the surface of the high-alloy steel is cleaned. Carrying out the process in a vacuum or an oxygen-free atmosphere prevents or slows down the formation of a new passive layer and / or the repassivation of the high-alloy steel. A depletion of hardness-increasing alloying elements close to the edge is thus additionally avoided.
  • holding phase is to be understood as the constant holding of a temperature at which the workpiece assumes the internal temperature of the vacuum furnace for carrying out the first and second treatment step.
  • a process gas and / or process gas mixture that emits hydrogen flows around the high-alloy steel in a first treatment step.
  • the injection of the gas preferably takes place constantly.
  • a pulsed, variable or pressure-controlled course of the flow is also conceivable.
  • the flow around the workpiece in the first treatment step represents a cleaning and activation step in order to promote the diffusion of nitrogen into the surface of the steel in the second processing step due to the surface cleaned and activated as a result and the high temperature in the vacuum furnace.
  • the first temperature for the first treatment step is between 800 and 1090 ° C., preferably 900 ° C., in order to ensure optimum interaction of the process gas and / or process gas mixture which emits hydrogen with the surface of the To ensure workpiece.
  • the oxide layer is broken up and repassivation of the surface is prevented with the aid of the vacuum.
  • the surface of the workpiece is therefore highly reactive towards the diffusion of nitrogen in the second treatment step.
  • the second treatment step begins at the constant first temperature of the furnace.
  • a nitrogen-releasing process gas and / or process gas mixture flows around the high-alloy steel to form a nitride-containing layer.
  • Alloyed or high-alloy steels are particularly suitable for nitriding, since the alloying elements of these steels preferentially combine with the atomic nitrogen to form nitrides.
  • unalloyed steels can form brittle nitriding layers that tend to flake off during nitriding.
  • Steels with a carbon content between 0.3 and 0.6 mass% and alloying elements such as chromium or vanadium, which form surface layer nitrides at high temperatures, are particularly suitable for nitriding.
  • the advantage resulting from the so-called pre-nitriding in the hardening process according to the invention over conventional production methods of workpieces made of high-alloy steels is that due to the vacuum environment and the cleaning and activation by the process gas and / or process gas mixture emitting hydrogen during nitriding in the second treatment step of the hardening process, a homogeneous and forms a dense nitride layer on the surface.
  • This nitride layer can be regarded as a seed layer or passivation layer, since the actual nitriding step only takes place after the tempering and before the hard machining of the workpiece.
  • the pre-nitriding in the hardening process also optimizes the gas nitriding in the downstream manufacturing step. Due to the homogeneous seed layer from the hardening process, a more compact connecting layer with a correspondingly lower proportion of pores is formed during gas nitriding in the chamber furnace.
  • the nitriding effect which is described with the help of the so-called nitriding index, is accordingly higher due to the pre-nitriding in the hardening process.
  • the nitriding index results from the partial pressures of the nitrogen emitting Process gas and / or process gas mixture and the partial pressure of the hydrogen. The higher the nitriding index, the greater the potential for nitride formation.
  • nitrides are formed. These nitride precipitates form the connecting layer directly on the surface. Starting from the surface, a decreasing nitrogen gradient forms, this area is called the diffusion layer. In this area there are small nitride precipitates as well as nitrogen dissolved in the metal lattice.
  • iron forms iron nitrides and in high-alloy steels, for example, chromium and vanadium combine to form corresponding nitrides.
  • nitrided seed layer is present as a result of the pre-nitriding in the hardening process, a lower nitriding index is required in the nitriding process, which simplifies and simplifies the process management.
  • the gas nitriding process can also be shortened and / or carried out at lower temperatures, which also makes the process more cost-effective.
  • the nitrided layer makes the tempering process less sensitive after the hardening process, as a renewed temperature increase below the transformation temperature reduces stresses, depending on the composition of the steel, further special carbides can be precipitated and a lower hardness can be set without the alloying elements on the surface of the base material interacting to risk with the furnace atmosphere.
  • the hardening process changes from the first holding phase to the second holding phase.
  • the high-alloy steel is heated to the second temperature.
  • the second temperature is also to be understood as the austenitizing temperature.
  • the high-alloy steel is essentially in the form of ferrite and carbide, which converts to austenite at high temperatures and the carbides partially dissolve. The aim is to take advantage of the high solubility of carbon at high temperatures in austenite.
  • the second treatment step ends with the second holding phase.
  • the duration of the second treatment step, the second temperature of the high-alloy steel during the second treatment step and / or the nitrogen partial pressure on the surface of the high-alloy steel during the second treatment step are selected so that the nitride-containing layer with a thickness of less than 2 ⁇ m, preferably with a thickness of 0.001 ⁇ m to 1 ⁇ m.
  • the nitride-containing layer preferably has sheet-like or crystalline nitrides. Chromium can form sheet-like nitrides, iron preferentially forming crystalline nitrides.
  • the hydrogen-releasing process gas and / or process gas mixture flows around the surface with a first treatment pressure and the nitrogen-releasing process gas and / or process gas mixture flows around the surface with a second treatment pressure, the respective treatment pressure being in a pressure range between 10 mbar and 3000 mbar.
  • the selected pressure range is strongly dependent on the properties of the workpiece.
  • the first treatment pressure is lower than the second treatment pressure.
  • the higher the second treatment pressure the greater the potential for nitride formation in the area of the workpiece near the edge and the deeper the nitrogen diffuses into the workpiece.
  • Figure 1 shows an example of the process control for an embodiment of the method according to the invention.
  • the left ordinate 4 describes the temperature axis
  • the right ordinate 5 describes the partial pressure axis
  • the abscissa 6 describes the time axis.
  • the upper continuous curve denotes the course of the temperature T over time.
  • the lower continuous curve denotes the course of the partial pressure p over time.
  • Sections A1, H1, A2, H2, F as well as B1 and B2 are defined along the time axis, in which different activities take place.
  • a first heating phase A1 the workpiece S is initially heated from room temperature to a temperature T1 of 900 ° C.
  • the heating rate is essentially constant.
  • the vacuum furnace in which the process is carried out is under a technical vacuum, with a negative pressure of less than 50 mbar ( Figure 2 ). Furthermore, it is also conceivable that the vacuum is only generated after a certain temperature has been reached.
  • the first temperature T1 is kept constant at approximately 900 ° C.
  • no process gas or process gas mixture G1, G2 containing hydrogen or nitrogen is fed in.
  • the first treatment step B1 begins, in which a hydrogen-containing process gas or process gas mixture G1 with a first treatment pressure P1 flows around the workpiece S.
  • the first treatment pressure corresponds to P1 the hydrogen partial pressure acting on the surface 1 of the workpiece S.
  • the partial pressure corresponds to the pressure that the individual gas component, in this case hydrogen, would exert if it were alone in a given volume.
  • the flow of the hydrogen-containing process gas or process gas mixture G1 is constant ( Figure 3 ).
  • the naturally formed oxide layer 7 or passive layer of the high-alloy steel is broken up and the surface 1 of the workpiece S is cleaned and activated against the diffusion of nitrogen in the subsequent second treatment step B2.
  • the first treatment step B1 is followed by the second treatment step B2, in which a nitrogen-containing process gas or process gas mixture G2 with a second treatment pressure P2 flows around the workpiece S.
  • the second treatment pressure P2 corresponds to the nitrogen partial pressure acting on the surface 1 of the workpiece S.
  • the flow of the nitrogen-containing process gas or process gas mixture G2 is constant ( Figure 4 ).
  • the second treatment pressure P2 is higher than the first treatment pressure P1, the respective treatment pressure P1, P2 being between 10 mbar and 3000 mbar.
  • the first holding phase H1 is followed by a second heating phase A2 with a subsequent second holding phase H2.
  • the heating rate is constant.
  • the workpiece S is first heated from the first temperature T1 to the second temperature T2, which is then kept constant.
  • the second temperature T2 corresponds to the austenitizing temperature of the workpiece S. In the edge area, while maintaining the austenitizing temperature, a phase transformation to an austenitic structure takes place.
  • the nitrogen-containing process gas or process gas mixture G2 continues to flow around the workpiece S in the second holding phase H2 with a second treatment pressure P2 and constant flow.
  • the second holding phase H2 corresponds to a nitriding phase.
  • atomic nitrogen diffuses from the nitrogen-containing process gas or process gas mixture G2 into the surface 1 of the workpiece S and combines with nitride-forming alloying elements such as for example chromium, vanadium or iron.
  • the duration of the second treatment step B2, the second temperature T2 of the workpiece S during the second treatment step B2 and the second treatment pressure B2 on the surface 1 of the workpiece S during the second treatment step B2 influence the thickness of the nitride-containing layer 2, which is between 0.001 ⁇ m and 1 ⁇ m located ( Figure 5 ).
  • the second holding phase H2 and the second treatment step B2 are then followed by a quenching phase F for setting an essentially martensitic structure.
  • the vacuum furnace 3 and the workpiece S are quenched to room temperature.
  • the Figures 2 to 5 describe the method steps according to the invention for heat treatment of a workpiece S made of a high-alloy steel in sectional drawing according to the in Figure 1 shown and explained process management.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Heat Treatment Of Articles (AREA)

Claims (3)

  1. Procédé de traitement thermique d'une pièce (S) en acier fortement allié, la pièce (S) étant chauffée à une première température (T1) dans un environnement sous vide, la première température (T1) étant maintenue constante pendant une première phase de maintien (H1), le composant (S) étant ensuite chauffé à une deuxième température (T2) qui est supérieure à la première température (T1), la deuxième température (T2) étant maintenue constante pendant une deuxième phase de maintien (H2), et la pièce (S) étant trempée après la deuxième phase de maintien (H2), un gaz de traitement et/ou mélange de gaz de traitement (G1), libérant de l'hydrogène, s'écoulant autour d'une surface (1) de la pièce (S) pendant la première phase (H1) à une première étape de traitement (B1) pour nettoyer et activer la surface (1), un gaz de traitement et/ou mélange de gaz de traitement (G2), libérant de l'azote, s'écoulant autour de la surface (1) pendant la première phase de maintien (Hl) à une deuxième étape de traitement (B2) pour former une couche (2) contenant du nitrure, et la couche (2) contenant du nitrure étant prévue pour optimiser un processus de nitruration gazeuse en aval,
    caractérisé en ce qu'un passage de la première phase de maintien (H1) à la deuxième phase de maintien (H2) est effectué pendant la deuxième étape de traitement (B2), en ce qu'un gaz de traitement et/ou mélange de gaz de traitement (G1), libérant de l'hydrogène, s'écoule autour de la surface (1) à une première pression de traitement (P1) et le gaz de traitement et/ou mélange de gaz de traitement (G2), libérant de l'azote, s'écoule autour de la surface (1) à une deuxième pression de traitement (P2), la pression de traitement respective (P1, P2) étant située dans une gamme de pressions comprise entre 10 mbar et 3000 mbar, en ce que la deuxième étape de traitement (B2) se termine par la deuxième phase de maintien (H2), en ce que la première température (T1) pendant la première phase de maintien (H1) est d'au moins 800 à 1090 °C, et de préférence de 900 °C, et en ce que la deuxième température (T2) est choisie comme température d'austénitisation de la pièce (S), la première pression de traitement (P1) étant la pression partielle d'hydrogène et la deuxième pression de traitement (P2) étant la pression partielle d'azote, et la première pression de traitement (P1) étant inférieure à la deuxième pression de traitement (P2).
  2. Procédé selon la revendication 1, caractérisé en ce que la durée de la deuxième étape de traitement (B2), la deuxième température (T2) de la pièce (S) pendant la deuxième étape de traitement (B2) et/ou la deuxième pression de traitement (P2) sur la surface (1) de la pièce (S) pendant la deuxième étape de traitement (B2) sont choisies de façon à former la couche (2) contenant du nitrure avec une épaisseur inférieure à 2 µm, de préférence avec une épaisseur de 0,001 µm à 1 µm.
  3. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que la couche (2) contenant du nitrure comporte des nitrures en forme de feuille ou précipités sous forme cristalline.
EP17800725.8A 2016-11-08 2017-10-30 Procédé de traitement thermique d'une pièce à usiner constituée d'un acier fortement allié Active EP3538676B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016221891.3A DE102016221891A1 (de) 2016-11-08 2016-11-08 Verfahren zur Wärmebehandlung eines aus einem hochlegierten Stahl bestehenden Werkstücks
PCT/EP2017/077741 WO2018086930A1 (fr) 2016-11-08 2017-10-30 Procédé de traitement thermique d'une pièce à usiner constituée d'un acier fortement allié

Publications (2)

Publication Number Publication Date
EP3538676A1 EP3538676A1 (fr) 2019-09-18
EP3538676B1 true EP3538676B1 (fr) 2022-01-05

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EP (1) EP3538676B1 (fr)
CN (1) CN109923219B (fr)
BR (1) BR112019008898B1 (fr)
DE (1) DE102016221891A1 (fr)
FR (1) FR3058423A1 (fr)
WO (1) WO2018086930A1 (fr)

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CN113840673A (zh) * 2019-02-26 2021-12-24 索尼奥环球控股有限责任公司 高氮钢粉及其制造方法
CN111172371B (zh) * 2020-01-16 2021-11-23 成都航宇超合金技术有限公司 一种降低零件表面金属贫化层深度的方法

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Publication number Priority date Publication date Assignee Title
DK0516899T3 (da) * 1991-06-04 1996-02-26 Daido Hoxan Inc Fremgangsmåde til nitrering af stål
ATE235581T1 (de) 2000-02-04 2003-04-15 Ipsen Int Gmbh Verfahren zum nitrieren und/oder nitrocarburieren von höher legierten stählen
CA2456520A1 (fr) * 2004-01-30 2005-07-30 Hubert Patrovsky Methode de nitruration visant a ameliorer certaines caracteristiques de surface d'alliages a base de cobalt et de chrome
EP1612290A1 (fr) * 2004-07-02 2006-01-04 METAPLAS IONON Oberflächenveredelungstechnik GmbH Procédé et installation pour la nitruration à l'aide de gaz d'un substrat et substrat obtenu.
JP5365023B2 (ja) * 2007-03-07 2013-12-11 日産自動車株式会社 遷移金属窒化物、燃料電池用セパレータ、燃料電池スタック、燃料電池車両、遷移金属窒化物の製造方法及び燃料電池用セパレータの製造方法
CN101338358B (zh) * 2007-07-05 2010-06-02 刘正贤 提升马氏体不锈钢表面硬度的方法

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Publication number Publication date
BR112019008898B1 (pt) 2022-08-09
WO2018086930A1 (fr) 2018-05-17
DE102016221891A1 (de) 2018-05-09
CN109923219B (zh) 2021-10-12
FR3058423A1 (fr) 2018-05-11
EP3538676A1 (fr) 2019-09-18
BR112019008898A2 (pt) 2019-08-13
CN109923219A (zh) 2019-06-21

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