EP2873475B1 - Method of manufacturing wires of Cu-Ag alloys - Google Patents

Method of manufacturing wires of Cu-Ag alloys Download PDF

Info

Publication number
EP2873475B1
EP2873475B1 EP14461523.4A EP14461523A EP2873475B1 EP 2873475 B1 EP2873475 B1 EP 2873475B1 EP 14461523 A EP14461523 A EP 14461523A EP 2873475 B1 EP2873475 B1 EP 2873475B1
Authority
EP
European Patent Office
Prior art keywords
casting
wires
hours
heat treatment
temperature
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
EP14461523.4A
Other languages
German (de)
French (fr)
Other versions
EP2873475A1 (en
Inventor
Artur Kawecki
Tadeusz Knych
Andrzej Mamala
Pawel Kwasniewski
Grzegorz Kiesiewicz
Beata Smyrak
Eliza Sieja-Smaga
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.)
INSTYTUT METALI NIEZELAZNYCH
Tele-Fonika Kable Spolka Akcyjna
Akademia Gomiczo Hutnicza
KGHM Polska Miedz SA
Original Assignee
Instytut Metali Niezelaznych
Tele-Fonika Kable Spolka Akcyjna
Instytut Nawozow Sztucznych
Akademia Gomiczo Hutnicza
KGHM Polska Miedz 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 Instytut Metali Niezelaznych, Tele-Fonika Kable Spolka Akcyjna, Instytut Nawozow Sztucznych, Akademia Gomiczo Hutnicza, KGHM Polska Miedz SA filed Critical Instytut Metali Niezelaznych
Priority to PL14461523T priority Critical patent/PL2873475T3/en
Priority to SI201431053T priority patent/SI2873475T1/en
Publication of EP2873475A1 publication Critical patent/EP2873475A1/en
Application granted granted Critical
Publication of EP2873475B1 publication Critical patent/EP2873475B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004Copper alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002Treatment with gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/005Continuous casting of metals, i.e. casting in indefinite lengths of wire
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059Mould materials or platings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12Accessories for subsequent treating or working cast stock in situ
    • B22D11/124Accessories for subsequent treating or working cast stock in situ for cooling
    • B22D11/1245Accessories for subsequent treating or working cast stock in situ for cooling using specific cooling agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • This invention concerns a method of manufacturing wires, including micro-wires, of Cu-Ag alloys, in particular of an alloy comprising Cu-((3 ⁇ 7.9)% Ag by weight.
  • These alloys having the form of rods and coming from a continuous melting and casting line are subject to properly selected heat treatment sequences and drawing into wires, featuring a set of excellent mechanical and electrical properties.
  • Cu-Ag alloys may be used as conductors in power supply applications, in the automotive industry, in power supply and signalling systems of high speed railways, in medical appliances and as power supply components of strong magnetic field generator windings.
  • copper-based conductor alloys which may also contain Nb, Be, Zn, Sn, Zr, Cr, etc. have been applied in the analysed fields of technology.
  • these alloys apart from their relatively high mechanical properties, are characterized by low electrical conductivity.
  • Cu-Ag alloys also show exceptionally high values of electrical conductivity.
  • a number of global solutions focus on developing these properties by selecting an appropriate technology of obtaining and processing materials. Research in scientific centres and research institutes worldwide is aimed at obtaining wires with excellent mechanical properties and, at the same time, the highest electrical conductivity possible. Production of ingots with various cross-section shapes and limited lengths, and continuous melting and casting systems ensuring that a material with theoretically endless length can be obtained, are amongst commonly known engineering solutions applied to obtain alloys.
  • a method for obtaining micro-wires of an alloy with the chemical composition of Cu-(2 ⁇ 14)% Ag by weight is known from a Japanese patent application JP 2000-199042 .
  • the description provides for a method of manufacturing microwires with a diameter of 0.01 ⁇ 0.1 mm using eight variants of treatment.
  • the research findings presented in the patent description have focused on a material in the form of cast rods with a diameter of 8mm and containing silver as an alloying constituent in the amount of 5 and 10% Ag by weight.
  • the scheme for obtaining microwires according to the referred description provides for executing the following treatment sequences. Cast rods of the alloy of Cu-10% Ag by weight were subjected to diameter reduction in the drawing process from 10mm to 5 mm, at a set reduction of 61%.
  • the deformed material was heat treated at 450 C for 10 h, in order to apply subsequent overall reduction of either 94.2% or 99%.
  • the final wire diameter was 1.2mm and 0.5mm, respectively.
  • the second of the variants expected, after the initial overall reduction of 61%, a heat treatment at 450 C /10h, the overall reduction of 84%, a heat treatment at 370 C/15 h, followed by the overall reduction of 97.8% to a diameter of 0.3mm, and a subsequent heat treatment 370 C/60 h, and the final overall reduction of 99.6% to a diameter of 0.02mm.
  • a heat treatment at 450 C /10h the overall reduction of 84%
  • a heat treatment at 370 C/15 h followed by the overall reduction of 97.8% to a diameter of 0.3mm
  • a subsequent heat treatment 370 C/60 h a subsequent heat treatment
  • the input material was a Cu-Ag alloy ingot with dimensions of 10x10x30mm, obtained by melting in an electric Tamman furnace at a temperature of 1250 C. Alloys from the range of Cu- (1 ⁇ 10)% Ag by weight, Cu-(2 ⁇ 6)% Ag by weight were subjected to a reduction in the drawing process. The heat treatment processes applied in the central phase of the reduction were carried out at temperatures of 400 ⁇ 500 C for a period from 1 to 50 hours in a vacuum or an inert gas atmosphere to avoid oxidation of the material surface.
  • the initial material is an ingot with the maximum content of impurities of 10 ppm or less, obtained in the process of mould casting.
  • the metal during casting is cooled at a cooling rate of 400 ⁇ 500 C/min.
  • the product according to this solution is further processed by e.g. drawing, rolling, etc.
  • the heat treatment operations following the plastic working processes are carried out at 300 ⁇ 350 C for 10 ⁇ 20 h, 350 ⁇ 450 C for 5 ⁇ 10 h, or at temperatures of 450 ⁇ 550 C for 0.5 ⁇ 5 h in an inert gas atmosphere.
  • the schedule of obtaining products of the Cu-(1 ⁇ 3.5)% Ag by weight according to this invention provides for drawing to a diameter of 0.05mm or less.
  • the tensile strength of the final material is within the range of 800 ⁇ 1200 MPa, while the electric conductivity is within the range of 80 ⁇ 84% IACS.
  • This solution also assumes, at a certain stage of obtaining wires from the alloy of Cu-(1 ⁇ 3.5)% Ag by weight, an additional holding process at temperatures of 600 ⁇ 900 C for a very short time, i.e. from 5 to 120 seconds.
  • a disadvantage shared by the solutions is underutilization of a possibility to advantageously develop the microstructure of Cu-Ag alloys, and a related possibility to manufacture wires with an even higher set of mechanical and electrical properties.
  • thermo-mechanical treatment processes conducted at unfavourably selected temperature ranges, combined with an overly extended heat treatment time, do not influence effectively the maximisation of mechanical and electrical properties.
  • additional intermediate heat treatments inherent to the whole production cost generation, used at an improper stage of wire production, do not translate fully into a high set of mechanical and electrical properties of the final product.
  • the objective of the invention is to present a consistent, integrated method for manufacturing wire components, including microwires, comprising the continuous melting and casting process of rods of Cu-Ag alloys and a sequential heat treatment combined with drawing, enabling wires, including micro-wires to be obtained with a tensile strength Rm within the range of 1100 ⁇ 1400 MPa and simultaneously an electrical conductivity within the range of 68 ⁇ 84% IACS.
  • the Cu-Ag alloys have the possibility of mutual limited solubility in the solid state of silver in copper and copper in silver.
  • the alloy microstructure consists of a matrix comprising mainly copper containing a certain amount of not precipitated silver, and precipitates rich in silver, containing also a small amount of not precipitated copper.
  • the structure at a longitudinal section of the wires (microwires) consists of very numerous, thin, considerably elongated fibres almost wholly comprising silver with a small admixture of copper and the matrix comprising almost wholly of copper.
  • the diameter of these fibres has nanometric dimensions.
  • the materials in the form of copper and silver with a high chemical purity are melted at a temperature of 1083 ⁇ 1300 C in a graphite crucible placed in a furnace, and subsequently continuously cast at a temperature of 1083 ⁇ 1300 C, in an inert gas atmosphere using a graphite mould, at primary cooling conditions (mould cooling) and secondary cooling conditions (the solidified alloy after leaving the mould), and subs the casting obtained with this method is subjected to a thermo-mechanical treatment during which the obtained casting is solution annealed at a temperature of 600 ⁇ 779.1 C for 0.5 ⁇ 100 hours, and subsequently quenched at a rate faster than the process of precipitating of its constituents from the solid solution, and then it is subjected to a further two-stage heat treatment processes in which first stage there is holding at 150 ⁇ 300 C for 0.1 ⁇ 100 hours, followed by - at the second stage - holding at a temperature of 300 ⁇ 500 C for 0.1 ⁇ 20 hours, and then slow cooling, followed by drawing into
  • the obtained casting after being solution annealed at a temperature of 600 ⁇ 779.1 C for 0.5 ⁇ 100 hours, and subsequently quenched and, subsequently, it is drawn, with a true strain measure of 0.1 ⁇ 1, and then subject to the further two-stage heat treatment processes, followed by drawing into wires of the final cross-section.
  • At least one intermediate heat treatment occurs within 200 ⁇ 600 C for 0.1 ⁇ 50 hours, followed by slow cooling.
  • At least one intermediate heat treatment occurs at 600 ⁇ 900 C for 0.1 ⁇ 1000 seconds, followed by quenching.
  • final cross-section wires are subjected to a heat treatment at a temperature of 50 ⁇ 300°C for 0.1 ⁇ 1000 hours.
  • the casting is water quenched.
  • the casting is oil quenched.
  • the casting is liquid nitrogen quenched.
  • the casting is emulsion quenched.
  • the graphite crucible is made of a high purity graphite, wherein alloying constituents are placed under a charcoal or graphite layer.
  • the graphite crucible is placed in protective atmosphere.
  • the graphite mould is cooled with a system that is mounted on it, through which a cooling agent flows (the primary cooling system).
  • the casting leaving the mould is additionally cooled by a cooling agent fed directly onto the casting (the secondary cooling system).
  • the following technical and functional effects have been obtained, namely a possibility to form a set of excellent electrical and mechanical properties of the product, reduction of manufacturing costs thanks to properly selected thermo-mechanical treatments, a possibility to select the optimum conditions of the thermo-mechanical treatment sequence in order to obtain the required mechanical and electrical properties, an advantageous ratio of weight to mechanical parameters of the obtained products.
  • the casting was solution-annealed at a temperature of 750 C for 20 hours, and subsequently oil quenched to preserve the homogeneous structure of the material.
  • a two-stage ageing process was carried out in order to extract as much silver as possible from the homogeneous solid solution of Cu-Ag.
  • the primary ageing (the first stage) was conducted at 300 C for 20 hours.
  • the secondary ageing (the second stage) was conducted at the temperature of 450 C for 10 hours.
  • the alloy microstructure consisted of very numerous fine silver precipitates in the copper matrix.
  • the material was drawn into wires with a true strain of 2.7, followed by an intermediate heat treatment that consisted in holding at a temperature of 400 C for 2 hours.
  • the material was drawn into the final diameter wires.
  • the final diameter wires were subjected to a heat treatment at a temperature of 240°C for 2 hours.
  • the final microstructure of the wire as observed on its longitudinal section, presented very numerous, elongated, thin silver bands and copper matrixes, favourable to obtain a set of high mechanical properties and a high electrical conductivity of the product.
  • the casting was solution-annealed at a temperature of 750 C for 10 hours, and subsequently it was water quenched in order to preserve the homogeneous structure of the material. After this process, it was necessary to conduct a two-stage ageing processes, in order to extract as much silver as possible from the homogeneous solid solution of Cu-Ag.
  • the primary ageing (the first stage) was conducted at 200 C for 20 hours.
  • the secondary ageing (the second stage) was conducted at a temperature of 450 C for 10 hours.
  • the alloy microstructure consisted of very numerous fine silver precipitates in the copper matrix. Next, the material was drawn into the final diameter wires.
  • the final diameter wires were subjected to a heat treatment at a temperature of 180°C for 10 hours.
  • the materials in the form of high purity silver pellets of 99.99% and OFE copper were melted at a temperature of 1220 C in a graphite crucible placed within an induction furnace.
  • the continuous casting process was conducted at a temperature of 1220°C in an inert gas atmosphere.
  • the continuous casting of rods with a chemical composition of Cu-7% Ag by weight, using a graphite mould was performed in primary cooling (mould cooling) and secondary cooling (of the solidified alloy after leaving the mould) conditions.
  • thermo-mechanical treatment processes were subjected to the thermo-mechanical treatment processes.
  • the casting was solution-annealed at a temperature of 750 C for 20 hours, and then quickly water quenched in order to preserve the homogeneous structure of the material.
  • the two-stage ageing process was carried out, which was to extract as much silver as possible from the homogeneous solid solution of Cu-Ag.
  • the primary ageing (the first stage) was conducted at 300 C for 20 hours.
  • the secondary ageing (the second stage) was conducted at a temperature of 450 C for 10 hours.
  • the alloy microstructure consisted of very numerous fine silver precipitates and a copper matrix.
  • the material was drawn into wires of the final diameter.
  • the wires of the final diameter were subjected to heat treatment at a temperature of 150°C for 100 hours.
  • the final microstructure of the wire as observed on its longitudinal section, presents very numerous, elongated, thin silver bands on the background of a copper matrix, favourable for obtaining a set of high mechanical properties and a high electrical conductivity of the product.
  • the solution according to the invention is a previously unknown, consistent, integrated method of manufacturing finished rods as a result of the continuous melting and casting process of Cu-Ag alloys that feature a high chemical purity with an allowable oxygen content in the alloy of 3 ppm or less and other impurities up to max. 20 ppm.
  • the chemical composition and the structure of Cu-Ag alloy rods obtained on the basis of the solution according to the invention are constant along the whole length of the casting.
  • the final product in the form of wires is only obtained by drawing of continuously cast rods, using dies with a round profile or other.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Metal Extraction Processes (AREA)
  • Continuous Casting (AREA)

Description

  • This invention concerns a method of manufacturing wires, including micro-wires, of Cu-Ag alloys, in particular of an alloy comprising Cu-((3÷7.9)% Ag by weight. These alloys having the form of rods and coming from a continuous melting and casting line are subject to properly selected heat treatment sequences and drawing into wires, featuring a set of excellent mechanical and electrical properties.
  • According to recent reports, Cu-Ag alloys may be used as conductors in power supply applications, in the automotive industry, in power supply and signalling systems of high speed railways, in medical appliances and as power supply components of strong magnetic field generator windings.
  • So far, copper-based conductor alloys, which may also contain Nb, Be, Zn, Sn, Zr, Cr, etc. have been applied in the analysed fields of technology. However, these alloys, apart from their relatively high mechanical properties, are characterized by low electrical conductivity. Apart from their high mechanical properties, Cu-Ag alloys also show exceptionally high values of electrical conductivity. A number of global solutions focus on developing these properties by selecting an appropriate technology of obtaining and processing materials. Research in scientific centres and research institutes worldwide is aimed at obtaining wires with excellent mechanical properties and, at the same time, the highest electrical conductivity possible. Production of ingots with various cross-section shapes and limited lengths, and continuous melting and casting systems ensuring that a material with theoretically endless length can be obtained, are amongst commonly known engineering solutions applied to obtain alloys.
  • An analysis of global solutions indicates that alloys obtained with those methods are subsequently processed by application of various technologies, in particular by plastic working, e.g. rolling, forging, drawing, extruding, in addition heat treatment operations are applied at various stages of mechanical processing in order to increase mechanical and electrical properties of the products.
  • A method for obtaining micro-wires of an alloy with the chemical composition of Cu-(2÷14)% Ag by weight is known from a Japanese patent application JP 2000-199042 . The description provides for a method of manufacturing microwires with a diameter of 0.01÷0.1 mm using eight variants of treatment. The research findings presented in the patent description have focused on a material in the form of cast rods with a diameter of 8mm and containing silver as an alloying constituent in the amount of 5 and 10% Ag by weight. The scheme for obtaining microwires according to the referred description provides for executing the following treatment sequences. Cast rods of the alloy of Cu-10% Ag by weight were subjected to diameter reduction in the drawing process from 10mm to 5 mm, at a set reduction of 61%. Next, the deformed material was heat treated at 450 C for 10 h, in order to apply subsequent overall reduction of either 94.2% or 99%. The final wire diameter was 1.2mm and 0.5mm, respectively. The wires with such a development history of thermo-mechanical treatment reached mechanical and electrical properties at a high level of 1530 MPa and 76% IACS (100% IACS = 58.0 MS/m). A separate treatment variant of cast rods with a bit lower silver content than in the previous version (6% Ag by weight) according to this solution, provided for the application of heat treatment conducted in the same conditions: 450 C/10 h applied to the initial material, i.e. the cast rod. Next, the overall reduction reaching 98.4% (for a diameter of 1.0mm) was set, which finally enabled a tensile strength of 1320MPa to be achieved. The electrical conductivity reached 78% IACS. Apart from the treatment variants described above, the authors of this patent introduced an additional stage of holding at 370 C/15 h. Beginning with a rod with an as-cast diameter of 8mm, the subsequent stages involved the overall reduction of 61% (to a diameter of 5mm), a heat treatment (450 C/10 h), again overall reduction of 84% (to a diameter of 2mm).
  • Next, additional one or two stages of heat treatment (370 C/15 h) was applied. One of the variants assumed, after the overall reduction of 84%, a heat treatment (370 C/15 h) and further working to diameters of 0.05÷0.03 mm (total reduction of 99,3÷99,8%). Such a procedure allows for a significant increase of mechanical properties within the range of 1420÷1735 MPa and an increase of electrical conductivity to 60÷65% IACS. The second of the variants expected, after the initial overall reduction of 61%, a heat treatment at 450 C /10h, the overall reduction of 84%, a heat treatment at 370 C/15 h, followed by the overall reduction of 97.8% to a diameter of 0.3mm, and a subsequent heat treatment 370 C/60 h, and the final overall reduction of 99.6% to a diameter of 0.02mm. Such a method of proceeding allowed the wires to achieve the tensile strength of 1250 MPa and the electrical conductivity of 71% IACS.
  • Another method for obtaining materials from a Cu-Ag alloy is presented in the international application description no. WO 2007-046378 . The input material was a Cu-Ag alloy ingot with dimensions of 10x10x30mm, obtained by melting in an electric Tamman furnace at a temperature of 1250 C. Alloys from the range of Cu- (1÷10)% Ag by weight, Cu-(2÷6)% Ag by weight were subjected to a reduction in the drawing process. The heat treatment processes applied in the central phase of the reduction were carried out at temperatures of 400÷500 C for a period from 1 to 50 hours in a vacuum or an inert gas atmosphere to avoid oxidation of the material surface. The relationships presented in the patent description refer to alloys mainly from the range of Cu-(1÷10)% Ag by weight. A Cu-Ag ingot with dimensions as mentioned above and a silver content of first 1%, 2% and 3% Ag by weight was subjected to a heat treatment at 450 C/20 h, and subsequently to an overall reduction with a logarithmic measure 0.6 (true strain is the natural logarithm of the elongation coefficient in the wire drawing process, the elongation coefficient means a square of the quotient of the initial wire diameter and the final wire diameter).
  • Then the material of Cu-4% Ag by weight was subjected to holding at 450 C/10 h and drawing with a strain of 0.6 in the logarithmic scale. As the silver content in the alloy increased, the time of the applied heat treatment decreased. An ingot of Cu-10% Ag by weight was subjected to holding at 450C for 5 hours. Each alloy described, at the subsequent stage of processing was subjected to a true strain of 8 or 12. As a result of the research, wires with a tensile strength of 1400MPa, and an electrical conductivity of 76.4% IACS were obtained, as well as with a tensile strength of 1200MPa and a conductivity of 81.7% IACS. In the opinion of the author of this solution, the quotient of strength of the Cu-Ag alloys exceeding 10% Ag by weight to the Ag content is disadvantageous, thus the selected range of the alloys tested was between 1 and 10% Ag by weight.
  • In the description of the American application no. US 2008/0202648 A1 research findings of Cu-Ag alloys with the silver content within the range of 1÷3.5% Ag by weight are presented. In this case, the initial material is an ingot with the maximum content of impurities of 10 ppm or less, obtained in the process of mould casting. The metal during casting is cooled at a cooling rate of 400÷500 C/min. The product according to this solution is further processed by e.g. drawing, rolling, etc.
  • The heat treatment operations following the plastic working processes are carried out at 300÷350 C for 10÷20 h, 350÷450 C for 5÷10 h, or at temperatures of 450÷550 C for 0.5÷5 h in an inert gas atmosphere. After the holding processes, the schedule of obtaining products of the Cu-(1÷3.5)% Ag by weight according to this invention provides for drawing to a diameter of 0.05mm or less. According to the referred-to description the tensile strength of the final material is within the range of 800÷1200 MPa, while the electric conductivity is within the range of 80÷84% IACS. This solution also assumes, at a certain stage of obtaining wires from the alloy of Cu-(1÷3.5)% Ag by weight, an additional holding process at temperatures of 600÷900 C for a very short time, i.e. from 5 to 120 seconds.
  • A disadvantage shared by the solutions is underutilization of a possibility to advantageously develop the microstructure of Cu-Ag alloys, and a related possibility to manufacture wires with an even higher set of mechanical and electrical properties.
  • Multi-sequential thermo-mechanical treatment processes conducted at unfavourably selected temperature ranges, combined with an overly extended heat treatment time, do not influence effectively the maximisation of mechanical and electrical properties. In addition, additional intermediate heat treatments (inherent to the whole production cost generation), used at an improper stage of wire production, do not translate fully into a high set of mechanical and electrical properties of the final product.
  • The objective of the invention is to present a consistent, integrated method for manufacturing wire components, including microwires, comprising the continuous melting and casting process of rods of Cu-Ag alloys and a sequential heat treatment combined with drawing, enabling wires, including micro-wires to be obtained with a tensile strength Rm within the range of 1100÷1400 MPa and simultaneously an electrical conductivity within the range of 68÷84% IACS.
  • The Cu-Ag alloys have the possibility of mutual limited solubility in the solid state of silver in copper and copper in silver. The alloy microstructure consists of a matrix comprising mainly copper containing a certain amount of not precipitated silver, and precipitates rich in silver, containing also a small amount of not precipitated copper. By using a multi-stage thermo-mechanical treatment of castings and properly selected temperature and time of the heat treatment (quenching and ageing), very numerous, fine silver precipitates may precipitate within the whole volume from the supersaturated silver solution in copper. The application of a significant plastic strain contributes to a substantial elongation of the precipitates formed as a result of the thermo-mechanical treatment of the alloy. The structure at a longitudinal section of the wires (microwires) consists of very numerous, thin, considerably elongated fibres almost wholly comprising silver with a small admixture of copper and the matrix comprising almost wholly of copper. The diameter of these fibres has nanometric dimensions.
  • In the solution according to this invention, the materials in the form of copper and silver with a high chemical purity are melted at a temperature of 1083÷1300 C in a graphite crucible placed in a furnace, and subsequently continuously cast at a temperature of 1083÷1300 C, in an inert gas atmosphere using a graphite mould, at primary cooling conditions (mould cooling) and secondary cooling conditions (the solidified alloy after leaving the mould), and subs the casting obtained with this method is subjected to a thermo-mechanical treatment during which the obtained casting is solution annealed at a temperature of 600÷779.1 C for 0.5÷100 hours, and subsequently quenched at a rate faster than the process of precipitating of its constituents from the solid solution, and then it is subjected to a further two-stage heat treatment processes in which first stage there is holding at 150÷300 C for 0.1÷100 hours, followed by - at the second stage - holding at a temperature of 300÷500 C for 0.1÷20 hours, and then slow cooling, followed by drawing into wires of the final cross-section.
  • Preferably, during the thermo-mechanical treatment, the obtained casting, after being solution annealed at a temperature of 600÷779.1 C for 0.5÷100 hours, and subsequently quenched and, subsequently, it is drawn, with a true strain measure of 0.1÷1, and then subject to the further two-stage heat treatment processes, followed by drawing into wires of the final cross-section.
  • Preferably, when deforming the material into the final cross-section wires, at least one intermediate heat treatment occurs within 200÷600 C for 0.1÷50 hours, followed by slow cooling.
  • Preferably, during the deformation of the material into the final cross-section wires at least one intermediate heat treatment occurs at 600÷900 C for 0.1÷1000 seconds, followed by quenching.
  • Preferably, final cross-section wires are subjected to a heat treatment at a temperature of 50÷300°C for 0.1÷1000 hours.
  • Preferably, after the solution annealing, the casting is water quenched.
  • Preferably, after the solution annealing, the casting is oil quenched.
  • Preferably, after the solution annealing, the casting is liquid nitrogen quenched.
  • Preferably, after the solution annealing, the casting is emulsion quenched.
  • Preferably, the graphite crucible is made of a high purity graphite, wherein alloying constituents are placed under a charcoal or graphite layer.
  • Preferably, the graphite crucible is placed in protective atmosphere.
  • Preferably, the graphite mould is cooled with a system that is mounted on it, through which a cooling agent flows (the primary cooling system).
  • Preferably, the casting leaving the mould is additionally cooled by a cooling agent fed directly onto the casting (the secondary cooling system).
  • Thanks to the application of the method according to the invention, the following technical and functional effects have been obtained, namely a possibility to form a set of excellent electrical and mechanical properties of the product, reduction of manufacturing costs thanks to properly selected thermo-mechanical treatments, a possibility to select the optimum conditions of the thermo-mechanical treatment sequence in order to obtain the required mechanical and electrical properties, an advantageous ratio of weight to mechanical parameters of the obtained products.
  • The solution according to the invention is presented in the embodiment examples in Table 1, wherein with an example of three Cu-Ag alloys with various silver contents within the range of this invention, the method of obtaining wires (including micro-wires) is presented, along with a list of mechanical and electrical properties at different stages of product manufacturing. Table 1
    Ag content in the alloy [% by weight] 3 5 7
    Diameter [mm] 9.5
    Casting properties Rm, MPa 190 210 240
    %IACS 89 87 84
    Heat treatment [°C/h] (solution annealing) 750/20 - oil quenching 750/10 - water quenching 750/20 - emulsion quenching
    True strain εrz 0.4 none 0.4
    Properties Rm, MPa 230 not applicable 260
    %IACS 94 not applicable 83
    Heat treatment [°C/h] (primary ageing) 300/20 - air cooling 200/20 - air cooling 300/20 - air cooling
    Heat treatment [°C/h] (secondary ageing) 450/10 - air cooling
    True strain εrz 2.7
    Properties Rm, MPa 510 540 570
    %IACS 90 87 83
    Heat treatment [°C/h] 400/2 - air cooling none none
    Properties Rm, MPa 400 not applicable not applicable
    %IACS 95 not applicable not applicable
    True strain εrz 7.7 6.5 7.7
    Final diameter of round wire [mm] 0.2 0.37 0.2
    Final heat treatment [°C/h] 240/2 180/10 150/100
    air cooling
    Properties Rm, MPa 1100 1220 1250
    %IACS 82 74 75
  • The method for obtaining microwires from Cu-Ag alloys is described with the embodiment examples below.
  • Example 1
  • Materials in the form of high purity silver pellets of 99.99% and OFE copper were melted at the temperature of 1200 C in a graphite crucible placed in an induction furnace. Continuous casting process was conducted at a temperature of 1200°C in an inert gas atmosphere. The continuous casting of rods with a chemical composition of Cu-3% Ag by weight, using a graphite mould was performed in primary cooling (mould cooling) and secondary cooling (the solidified alloy after leaving the mould) conditions. Round rods obtained as a result of the continuous casting process had a diameter of 9.5mm and a tensile strength Rm=190 MPa, and the electric conductivity of 89% IACS. The material was then subjected to the thermo-mechanical treatment processes. The casting was solution-annealed at a temperature of 750 C for 20 hours, and subsequently oil quenched to preserve the homogeneous structure of the material. The further procedure included setting a strain in the drawing process, with the true strain measure of 0.4. After this process, the rods demonstrated the tensile strength of Rm=230 MPa, and the electric conductivity of 94% IACS. Next, a two-stage ageing process was carried out in order to extract as much silver as possible from the homogeneous solid solution of Cu-Ag. The primary ageing (the first stage) was conducted at 300 C for 20 hours. The secondary ageing (the second stage) was conducted at the temperature of 450 C for 10 hours. After the completed preliminary heat treatments, the alloy microstructure consisted of very numerous fine silver precipitates in the copper matrix. Next, the material was drawn into wires with a true strain of 2.7, followed by an intermediate heat treatment that consisted in holding at a temperature of 400 C for 2 hours. Next, the material was drawn into the final diameter wires. In order to enhance the electric properties, the final diameter wires were subjected to a heat treatment at a temperature of 240°C for 2 hours. In the end, wires with a diameter of 0.2mm and a true strain of 7.7 had a tensile strength Rm=1100 MPa, and an electric conductivity of 82% IACS. The final microstructure of the wire, as observed on its longitudinal section, presented very numerous, elongated, thin silver bands and copper matrixes, favourable to obtain a set of high mechanical properties and a high electrical conductivity of the product.
  • Example 2
  • Materials in the form of high purity silver pellets of 99.99% and OFE copper were melted at a temperature of 1200 C in a graphite crucible placed in an induction furnace. The continuous casting process was conducted at a temperature of 1210°C in an inert gas atmosphere. The continuous casting of rods with a chemical composition of Cu-5% Ag by weight, using a graphite mould was performed in the primary cooling (mould cooling) and secondary cooling (of the solidified alloy after leaving the mould) conditions. The round rods obtained as a result of the continuous casting process had a diameter of 9.5mm and a tensile strength Rm=210 MPa, and an electric conductivity of 87% IACS. Thus obtained material was subjected to the thermo-mechanical treatment processes. The casting was solution-annealed at a temperature of 750 C for 10 hours, and subsequently it was water quenched in order to preserve the homogeneous structure of the material. After this process, it was necessary to conduct a two-stage ageing processes, in order to extract as much silver as possible from the homogeneous solid solution of Cu-Ag. The primary ageing (the first stage) was conducted at 200 C for 20 hours. The secondary ageing (the second stage) was conducted at a temperature of 450 C for 10 hours. After the preliminary heat treatments, the alloy microstructure consisted of very numerous fine silver precipitates in the copper matrix. Next, the material was drawn into the final diameter wires. In order to enhance the electric properties, the final diameter wires were subjected to a heat treatment at a temperature of 180°C for 10 hours. Finally, the wires with a diameter of 0.37mm and a true strain of 6.5 had a tensile strength Rm=1220 MPa, and an electric conductivity of 74% IACS. The final wire microstructure, as observed on its longitudinal section, presented very numerous, elongated, thin silver bands and copper matrixes, favourable to obtain a set of high mechanical properties and a high electrical conductivity of the product.
  • Example 3
  • The materials in the form of high purity silver pellets of 99.99% and OFE copper were melted at a temperature of 1220 C in a graphite crucible placed within an induction furnace. The continuous casting process was conducted at a temperature of 1220°C in an inert gas atmosphere. The continuous casting of rods with a chemical composition of Cu-7% Ag by weight, using a graphite mould was performed in primary cooling (mould cooling) and secondary cooling (of the solidified alloy after leaving the mould) conditions. The round rods obtained as a result of the continuous casting process had a diameter of 9.5mm and a tensile strength Rm=240 MPa, and an electrical conductivity of 84% IACS. Thus obtained material was subjected to the thermo-mechanical treatment processes. The casting was solution-annealed at a temperature of 750 C for 20 hours, and then quickly water quenched in order to preserve the homogeneous structure of the material. The further procedure included setting a strain in the drawing process, with the true strain measure of 0.4. After this process the rods had a tensile strength Rm=260 MPa, and an electrical conductivity of 83% IACS. Next, the two-stage ageing process was carried out, which was to extract as much silver as possible from the homogeneous solid solution of Cu-Ag. The primary ageing (the first stage) was conducted at 300 C for 20 hours. The secondary ageing (the second stage) was conducted at a temperature of 450 C for 10 hours. After the preliminary heat treatments, the alloy microstructure consisted of very numerous fine silver precipitates and a copper matrix. Next, the material was drawn into wires of the final diameter. In order to enhance the electric properties, the wires of the final diameter were subjected to heat treatment at a temperature of 150°C for 100 hours. Finally, the wires with a diameter of 0.2mm and a true strain of 7.7 had a tensile strength Rm=1250 MPa, and an electric conductivity of 75% IACS. The final microstructure of the wire, as observed on its longitudinal section, presents very numerous, elongated, thin silver bands on the background of a copper matrix, favourable for obtaining a set of high mechanical properties and a high electrical conductivity of the product.
  • The solution according to the invention is a previously unknown, consistent, integrated method of manufacturing finished rods as a result of the continuous melting and casting process of Cu-Ag alloys that feature a high chemical purity with an allowable oxygen content in the alloy of 3 ppm or less and other impurities up to max. 20 ppm. The chemical composition and the structure of Cu-Ag alloy rods obtained on the basis of the solution according to the invention are constant along the whole length of the casting. The final product in the form of wires (including micro-wires), is only obtained by drawing of continuously cast rods, using dies with a round profile or other.

Claims (13)

  1. A method of manufacturing wires, including microwires, of Cu-Ag alloys, in particular of alloys with Cu-(3÷7.9)% Ag by weight characterised in that the materials in the form of copper and silver with a high chemical purity are melted at a temperature of 1083÷1300 C in a graphite crucible placed in a furnace, and subsequently continuously cast at a temperature of 1083÷1300 C, in an inert gas atmosphere using a graphite mould, in primary cooling (mould cooling) and secondary cooling conditions (the solidified alloy after leaving the mould), and then the casting thus obtained is subjected to a thermo-mechanical treatment during which the obtained casting is solution annealed at a temperature of 600÷779.1 C for 0.5÷100 hours, and subsequently quenched at a rate faster than the process of precipitating of its constituents from the solid solution, and then it is subjected to a further two-stage heat treatment processes in which first stage there is holding at 150÷300 C for 0.1÷100 hours, followed by - at the second stage - holding at a temperature of 300÷500 C for 0.1÷20 hours, and then slow cooling, followed by drawing into wires of the final cross-section.
  2. A method as claimed in the claim 1 characterised in that during the thermo-mechanical treatment the obtained casting, after being solution annealed at a temperature of 600÷779.1 C for 0.5÷100 hours, and subsequently quenched at a rate faster than the process of precipitating of its constituents from the solid solution, is then drawn, with a true strain measure of 0.1÷1, and then subject to the further two-stage heat treatment processes, followed by drawing into wires of the final cross-section.
  3. A method as claimed in claim 1 characterised in that during drawing of the material into wires of the final cross-section, at least one intermediate heat treatment occurs within the range of 200÷600 C for 0.1÷20 hours, followed by either slow cooling or quenching.
  4. A method as claimed in claim 1 characterised in that during the drawing of the material into wires of the final cross-section, at least one intermediate heat treatment occurs within 600÷900 C for 0.1÷1000 hours, followed either by slow cooling or quenching.
  5. A method as claimed in claim 2 or 1 characterised in that the wires of the final cross-section are subjected to a heat treatment at a temperature of 50÷250°C for 0.1÷1000 hours.
  6. A method as claimed in claim 2 characterised in that after the solution annealing the casting is water quenched.
  7. A method as claimed in claim 2 characterised in that after the solution annealing the casting is oil quenched, in particular with a process oil.
  8. A method as claimed in claim 2 characterised in that after the solution annealing the casting is liquid nitrogen quenched.
  9. A method as claimed in claim 2 characterised in that after the solution annealing the casting is emulsion quenched, with the oil in water concentration of between 3 and 25%.
  10. A method as claimed in claim 1 characterised in that the graphite crucible is made of a high purity graphite, wherein alloying constituents are placed under a charcoal or graphite layer.
  11. A method as claimed in claim 1 characterised in that the graphite crucible is placed in a protective atmosphere.
  12. A method as claimed in claim 1 characterised in that the graphite mould is cooled with a system that is mounted on it, through which a cooling agent flows (the primary cooling system).
  13. A method as claimed in claim 1 characterised in that the casting leaving the mould is additionally cooled by a cooling agent applied directly onto the casting (the secondary cooling system).
EP14461523.4A 2013-04-05 2014-04-04 Method of manufacturing wires of Cu-Ag alloys Active EP2873475B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL14461523T PL2873475T3 (en) 2013-04-05 2014-04-04 Method of manufacturing wires of Cu-Ag alloys
SI201431053T SI2873475T1 (en) 2013-04-05 2014-04-04 Method of manufacturing wires of Cu-Ag alloys

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL403443A PL221274B1 (en) 2013-04-05 2013-04-05 Method for producing wires from Cu-Ag alloys

Publications (2)

Publication Number Publication Date
EP2873475A1 EP2873475A1 (en) 2015-05-20
EP2873475B1 true EP2873475B1 (en) 2018-10-17

Family

ID=50897521

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14461523.4A Active EP2873475B1 (en) 2013-04-05 2014-04-04 Method of manufacturing wires of Cu-Ag alloys

Country Status (6)

Country Link
EP (1) EP2873475B1 (en)
ES (1) ES2706474T3 (en)
HU (1) HUE041639T2 (en)
LT (1) LT2873475T (en)
PL (2) PL221274B1 (en)
SI (1) SI2873475T1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108368565A (en) * 2016-05-16 2018-08-03 古河电气工业株式会社 Copper series alloy wire rod

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113736970B (en) * 2021-09-01 2023-03-03 西安斯瑞先进铜合金科技有限公司 Preparation method of high-softening-resistance copper-chromium-zirconium alloy rod
CN114645153B (en) * 2022-03-17 2023-01-24 东北大学 High-strength high-conductivity copper-silver alloy wire and preparation method thereof
CN115141946B (en) * 2022-08-03 2023-07-25 中南大学 Short-process preparation and processing method for high-performance copper alloy wire

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2726939B2 (en) * 1989-03-06 1998-03-11 日鉱金属 株式会社 Highly conductive copper alloy with excellent workability and heat resistance
JP2000199042A (en) 1998-11-04 2000-07-18 Showa Electric Wire & Cable Co Ltd PRODUCTION OF Cu-Ag ALLOY WIRE ROD AND Cu-Ag ALLOY WIRE ROD
JP2000239766A (en) * 1999-02-19 2000-09-05 Sumitomo Electric Ind Ltd Production of wear resistant trolley wire
JP4311277B2 (en) 2004-05-24 2009-08-12 日立電線株式会社 Manufacturing method of extra fine copper alloy wire
WO2007046378A1 (en) 2005-10-17 2007-04-26 National Institute For Materials Science Cu-Ag ALLOY WIRE HAVING HIGH STRENGTH AND HIGH CONDUCTIVITY AND METHOD FOR MANUFACTURE THEREOF
US7544886B2 (en) * 2005-12-20 2009-06-09 Hitachi Cable, Ltd. Extra-fine copper alloy wire, extra-fine copper alloy twisted wire, extra-fine insulated wire, coaxial cable, multicore cable and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108368565A (en) * 2016-05-16 2018-08-03 古河电气工业株式会社 Copper series alloy wire rod

Also Published As

Publication number Publication date
HUE041639T2 (en) 2019-05-28
ES2706474T3 (en) 2019-03-29
PL221274B1 (en) 2016-03-31
EP2873475A1 (en) 2015-05-20
LT2873475T (en) 2019-03-25
PL403443A1 (en) 2014-10-13
SI2873475T1 (en) 2019-05-31
PL2873475T3 (en) 2019-04-30

Similar Documents

Publication Publication Date Title
JP4311277B2 (en) Manufacturing method of extra fine copper alloy wire
CN104781431B (en) The manufacturing method of aluminium alloy conductor, aluminium alloy stranded conductor, coated electric wire, harness and aluminium alloy conductor
CN106029930B (en) Copper-alloy stranded conductor and its manufacture method, electric wire for automobiles
JP5840235B2 (en) Copper alloy wire and method for producing the same
JP5117604B1 (en) Cu-Ni-Si alloy and method for producing the same
JP5051647B2 (en) High-strength and high-conductivity Cu-Ag alloy wire and method for producing the same
EP2873475B1 (en) Method of manufacturing wires of Cu-Ag alloys
CN102751046B (en) Extra-high-strength aluminium-clad steel wire production method
CN105603242B (en) A kind of copper silver magnesium alloy contact wire and preparation method thereof
JP6240424B2 (en) Method for producing Al alloy conductive wire
JP2014156617A (en) Copper alloy wire, copper alloy twisted wire, coated electric wire, and coated electric wire having terminal
WO2014007258A1 (en) Copper-alloy wire rod and manufacturing method therefor
JP2015021138A (en) Method for manufacturing copper-silver alloy wire and copper-silver alloy wire
CN106574352A (en) Method for producing aluminum wire
CN111411256B (en) Copper-zirconium alloy for electronic components and preparation method thereof
US4080222A (en) Aluminum-iron-nickel alloy electrical conductor
US4082573A (en) High tensile strength aluminum alloy conductor and method of manufacture
US4080223A (en) Aluminum-nickel-iron alloy electrical conductor
CN109136634B (en) High-performance copper alloy material and preparation method thereof
JP6635732B2 (en) Method for manufacturing aluminum alloy conductive wire, aluminum alloy conductive wire, electric wire and wire harness using the same
RU2015110053A (en) MECHANICAL PROCESSABLE COPPER ALLOYS FOR ELECTRICAL CONNECTORS
US4437901A (en) Method and apparatus for improved heat treatment of aluminum alloy rod
JP2010198873A (en) Conductor for electric wire
JP6023901B2 (en) Electric wire or cable, wire harness, and aluminum alloy strand manufacturing method
JP4143010B2 (en) Method for producing copper alloy conductor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140404

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

R17P Request for examination filed (corrected)

Effective date: 20151120

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: B22D 11/00 20060101AFI20171121BHEP

Ipc: B22D 11/041 20060101ALI20171121BHEP

Ipc: B22D 11/04 20060101ALI20171121BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180103

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KAWECKI, ARTUR

Inventor name: KNYCH, TADEUSZ

Inventor name: SMYRAK, BEATA

Inventor name: KWASNIEWSKI, PAWEL

Inventor name: KIESIEWICZ, GRZEGORZ

Inventor name: MAMALA, ANDRZEJ

Inventor name: SIEJA-SMAGA, ELIZA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INSTYTUT METALI NIEZELAZNYCH

Owner name: TELE-FONIKA KABLE SPOLKA AKCYJNA

Owner name: KGHM POLSKA MIEDZ SPOLKA AKCYJNA

Owner name: AKADEMIA GORNICZO-HUTNICZA IM. STANISLAWA STASZICA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014034177

Country of ref document: DE

Ref country code: AT

Ref legal event code: REF

Ref document number: 1053392

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2706474

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20190329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190117

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190117

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190217

REG Reference to a national code

Ref country code: EE

Ref legal event code: FG4A

Ref document number: E017084

Country of ref document: EE

Effective date: 20190115

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E041639

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190217

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014034177

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

26N No opposition filed

Effective date: 20190718

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190404

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1053392

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181017

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20230317

Year of fee payment: 10

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230529

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230426

Year of fee payment: 10

Ref country code: FR

Payment date: 20230424

Year of fee payment: 10

Ref country code: ES

Payment date: 20230627

Year of fee payment: 10

Ref country code: DE

Payment date: 20230420

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SI

Payment date: 20230323

Year of fee payment: 10

Ref country code: LV

Payment date: 20230413

Year of fee payment: 10

Ref country code: HU

Payment date: 20230421

Year of fee payment: 10

Ref country code: AT

Payment date: 20230420

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20230419

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LT

Payment date: 20240229

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20240301

Year of fee payment: 11

Ref country code: EE

Payment date: 20240229

Year of fee payment: 11

Ref country code: CZ

Payment date: 20240307

Year of fee payment: 11

Ref country code: GB

Payment date: 20240306

Year of fee payment: 11

Ref country code: SK

Payment date: 20240306

Year of fee payment: 11