EP2887361A1 - Längliches elektrisch leitendes Element, das rostsicher ist - Google Patents

Längliches elektrisch leitendes Element, das rostsicher ist Download PDF

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Publication number
EP2887361A1
EP2887361A1 EP14198093.8A EP14198093A EP2887361A1 EP 2887361 A1 EP2887361 A1 EP 2887361A1 EP 14198093 A EP14198093 A EP 14198093A EP 2887361 A1 EP2887361 A1 EP 2887361A1
Authority
EP
European Patent Office
Prior art keywords
electrically conductive
layer
conductive element
copper
white bronze
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.)
Withdrawn
Application number
EP14198093.8A
Other languages
English (en)
French (fr)
Inventor
Christophe Brismalein
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.)
Nexans SA
Original Assignee
Nexans SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nexans SA filed Critical Nexans SA
Publication of EP2887361A1 publication Critical patent/EP2887361A1/de
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/2806—Protection against damage caused by corrosion
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0607—Wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables
    • H01B9/006—Constructional features relating to the conductors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y10T428/1291—Next to Co-, Cu-, or Ni-base component

Definitions

  • the present invention relates to an elongate electrically conductive member comprising a core of copper or copper alloy and at least one layer of white bronze, and to an electrical cable comprising at least one such elongated electrically conductive member.
  • the invention relates to an electric cable having a good resistance to corrosion while ensuring good mechanical and electrical properties, particularly in terms of temperature resistance and electrical conductivity.
  • a metal part eg brass high frequency coaxial connector body
  • an anti-corrosion coating comprising a layer of white bronze, a palladium layer covering said white bronze layer, and a gold layer covering said palladium layer.
  • the white bronze is an alloy of copper and tin generally comprising between 20 and 40% by weight of tin. With this coating, said metal part is resistant to corrosion while retaining good brazeability.
  • the chemical composition of the white bronze layer used is not described, the presence of a layer of palladium and / or a gold layer in said part decreases its electrical conductivity, and the presence of a layer of gold as the outermost layer of the metal part decreases its resistance to deformation.
  • this metal part has the disadvantage of being very expensive by the use of precious metals such as palladium and gold, and by its method of preparation which requires several steps to form the different metal layers. Finally, this metal part is not used to design an electric cable.
  • the object of the present invention is to overcome the drawbacks of the techniques of the prior art by providing an elongate electrically conductive element comprising a core of copper or copper alloy and at least one layer of white bronze, said elongate electrically conductive element being economic and having a good resistance to corrosion while ensuring good electrical properties, especially in terms of electrical conductivity, and good mechanical properties, especially in terms of temperature resistance.
  • the elongate electrically conductive element (s) are generally isolated by means of an electrically insulating layer of plastic material such as a layer comprising polytetrafluoroethylene (PTFE) whose application (eg by extrusion) requires a heat treatment step at a temperature of about 370 ° C for 10 minutes, which requires that the electric cable can withstand such a temperature.
  • PTFE polytetrafluoroethylene
  • the present invention therefore has for its first object an elongate electrically conductive element comprising a core made of copper or copper alloy and at least one layer of white bronze surrounding said core of copper or copper alloy, characterized in that said layer of bronze white is the outermost layer of the elongated electrically conductive element.
  • the term "elongated electrically conductive element” means an electrically conductive element having a longitudinal axis.
  • the electrically conductive element is elongated because it has undergone at least one drawing step (cold deformation step, in particular through diamond dies).
  • the term "white bronze layer” means a layer comprising copper and at least 20% by weight of tin.
  • the expression "said white bronze layer is the outermost layer of the elongated electrically conductive element” means that the white bronze layer of the elongated electrically conductive element of the invention is not covered by any other metal layer.
  • the entire outer surface of the white bronze layer i.e. the whole of the farthest surface of the elongated electrically conductive element
  • the entire outer surface of the white bronze layer is not covered by any other metal layer.
  • said white bronze layer is not covered by any layer of palladium and / or any gold layer and / or any layer of tin.
  • the air oxidation of the elongate electrically conductive element of the invention is avoided both at room temperature (ie 20 ° C.), at elevated temperatures ranging from 200 ° C to 400 ° C.
  • the white bronze layer used in the elongated electrically conductive element of the invention unlike other anti-corrosion coatings of the prior art (e.g. nickel), is not toxic to the environment.
  • the elongated electrically conductive element of the invention retains good electrical properties, especially in terms of electrical conductivity, resistivity and linear resistance, good mechanical properties, especially in terms of breaking strength, and good performance. brazing.
  • the white bronze layer extends in particular along the longitudinal axis of the elongated electrically conductive element.
  • the white bronze layer preferably has a substantially regular surface.
  • the white bronze layer forms a continuous envelope (without irregularities or roughness) surrounding said copper core or copper alloy.
  • the white bronze layer of the elongated electrically conductive element comprises at most 57% by weight of tin, and preferably at most 40% by weight of tin.
  • the white bronze layer of the elongated electrically conductive element of the invention further comprises zinc.
  • the combination of copper, at least 20% by weight of tin and zinc provides a layer having both good temperature resistance and good corrosion resistance.
  • said white bronze layer comprises only tin (at least 20% by weight), copper and zinc. Indeed, if we add other elements in said layer, the electrical conductivity and / or the breaking strength can drop significantly, especially at high temperatures.
  • the white bronze layer of the elongated electrically conductive element of the invention comprises from 40 to 55% by weight of copper, and preferably from 45 to 53% by weight of copper. If the amount of copper in the white bronze layer is greater than 55% by weight, the elongate electrically conductive member of the invention may exhibit decreased corrosion resistance. If the amount of copper is less than 40% by weight, the elongated electrically conductive element of the invention may have decreased electrical conductivity.
  • the white bronze layer of the elongated electrically conductive element of the invention comprises from 30 to 57% by weight of tin, and preferably from 31 to 38% by weight of tin. . If the amount of tin is greater than 57% by weight, the elongated electrically conductive element of the invention may have a reduced temperature resistance. If the amount of tin is less than 30% by weight, the elongate electrically conductive member of the invention may exhibit low corrosion resistance.
  • the white bronze layer of the elongate electrically conductive element of the invention comprises from about 3 to about 20 weight percent zinc, and preferably from about 13 to about 18 weight percent zinc. If the amount of zinc in the white bronze layer is greater than 20% by weight, the elongated electrically conductive element of the invention may exhibit decreased corrosion resistance. If the amount of zinc is less than 3% by weight, the elongated electrically conductive member of the invention may have decreased temperature resistance and tensile strength.
  • the white bronze layer of the elongated electrically conductive element of the invention may have a thickness ranging from 0.1 ⁇ m to 100 ⁇ m, preferably from 2 to 10 ⁇ m, and more preferably from 3 to 7 ⁇ m.
  • the elongate electrically conductive element does not comprise a layer consisting of nickel and / or copper layer, in particular surrounding the copper or copper alloy core.
  • the presence of a nickel layer can alter the electrical conductivity properties of the elongated electrically conductive element.
  • the white bronze layer is directly in contact (i.e. in direct physical contact) with the copper or copper alloy core.
  • the elongated electrically conductive element of the invention does not include an intermediate layer (s) positioned between the copper or copper alloy core and the white bronze layer.
  • the copper or copper alloy core may have a cross section ranging from 0.3 mm 2 to 85 mm 2 , and preferably ranging from 0.3 mm 2 to 70 mm 2 .
  • the copper or copper alloy core preferably has a round cross-sectional shape.
  • the white bronze layer is deposited on the core of copper or copper alloy by electroplating.
  • the electroplating is carried out by techniques well known to those skilled in the art.
  • the electrodeposition is carried out in an alkaline medium (ie pH> 7), and preferably at a pH ranging from 13.1 to 13.5.
  • the electrodeposition can also be carried out in an acid medium (i.e. pH ⁇ 7), and preferably at a pH ranging from 2 to 5.
  • an acid medium i.e. pH ⁇ 7
  • the copper or copper alloy core may be immersed in an aqueous electrolysis bath comprising a copper precursor, a zinc precursor and a tin precursor.
  • the copper precursor may be selected from copper cyanide and copper sulphate
  • the zinc precursor may be zinc sulphate
  • the tin precursor may be tin sulphate.
  • the copper, the zinc and the tin are then codéposés on said soul, that is to say that the tin, the zinc and the copper are alloys during their deposit on the soul of copper or alloy of copper.
  • the electrolytic bath contains the precursors of copper, zinc and tin in the proportions chosen respectively identical to those of the alloy constituting the white bronze layer.
  • the bath may comprise from 10 to 15 g / l approximately copper precursor (s), from 10 to 20 g / l approximately tin precursor (s), and from 0 to 5 g / l about one precursor (s) of zinc.
  • the electrolytic parameters used during electroplating are dictated by a current density and a conductivity of the electrolysis bath.
  • the current density is preferably set from about 0.5 to 60 A / dm 2 , and more preferably from about 1 to 5 A / dm 2 .
  • the temperature of the electrolysis bath may range from 25 ° C to 65 ° C, and preferably from 55 to 65 ° C.
  • the electroplating method makes it possible to control and favor the formation of a continuous envelope (without irregularities or roughness) around the copper or copper alloy core.
  • the white bronze layer is preferably not formed around the copper or copper alloy core by diffusion by heat treatment (a step well known under the Anglicism " reflow treatment ”) .
  • this type of process consists in depositing on a metal part a copper layer and then a layer of tin, and in heating the assembly, in particular at a temperature of at least 150 ° C., in order to allow diffusion of the copper in the tin layer and thus form an intermetallic layer of copper alloy and tin between the copper layer and the tin layer.
  • the copper-tin alloy layer is formed in situ and it is difficult to control its thickness and to obtain a substantially regular surface.
  • the intermetallic layer obtained by this method is brittle or brittle, which reduces the bending strength of the electrically conductive element.
  • this method does not make it possible to form a layer of white bronze which further comprises zinc.
  • the second subject of the present invention is an electrical cable comprising at least one elongated electrically conductive element as defined in the present invention, and at least one polymer layer surrounding said electrically conductive element.
  • said polymer layer is directly in contact with the white bronze layer of the elongated electrically conductive member.
  • the polymer layer may be an electrically insulating layer.
  • the polymer layer comprises polytetrafluoroethylene (PTFE) or a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP).
  • PTFE polytetrafluoroethylene
  • FEP hexafluoropropylene
  • the polymeric layer is preferably an extruded layer by techniques well known to those skilled in the art.
  • the electrical cable of the invention is preferably a low-voltage (in particular less than 6kV) or medium voltage (in particular 6 to 45-60 kV) energy cable.
  • the figure 1 schematically represents a structure, in cross section, of an electric cable according to the invention.
  • the figure 1 shows an electrical cable comprising an elongate electrically conductive member comprising a core of copper or copper alloy (1-1) and a layer of white bronze (1-2) surrounding said core of copper or copper alloy (1- 1); and a polymer layer (2) surrounding said elongate electrically conductive member.
  • the thickness of the white bronze layer is indicated by the arrow and the reference e.
  • a 5 ⁇ m thick white bronze layer was applied by electrodeposition on a 2.57 mm diameter copper wire.
  • the alkaline electrolysis bath prepared consisted of about 14 g / l of copper, about 55 g / l of free cyanide, about 19 g / l of free potash, about 20 g / l of tin and about 4 g / l of zinc. .
  • the bath pH was about 13.3.
  • the current density was about 1.5A / dm 2 and the temperature of the electrolysis bath was about 62 ° C.
  • the composition of the white bronze layer surrounding the copper core was 51% by weight of copper, 33% by weight of tin and 16% by weight of zinc. This composition was analyzed using an EDX energy dispersion spectrometer (20 kV, x1000, ⁇ 1% by weight) sold under the trade name 227A 1SUS by the company Noran Instruments and with the aid of a SEM scanning electron microscope sold under the trade name JSM5310 by the company JEOL.
  • Example 2 Corrosion resistance and temperature resistance of the elongated electrically conductive element according to the invention
  • the elongate electrically conductive member as prepared above in Example 1 was temperature-enhanced for 2 hours at 200 ° C, or for 10 minutes at 300 ° C, or for 10 minutes at 370 ° C.
  • Table 1 below indicates the chemical composition of the white bronze layer before aging and its evolution as a function of aging.
  • ⁇ b> TABLE 1 ⁇ / b> chemical composition of the white bronze layer of the electrically conductive element of the invention Cu (% by mass) Sn (% by weight) Zn (% by weight) Before aging 51 33 16 200 ° C / 2h 51 34 15 300 ° C / 10min 53 30 17 370 ° C / 10min 48 36 16
  • the white bronze layer of the invention does not see its chemical composition change, and thus has a good temperature resistance.
  • Table 2 shows the electrical and mechanical characteristics of the elongated electrically conductive element as prepared above in Example 1 before aging and after temperature aging at 370 ° C. for 10 minutes, and by comparison with electrical and mechanical characteristics of a bare copper wire before aging and after temperature aging at 370 ° C for 10 minutes.
  • the linear resistance (RL) was measured using a resistivity bench equipped with a microohmeter sold under the trade name MGR10 by the company SEFELEC.
  • the electrical resistivity (in ⁇ .cm) of the coated elongated electrically conductive element was calculated from the linear resistance RL, the diameter of the elongated electrically conductive element, and the length of said element.
  • Electrical conductivity was calculated from the electrical resistivity of the coated elongated electrically conductive member and the electrical resistivity of the copper.
  • Table 2 shows that the presence of the white-bronze layer in the elongate electrically conductive element of the invention makes it possible to improve the resistance to corrosion (appearance of the wire) while retaining good electrical properties (electrical conductivity , linear resistance and resistivity) and mechanical (breaking strength, elongation at break) with respect to an electrically conductive element which would contain only a copper core (ie without the white bronze layer).
  • the wire drawing process is a cold forming process that involves stretching a wire by progressively reducing its diameter through tools called dies.
  • the diameter of the element electrically Elongated conductor as obtained above is then decreased from 2.57 mm to 1.024 mm thanks to a die sold by the Esteves Company. This simulates the compression that usually occurs during the formation of an electric cable.
  • the elongated electrically conductive element according to the invention is well drawn.
  • said white bronze layer remains on the entire surface of the copper core without discontinuities and no crack is observed, which reflects a good adhesion of said white bronze layer to the copper core.
  • the white bronze layer has the ability to withstand the compressive force caused by cable formation.
  • the wetting time obtained was less than 1 second, indicating good solderability of the elongate electrically conductive element of the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
EP14198093.8A 2013-12-19 2014-12-16 Längliches elektrisch leitendes Element, das rostsicher ist Withdrawn EP2887361A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1363053A FR3015762B1 (fr) 2013-12-19 2013-12-19 Element electriquement conducteur allonge resistant a l'oxydation

Publications (1)

Publication Number Publication Date
EP2887361A1 true EP2887361A1 (de) 2015-06-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP14198093.8A Withdrawn EP2887361A1 (de) 2013-12-19 2014-12-16 Längliches elektrisch leitendes Element, das rostsicher ist

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US (1) US9514858B2 (de)
EP (1) EP2887361A1 (de)
FR (1) FR3015762B1 (de)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516408A (en) * 1993-04-19 1996-05-14 Magma Copper Company Process for making copper wire
EP0893187A1 (de) 1997-07-25 1999-01-27 Radiall Verfahren zum Beschichten von zu lötenden metallischen Werkstücken, Beschichtung dafür, und hergestelltes beschichtetes Werkstück
JP2006077307A (ja) * 2004-09-10 2006-03-23 Kobe Steel Ltd 接続部品用導電材料及びその製造方法
US20130189540A1 (en) * 2010-10-07 2013-07-25 Jarden Zinc Products, LLC Cooper-Zinc-Manganese Alloys with Silvery-White Finish for Coinage and Token Applications

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3097965A (en) * 1961-06-27 1963-07-16 Richard A Wilkins Conductive wire coating alloys, wires coated therewith and process for improving solderability therefor
KR920010862B1 (ko) * 1988-06-30 1992-12-19 미쯔비시 덴끼 가부시기가이샤 와이어컷방전 가공용 와이어전극
US6319604B1 (en) * 1999-07-08 2001-11-20 Phelps Dodge Industries, Inc. Abrasion resistant coated wire
JP4000729B2 (ja) * 1999-12-15 2007-10-31 日立電線株式会社 同軸ケーブル及びその製造方法
ITMI20022672A1 (it) * 2002-12-18 2004-06-19 Paolo Agostinelli Conduttori elettrici.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516408A (en) * 1993-04-19 1996-05-14 Magma Copper Company Process for making copper wire
EP0893187A1 (de) 1997-07-25 1999-01-27 Radiall Verfahren zum Beschichten von zu lötenden metallischen Werkstücken, Beschichtung dafür, und hergestelltes beschichtetes Werkstück
JP2006077307A (ja) * 2004-09-10 2006-03-23 Kobe Steel Ltd 接続部品用導電材料及びその製造方法
US20130189540A1 (en) * 2010-10-07 2013-07-25 Jarden Zinc Products, LLC Cooper-Zinc-Manganese Alloys with Silvery-White Finish for Coinage and Token Applications

Also Published As

Publication number Publication date
FR3015762B1 (fr) 2017-12-15
US9514858B2 (en) 2016-12-06
US20150179303A1 (en) 2015-06-25
FR3015762A1 (fr) 2015-06-26

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