EP3540745A1 - Draht zur beförderung von elektrischer energie aus aluminiumlegierung mit hoher elektrischer leitfähigkeit - Google Patents

Draht zur beförderung von elektrischer energie aus aluminiumlegierung mit hoher elektrischer leitfähigkeit Download PDF

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Publication number
EP3540745A1
EP3540745A1 EP19167496.9A EP19167496A EP3540745A1 EP 3540745 A1 EP3540745 A1 EP 3540745A1 EP 19167496 A EP19167496 A EP 19167496A EP 3540745 A1 EP3540745 A1 EP 3540745A1
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EP
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Prior art keywords
alloy
transport wire
electrical
zirconium
aluminum alloy
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EP19167496.9A
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English (en)
French (fr)
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EP3540745B1 (de
Inventor
Emilien Comoret
Rodrigue Sumera
Nicolas MASQUELIER
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Nexans SA
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Nexans SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00—Power cables
    • H01B9/008—Power cables for overhead application
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • B21C37/045—Manufacture of wire or bars with particular section or properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • 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
    • H01B1/023—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0036—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/32—Filling or coating with impervious material
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49988—Metal casting
    • Y10T29/49991—Combined with rolling

Definitions

  • the invention relates to an electrical cable comprising at least one aluminum alloy electrical transport wire, a method of manufacturing said electric transport wire, and a method of manufacturing said electric cable.
  • These cables are conventionally composed of a central reinforcing element, surrounded by at least one electrically conductive layer.
  • the central reinforcing element may be a composite or metallic element.
  • the electrically conductive layer can in turn typically comprise an assembly of metal strands, preferably twisted around the central element.
  • the metal strands may be strands of aluminum, copper, aluminum alloy or copper alloy. That said, the electrically conductive layer is generally made of aluminum or an aluminum alloy, since this material has a relatively low weight compared to other electrically conductive materials.
  • EP 0 787 811 is known an electric transport wire aluminum alloy ensuring good breaking strength, and good temperature resistance.
  • This alloy contains 0.28 to 0.80 percent by weight of zirconium, 0.10 to 0.80 percent by weight of manganese and 0.10 to 0.40 percent by weight of copper.
  • This alloy is obtained by a process comprising a casting step of the molten aluminum alloy, then an extrusion or rolling step, then a heating step, and finally a cold working step in order to obtain alloy wires 4 mm in diameter.
  • the heating step can be performed after the cold working step.
  • this alloy has the disadvantage of having an electrical conductivity lower than 56.5% IACS (International Annealed Copper Standard ), less than 51% IACS depending on the operating conditions used. Furthermore, the method of manufacturing said alloy does not allow on the one hand to control the microstructure of zirconium precipitates (Al 3 Zr), and on the other hand to produce sufficient zirconium precipitates in said alloy. As a result, this method induces a breaking strength and an electrical conductivity of said alloy which are not optimized.
  • IACS International Annealed Copper Standard
  • the object of the present invention is to overcome the disadvantages of the techniques of the prior art by proposing an aluminum alloy, in particular used as an electric transport wire in an electric cable, comprising aluminum and zirconium, easy to manufacture, having improved electrical properties (in terms of electrical capacity and electrical conductivity), while ensuring good mechanical properties, especially in terms of breaking strength and resistance to hot creep and good temperature resistance.
  • the present invention firstly relates to an electric aluminum alloy wire comprising aluminum, zirconium and unavoidable impurities, characterized in that said alloy comprises at least 80 parts by weight of zirconium under form of precipitates (Al 3 Zr) per 100 parts by weight of zirconium in said aluminum alloy.
  • the aluminum alloy of the electrical transport wire of the The invention has a higher electrical conductivity than prior art aluminum alloys while ensuring good electrical properties.
  • said electric transport wire comprises at the surface a porous layer of alumina hydroxide.
  • the alumina hydroxide layer is an aluminum oxide hydroxide layer, or in other words, a hydrated alumina layer.
  • the thermal emissivity is optimized and the thermal absorption is minimized, which is favorable to a significant reduction in the heating of the transport wire. electric that could be weakened at high temperatures.
  • the second subject of the present invention is an electric transport wire made of aluminum alloy comprising aluminum, zirconium precipitates and unavoidable impurities, characterized in that the said electric transport wire comprises at the surface a porous layer of hydroxide alumina.
  • the thermal emissivity is optimized and the thermal absorption is minimized, which is favorable to a significant reduction in the heating of the electric transport wire which could be embrittled at high temperatures. and thus to the improvement of electrical properties while guaranteeing good mechanical properties.
  • said alloy comprises at least 80 parts by weight of zirconium in the form of precipitates (Al 3 Zr) per 100 parts by weight of zirconium in said aluminum alloy.
  • the aluminum alloy of the electric transport wire conforming to The second object of the invention has a higher electrical conductivity than aluminum alloys of the prior art.
  • the aluminum alloy electrical transport wire according to the first object or the second subject of the invention is an electric transport wire made of said aluminum alloy.
  • the hydrated alumina layer is a monohydrated layer.
  • boehmite which is the gamma polymorph of AlO (OH) or Al 2 O 3 .H 2 O
  • diaspore which is the alpha polymorph of AlO (OH) or Al 2 O 3 .H 2 O.
  • the hydrated alumina layer is a polyhydrated layer, and preferably a trihydrate layer.
  • alumina trihydrate of gibbsite or hydrargillite, which is the gamma polymorph of Al (OH) 3 ; the bayerite that is the alpha polymorph of Al (OH) 3 ; or nordstrandite, which is the beta polymorph of Al (OH) 3 .
  • the electric transport wire comprises a controlled microstructure dispersion of zirconium precipitates (Al 3 Zr).
  • the aluminum alloy may comprise from 0.05% to 0.6% by weight of zirconium, preferably from 0.05% to 0.5% by weight of zirconium, and more preferably from 0.2% to 0.5% by weight of zirconium.
  • the aluminum alloy When the amount of zirconium in said aluminum alloy is less than 0.05% by weight, the aluminum alloy may not include enough zirconium precipitates, inducing a random distribution of said precipitates in the alloy and thus, a decrease in its electrical conductivity.
  • the amount of zirconium in said aluminum alloy is greater than 0.5% by weight, large zirconium precipitates (Al 3 Zr) can be formed, inducing a decrease in the mechanical properties of the alloy, particularly in terms of Tear resistant.
  • the diameter of the zirconium precipitates (Al 3 Zr) in said alloy of the electric transport wire according to the first object or the second subject of the invention ranges from 1 to 100 nm, preferably from 1 to at 20 nm, and more preferably from 1 to 5 nm.
  • the temperature resistance of the alloy of the electrical transport wire of the invention is improved.
  • the alloy of the electric transport wire according to the first object or object of the invention can withstand a temperature of 150 ° C, and preferably a temperature of 210 ° C.
  • said zirconium precipitates (Al 3 Zr) are spherical.
  • the aluminum alloy of the electrical transport wire conforms to the first object or second object of the invention further comprises a member selected from copper, iron and their mixture.
  • the aluminum alloy of the electric transport wire according to the first object or subject of the invention may comprise from 0.15% to 0.4% by weight of iron, and preferably from 0.25% to 0% by weight. 35% by weight of iron.
  • the presence of the copper in the aluminum alloy of the electric transport wire according to the first object or the second subject of the invention makes it possible to improve the mechanical properties with respect to the resistance to hot creep, while maintaining good electrical conductivity.
  • An alloy having good creep resistance withstands deformation under long-term mechanical stresses at elevated temperatures.
  • the aluminum alloy of the electric transport wire according to the first object or subject of the invention may comprise from 0.05% to 0.35% by weight of copper, and preferably from 0.12% to 0%. 22% by weight of copper.
  • the electrical conductivity of the aluminum alloy of the electric transport wire according to the first object or subject of the invention may be at least 57% International Annealed Copper Standard (IACS), preferably at least 58%. % IACS, and preferably at least 59% IACS.
  • IACS International Annealed Copper Standard
  • the aluminum alloy of the electrical transport wire according to the first object or object of the invention comprises only aluminum; zirconium; unavoidable impurities; and optionally an element selected from iron, copper and their mixture. Indeed, if we add other elements in the alloy, the electrical conductivity can drop sharply. For electrical applications, it is important to keep the aluminum alloy as pure as possible.
  • the aluminum content of the aluminum alloy of the electric transport wire according to the first object or second subject of the invention may be at least 95.00% by weight, preferably at least 98.00. % by weight, preferably at least 99.00% by weight, preferably at least 99.40%.
  • the unavoidable impurity content in the aluminum alloy of the electric transport wire according to the first object or subject of the invention may be at most 1.50% by weight, preferably at most 1, 10% by weight, preferably at most 0.60% by weight, preferably at most 0.30% by weight, and preferably at most 0.10% by weight.
  • the term "unavoidable impurities" means the sum of metallic or non-metallic elements included in the alloy, excluding aluminum, zirconium, iron, copper, and possibly oxygen, during the manufacture of said alloy.
  • These unavoidable impurities may be for example one or more of the following elements: Ag, Cd, Cr, Mg, Mn, Pb, Si, Ti, V, Ni, S, and / or Zn.
  • the aluminum alloy comprises at most 0.08% by weight, and preferably at most 0.05% by weight of Mn and / or Si. In fact, these unavoidable impurities can decrease the electrical conductivity of said alloy.
  • the third subject of the present invention is an electrical cable comprising at least one electric transport wire conforming to the first object or the second subject of the invention, characterized in that the said electric cable further comprises an elongated reinforcing element.
  • an elongate reinforcing element makes it possible in particular to form an aerial power transmission cable (i.e. OHL cable).
  • the elongate reinforcing member is surrounded by said aluminum alloy electrical transport wire.
  • the elongate reinforcing element is a central element.
  • the elongated reinforcing element is preferably a central mechanical support rod.
  • aluminum alloy electrical transport wire according to the first object or second object of the invention
  • a metal strand or “an element electrically elongated driver”
  • the electric cable according to the third subject of the invention comprises an assembly (ie a plurality) of aluminum alloy electrical transport wires conforming to the first object or the second subject of the invention, these wires being in particular wound on the elongated reinforcing element.
  • This assembly may in particular form at least one layer of the continuous envelope type, for example of circular or oval or square cross section.
  • the electrical cable of the invention comprises an elongated reinforcing member
  • said assembly may be positioned around the elongate reinforcing member.
  • the metal strands may be of round, trapezoidal or Z-shaped cross section.
  • the strands When the strands are of round cross section, they can have a diameter ranging from 2.25 mm to 4.75 mm. When the strands are of non-round cross section, their equivalent diameter in round section can also range from 2.25 mm to 4.75 mm.
  • the elongate reinforcing member is surrounded by at least one layer of an aluminum alloy wire assembly conforming to the first object or second object of the invention.
  • the metal strands constituting at least one layer of an assembly of aluminum alloy metal strands of the invention are capable of conferring on said layer a substantially regular surface, each constituent strand of the layer being able to have a cross-section of complementary shape to the (s) strand (s) which is / are adjacent (s).
  • each constituent strand of the layer may in particular have a cross section of shape complementary to the (x) strand (s) which is / are adjacent thereto ( (s) 'means that: the juxtaposition or the nesting of all the constituent strands of the layer forms a continuous envelope (without irregularities), for example of circular or oval or square section.
  • the Z-shaped or trapezoid-shaped cross-section strands make it possible to obtain a regular envelope, unlike the round cross-section strands.
  • strands of Z-shaped cross-section are preferred.
  • said layer formed by the assembly of the metal strands has a cross section in the form of a ring.
  • the elongated reinforcing member may be typically a composite or metallic member.
  • a composite or metallic member By way of example, mention may be made of steel strands or composite strands of aluminum in an organic matrix.
  • the electrical transport wire of the invention may be twisted around the elongated reinforcing element, in particular when the electrical cable of the invention comprises an assembly of aluminum alloy electrical transport wires conforming to the first or second object. of the invention (ie metal strands).
  • the inventors of this application have discovered surprising that the electrical conductivity of the alloy obtained at the end of the heating step iv) is increased.
  • sufficient zirconium precipitates are formed to allow the increase of the electrical conductivity with respect to an alloy of the prior art comprising zirconium.
  • the addition of iron and / or copper in the alloy, associated with the heating step iv) of the process of the invention leads to an alloy having both improved mechanical properties, especially in terms of resistance to hot creep and breaking strength, and better electrical conductivity.
  • Step i) can be conventionally carried out by incorporating a parent alloy (ie "master alloy " in English) comprising aluminum; zirconium; optionally iron and / or copper; in a bath of molten aluminum, substantially pure. It is also possible to perform step i) by adding zirconium, and optionally an element chosen from copper, iron and their mixture, to molten aluminum, and then mixing.
  • a parent alloy ie " master alloy " in English
  • step i) by adding zirconium, and optionally an element chosen from copper, iron and their mixture, to molten aluminum, and then mixing.
  • Stage ii) makes it possible in particular to form, by cooling the casting (ie solidification), a cast aluminum alloy, in particular in the form of bar or bar, preferably cylindrical.
  • the cross section of the bar can range for example from 500 mm 2 to 2500 mm 2 or more.
  • the casting temperature in step ii) is from about 680 ° C to about 850 ° C, and preferably from about 710 ° C to about 770 ° C.
  • the cooling during the casting step ii) is carried out at a speed of at least 50 ° C / min, from the casting temperature up to about 500 ° C.
  • the casting step can be carried out continuously, in particular using a rotating wheel, called "casting".
  • Step iii) rolls said cast aluminum alloy into a rolled alloy.
  • the steps of casting ii) and rolling iii) make it possible to control the microstructure of the zirconium precipitates in said alloy while avoiding the formation of large zirconium precipitates, and thus guarantee the production of an aluminum alloy having good mechanical properties, especially in terms of breaking strength.
  • Said laminated alloy preferably has a cross section, round.
  • the diameter of the cross section may be, for example, from about 7 mm to about 26 mm.
  • the step iii) of rolling can be carried out hot, especially at a temperature ranging from 400 to 550 ° C.
  • said aluminum alloy manufactured according to the process of the invention comprises at least 80 parts by weight of zirconium in the form of precipitates per 100 parts by weight of zirconium in said alloy. 'aluminum.
  • this step iv) makes it possible to obtain at least 90 parts by weight of zirconium in the form of precipitates per 100 parts by weight of zirconium in the aluminum alloy manufactured according to the method of the invention.
  • This step iv) may preferably be a so-called "income” step, well known to those skilled in the art; said income stage being in particular different from a so-called “annealing” step also known under the anglicism " annealing step " .
  • the annealing step makes it possible to increase the mechanical elongation of an alloy by heating it, and thus to be able to easily deform it once annealed, while the income step makes it possible, in turn, to increase the resistance. mechanical alloy.
  • step iv) is carried out at a temperature ranging from 300 to 500 ° C, preferably from 350 to 450 ° C, and even more preferably from 400 to 450 ° C.
  • the duration of the heating step iv) ranges from 100 to 500 hours, preferably from 100 to 350 hours, and even more preferably from 100 to 300 hours.
  • step iv) the temperature and times used in said step iv) are interdependent.
  • time / temperature pairs used during step iv the following time / temperature combinations can notably be mentioned: 100 hours / 450 ° C., 200 hours / 400 ° C., and 340 hours / 350 ° C. vs.
  • the control of the heating time during step iv) for a given temperature can be carried out by transmission electron microscopy.
  • the heating according to step iv) can be carried out using an electric furnace (i.e. resistance furnace) and / or an induction furnace and / or a gas oven.
  • an electric furnace i.e. resistance furnace
  • an induction furnace i.e. induction furnace
  • a gas oven i.e. induction furnace
  • step iv) can be carried out by carrying out a slow rise in temperature, in particular by about 5 ° C. per minute.
  • the method of manufacturing the electric transport wire according to the first subject of the invention further comprises the following step: v) cold-working said electric transport wire of step iv), to obtain an electric transport wire with the desired dimensions.
  • the cold working step v) may be a drawing step in order to obtain said electric transport wire with the desired dimensions (e.g. final diameter). It can be performed at a temperature of at most 80 ° C.
  • step v) makes it possible to obtain metal alloy strands (or electrical transport wires) of aluminum alloy, in particular of round or trapezoidal or Z-shaped cross section.
  • the diameter of the cross section can range from 0.2mm to 5.0mm.
  • the method according to the fourth subject of the invention further comprises the following step: vi) forming by chemical conversion a porous layer of alumina hydroxide on the surface of said electric transport wire.
  • Step vi) may be performed with the electrical transport wire from step iv) or from step v) if it exists.
  • the porous layer of alumina hydroxide surrounding said electrical transport wire and formed in step vi), is preferably a layer that is in direct physical contact with said electrical transport wire. in aluminum alloy.
  • the electrical cable thus formed does not preferably comprise a layer interposed between the porous layer of alumina hydroxide and said aluminum alloy electrical transport wire.
  • pores of said porous alumina hydroxide layer are optionally arranged substantially evenly (or homogeneously) all along the outer surface of the porous alumina hydroxide layer, and they may all have substantially the same dimensions .
  • Step A) may be conventionally carried out by incorporating a master alloy (ie "master alloy " in English) comprising aluminum; zirconium; optionally iron and / or copper; in a bath of molten aluminum, substantially pure. It is also possible to carry out step A) by adding zirconium, and optionally an element chosen from copper, iron and their mixture, to molten aluminum, and then mixing.
  • a master alloy ie " master alloy " in English
  • step A) by adding zirconium, and optionally an element chosen from copper, iron and their mixture, to molten aluminum, and then mixing.
  • Stage B) makes it possible in particular to form, by cooling the crude casting (ie solidification), a cast aluminum alloy, especially in the form of bar or bar, preferably cylindrical.
  • the cross section of the bar can range for example from 500 mm 2 to 2500 mm 2 or more.
  • the casting temperature in step B) ranges from about 680 ° C to about 850 ° C, and preferably from about 710 ° C to about 770 ° C.
  • the cooling in the casting step B) is carried out at a speed of at least 50 ° C / min, from the casting temperature up to about 500 ° C.
  • the casting step can be carried out continuously, in particular using a rotating wheel, called "casting".
  • the casting steps B) and the rolling step C) make it possible to control the microstructure of the zirconium precipitates in said alloy by avoiding the formation of large zirconium precipitates, and thus guarantee the obtaining of an aluminum alloy having good properties. mechanical, especially in terms of breaking strength.
  • Said laminated alloy preferably has a cross section, round.
  • the diameter of the cross section may be, for example, from about 7 mm to about 26 mm.
  • the rolling step C) can be carried out hot, in particular at a temperature ranging from 400 to 550 ° C.
  • step D) is carried out at a temperature ranging from 300 to 500 ° C, preferably from 350 to 450 ° C, and even more preferably from 400 to 450 ° C.
  • the duration of the heating step D) ranges from 100 to 500 hours, preferably from 100 to 350 hours, and even more preferably from 100 to 300 hours.
  • step D) is carried out at a temperature between 400 and 450 ° C, for 100 to 500 hours.
  • step D the temperature and time parameters used in said step D) are interdependent.
  • the following time / temperature combinations can notably be mentioned: 100 hours / 450 ° C. and 200 hours / 400 ° C.
  • the control of the heating time in step D) for a given temperature can be carried out by transmission electron microscopy.
  • Stage D) for heating the rolled alloy i.e. heat treatment step
  • said aluminum alloy manufactured according to the process according to the fifth subject of the invention may comprise at least 80 parts by weight of zirconium in the form of precipitates per 100 parts by weight of zirconium in said aluminum alloy.
  • the heating of stage D) can be carried out by carrying out a slow rise in temperature, in particular by approximately 5 ° C. per minute.
  • this step D) makes it possible to obtain at least 90 parts by weight of zirconium in the form of precipitates per 100 parts by weight of zirconium in the aluminum alloy manufactured according to the process according to the fifth subject of the invention.
  • This step D) may preferably be a so-called "income” step, well known to those skilled in the art; said income stage being in particular different from a so-called “annealing” step also known under the anglicism " annealing step " .
  • the annealing step makes it possible to increase the mechanical elongation of an alloy by heating it, and thus to be able to easily deform it once annealed, while the income step makes it possible, in turn, to increase the resistance. mechanical alloy.
  • the heating according to step D) can be carried out using an electric furnace (ie resistance furnace) and / or an induction furnace and / or a gas oven.
  • an electric furnace ie resistance furnace
  • an induction furnace ie resistance furnace
  • a gas oven ie resistance furnace
  • the drawing step E) makes it possible to obtain said electric transport wire with the desired dimensions (e.g. final diameter). It can be performed at a temperature of at most 80 ° C.
  • step E) makes it possible to obtain metal alloy strands (or electrical transport wires) of aluminum alloy, in particular of round or trapezoidal or Z-shaped cross section.
  • the diameter of the cross section can range from 0.2mm to 5.0mm.
  • the porous layer of alumina hydroxide surrounding said electrical transport wire and formed in step F) is preferably a layer that is in direct physical contact with said electrical transport wire. in aluminum alloy.
  • the electrical cable thus formed does not preferably comprise a layer interposed between the porous layer of alumina hydroxide and the aluminum alloy electrical transport wire.
  • pores of said porous alumina hydroxide layer are optionally arranged substantially evenly (or homogeneously) all along the outer surface of the porous alumina hydroxide layer, and they may all have substantially the same dimensions .
  • step vi) of the method according to the fourth subject of the invention or step F) of the process according to the fifth subject of the invention is carried out by anodization.
  • Anodizing is a surface treatment that can be formed by anodic oxidation, from the electrical transport wire from step iv) (or step D)) or step v) (or from step E)) if it exists, the porous layer of alumina hydroxide.
  • the anodizing will consume a portion of the electrical transport wire to form said porous layer of alumina hydroxide.
  • the porous layer of alumina hydroxide is formed from the surface of said electric transport wire to the core of said electric transport wire, in contrast to an electrolytic deposition.
  • Anodizing is conventionally based on the principle of electrolysis of water. It consists of immersing the electric transport wire in a bath anodizing, said electric transport wire being placed at the positive pole of a DC generator.
  • the anodizing bath is more particularly an acid bath, preferably a phosphoric acid bath or a sulfuric acid bath. These are respectively phosphoric anodizing or sulfuric anodizing.
  • the electrolytic parameters are imposed by a current density and a conductivity of the bath.
  • the current density is preferably set at 55 to 65 A / dm 2
  • the voltage is set at 20 to 21 V
  • the intensity is fixed at 280 to 350 A.
  • This current density makes it possible to ensure that a sufficient quantity of pores has been formed.
  • step a) and step b) can be carried out concomitantly.
  • the method according to the fourth object or fifth object of the invention may further comprise the following step, prior to the chemical conversion step vi) or F): c) Neutralizing said electric transport wire.
  • the method according to the fourth object or fifth object of the invention may comprise said three steps a), b) and c), step c) being performed after steps a) and b ).
  • the purpose of the degreasing step a) is to eliminate the various bodies and particles contained in the greases that may be present on the surface of the electric transport wire.
  • the degreasing step a) can be carried out by at least partially immersing the electric transport wire in a solution comprising at least one surfactant as a degreasing agent.
  • the stripping step b) serves to remove oxides that may be present on the surface of the electric transport wire.
  • a chemical etching may be used consisting of removing the oxides by dissolution, or even bursting of the oxide layer, without attacking the material of the underlying electrical transport wire.
  • the stripping step b) can be carried out by at least partially immersing the electric transport wire in a solution comprising a base as a stripping agent.
  • step a) and step b) are carried out concomitantly, a single solution comprising a degreasing agent and a etchant may be used to both etch and degrease the electrical transport wire.
  • the neutralization step c) makes it possible to condition the electric transport wire before the chemical conversion step vi) or F).
  • the step c) of neutralization consists in conditioning the electric transport wire by plunging it at least partially into a solution identical to the bath of anodizing provided in the chemical conversion step vi) or F), in order to put the surface of the electric transport wire at the same pH as the anodizing bath of the anodizing step vi) or F).
  • the neutralization step c) can be carried out by at least partially immersing the electric transport wire in a solution comprising an acid as neutralizing agent.
  • said aluminum electrical transport wire it is preferable first of all to strip and degrease said aluminum electrical transport wire, by immersing it in a soda solution and surfactants such as for example the GARDOCLEAN referenced solution marketed by the Company CHEMETALL (30-50 g / L of sodium hydroxide), especially at a temperature ranging from 40 to 60 ° C, for a period of about 30 seconds.
  • said electric transport wire can be immersed in a solution of sulfuric acid (20% by weight of sulfuric acid in distilled water) to perform the step c) of neutralization, preferably at room temperature (ie 25 ° C), for 10 seconds.
  • said electric transport wire Prior to the anodizing step vi) or F), said electric transport wire can then be smoothed to have a glossy appearance and then rinsed.
  • Brightening eliminates a surface roughness that impacts the gloss associated with the reflection of light.
  • the brightening can be carried out in a solution of acid assisted or not current. In the first case, it is an electrochemical brilliance.
  • the samples tested in the laboratory were made from the LUMIA range of the company COVENTYA.
  • the anodizing step vi) or F) can then be performed.
  • the electrical transmission wire made of aluminum alloy for example with a diameter of 3 mm, will be anodized by forming a porous layer of alumina hydroxide all around said electric transport wire, by sulfuric anodizing ( 20 to 30% by weight of sulfuric acid in distilled water) at a temperature of 30 ° C, or by phosphoric anodization (8 to 30% by weight of phosphoric acid in distilled water) at room temperature (ie 25 ° C), under the application of a current density between 55 and 65 A / dm 2 .
  • Said aluminum alloy electrical transport wire obtained is thus covered with a porous layer of alumina hydroxide.
  • the method according to the fourth object or fifth object of the invention further comprises after the chemical conversion step vi) or F), and in particular anodizing, the following step: vii) sealing the pores of said porous layer of alumina hydroxide.
  • This step vii) makes it possible to improve the compactness of the alumina hydroxide layer. Following this step vii), all the pores on the surface of the alumina hydroxide layer are capped.
  • Step vii) may for example be performed by performing hot hydration of said electrical transport wire, by dipping said electrical transport wire into boiling water or hot water.
  • the clogging may be carried out in water optionally with an additive, for example nickel salt at a temperature above 80 ° C, preferably between 90 and 95 ° C.
  • an additive for example nickel salt at a temperature above 80 ° C, preferably between 90 and 95 ° C.
  • said electric transport wire obtained after the chemical conversion step vi) or F) or said electric transport wire obtained after the sealing step vii), is rinsed with osmosis water.
  • the method of manufacturing the electric cable of the invention is an easy process to implement.
  • it provides an electrical cable having both good electrical properties (in terms of electrical capacitance and conductivity) and good mechanical properties (in terms of breaking strength and resistance to hot creep). .
  • step Y) makes it possible to obtain said electrical transport wires optionally covered with a layer of alumina hydroxide
  • step Z) is to position the electrical transport son around the reinforcing element, so as to form at least one layer of said electrical transport son around said reinforcing element.
  • the electric transport wires are twisted around said reinforcing element.
  • each electric transport wire has a cross section of complementary shape to the (s) strand (s) adjacent thereto, and being capable of conferring on said layer a substantially regular surface.
  • the electric cable according to the invention may have an apparent diameter (that is to say outside diameter) ranging from 10 to 100 mm.
  • the electric cable of the invention may be more particularly a high voltage electrical transmission cable, in particular of high voltage overhead line type of at least 225 kV and up to 800 kV (i.e. OHL cables). This type of cable is usually stretched between two pylons.
  • the figure 1 schematically represents a structure, in cross section, of a first variant of an electric cable according to the invention.
  • the figure 2 schematically represents a structure, in cross section, of a second variant of an electric cable according to the invention.
  • the figure 3 schematically represents a structure, in cross section, of a third variant of an electric cable according to the invention.
  • the figure 4 represents a transmission electron microscopy (TEM) view of the aluminum alloy electrical transport wire of the electrical cable of the invention.
  • TEM transmission electron microscopy
  • the figure 5 represents the curves of the electrical conductivity of the electric transport wire of the electric cable of the invention as a function of the heating time of step iv) of the fourth subject of the invention for different heating temperatures.
  • the figure 1 represents a first variant of a high voltage electric transmission electric cable of the OHL 100A type according to the invention, seen in cross section, comprising three layers of a 10A assembly of aluminum alloy wire strands 1A of the invention. These three layers surround an elongate central reinforcing element 20A.
  • the metal strands 1A constituting said layers have a cross section of round shape.
  • the figure 2 represents a second variant of a high-voltage electric transmission electric cable of the OHL 100B type according to the invention, seen in cross-section, comprising two layers of an assembly 10B of metal strands 1B of aluminum alloy of the invention. These two layers surround an elongated central reinforcing element 20B.
  • the metal strands 1B constituting said layers have a trapezoidal cross section.
  • the figure 3 represents a third variant of a high-voltage electric transmission electric cable of the OHL 100C type according to the invention, seen in cross-section, comprising two layers of a 10C assembly of metal strands 1C of aluminum alloy of the invention. These two layers surround an elongated central reinforcing element 20C.
  • the constituent metal strands 1C of said layers have a Z-shaped cross section (or of "S" shape according to the orientation of the Z).
  • the geometry of the strands in the shape of "Z” makes it possible to obtain a surface practically provided with no gaps that can generate accumulations of moisture and thus poles of corrosion.
  • the central element 20A, 20B, 20C which is an elongated reinforcement, represented in the Figures 1, 2 and 3 may be for example steel strands 2A, 2B, 2C or composite strands 2A, 2B, 2C of aluminum in an organic matrix.
  • the aluminum alloy of the electric transport wire included at most 0.8% by weight of unavoidable impurities.
  • the figure 4 shows a transmission electron microscopic view (TEM) of the aluminum alloy as prepared above bright field mode (English “BF: Bright Field”) ( figure 4a ) and in dark field mode (in English “ DF: Dark Field ”) ( figure 4b ).
  • TEM transmission electron microscopic view
  • TEM Transmission electron microscopy
  • the diameter of the zirconium precipitates in the alloy was determined by TEM. To do this, an alloy sample as prepared above was taken, polished to obtain an alloy thickness of about 100 microns, and electrochemically pierced to obtain a transparent sample thickness to electrons ranging from 50 to about 100 nm.
  • the zirconium precipitates obtained at the end of step iv) were coarse, in particular with a diameter greater than 100 nm.
  • Table 1 shows the tensile strength (in MPa) of several aluminum alloy electrical transport wires A1, A2, A3, A4 and A01, their electrical conductivity (in% IACS) and the loss of their properties mechanical after aging at 230 ° C for 1 hour (ie loss of breaking strength, in ⁇ UTS).
  • A1, A2, A3 and A4 were manufactured according to the process of the invention as described in the example above with different heating parameters according to the amount of zirconium they contained, and A01 was marketed under the reference AI1120 by Nexans. A01 is not part of the invention since it does not contain zirconium.
  • A1, A2, A3 and A4 were respectively obtained with the following heating parameters of step iv): 400 ° C / 300 hours, 400 ° C / 250 hours, 400 ° C / 220 hours and 400 ° C / 180 hours.
  • the aluminum alloy electrical transport wires manufactured according to the process according to the invention have good mechanical properties before and after aging and good electrical properties. .
  • the presence of zirconium in the aluminum alloy reduces the loss of mechanical properties after aging, while ensuring good electrical properties.
  • the figure 5 shows the electrical conductivity of the aluminum alloy electrical transport wire of the invention as a function of the heating time of step iv) of the process according to the invention when step iv) is carried out at a heating temperature 450 ° C (curve A), 400 ° C (curve B) and 350 ° C (curve C).
  • the alloy used in this example was prepared as in the examples described above and included 0.35% zirconium, 0.27% iron and 0.17% copper.
  • step iv) the temperature and time parameters used during said step iv) are interdependent and have a direct impact on the electrical conductivity of the alloy obtained.
  • time / temperature pairs allowing in step iv) to form sufficient zirconium precipitates and thus to obtain a conductivity of at least 57% IACS, the following time / temperature pairs are found: About 100 hours / 450 ° C, about 200 hours / 400 ° C, and about 340 hours / 350 ° C.
  • the aluminum alloy A5 of the electric transport wire included at most 0.8% by weight of unavoidable impurities.
  • the diameter of the zirconium precipitates was determined by the MET method as described in Example 1, on the alloy A5 as prepared at the end of the drawing step E) (ie before the stripping steps, degreasing, neutralization, anodizing and clogging).
  • the process according to the invention makes it possible to obtain a homogeneous dispersion of controlled microstructure of zirconium precipitates and in particular to obtain spherical zirconium precipitates with a diameter of from 1 to about 20 nm.
  • Table 2 below shows the temperature resistance (in ° C) of several aluminum alloy electrical transport wires A5, A6, A02 and A03, their electrical conductivity (in% IACS), their emissivity, their absorption, their diameter, the diameter and the cross-section of the corresponding cables (in mm), the intensity (in A) and the intensity gain (in%) of the cables respectively comprising the aluminum alloy electrical transport wires A03, A5 and A6 with respect to the cable comprising the aluminum alloy electrical transport wire A02.
  • A6 was manufactured according to the method according to the fourth subject of the invention and as described in the first example of the present application (with the heating parameters of step iv) following: 400 ° C / 180 hours).
  • A6 did not include a porous layer of alumina hydroxide.
  • A02 pure aluminum was marketed under the reference Al1350 by Nexans. A02 did not include a porous layer of alumina hydroxide.
  • A03 was made from A02, performing only steps a), b), c), F) and vii) described above in this example.
  • A03 thus included a porous layer of alumina hydroxide.
  • A02 and A03 do not form part of the invention since they do not include zirconium.
  • the maximum allowable intensity is particularly increased thanks to the invention, as shown by the calculations in Table 2 above. , made on round electric transport wires.

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EP19167496.9A 2012-10-17 2013-10-16 Draht zur beförderung von elektrischer energie aus aluminiumlegierung mit hoher elektrischer leitfähigkeit Active EP3540745B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1259882A FR2996951B1 (fr) 2012-10-17 2012-10-17 Fil de transport d'electricite en alliage d'aluminium
EP13789858.1A EP2909842B1 (de) 2012-10-17 2013-10-16 Elektrischer transportdraht aus einer aluminiumlegierung mit hoher elektrischer leitfähigkeit
PCT/FR2013/052475 WO2014064370A1 (fr) 2012-10-17 2013-10-16 Fil de transport électrique en alliage d'aluminium a conductivite electrique elevee

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EP13789858.1A Division-Into EP2909842B1 (de) 2012-10-17 2013-10-16 Elektrischer transportdraht aus einer aluminiumlegierung mit hoher elektrischer leitfähigkeit

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SE538433C2 (en) * 2014-08-05 2016-06-21 Mee Invest Scandinavia Ab Electrical wire
TW201621093A (zh) * 2014-08-07 2016-06-16 亨克爾股份有限及兩合公司 用於電陶瓷塗布金屬線圈或金屬線之連續塗布裝置
BR112018006233A2 (pt) 2015-10-14 2018-10-09 General Cable Technologies Corporation cabos e fios com elementos condutivos formados de ligas de alumínio-zircônio melhoradas
FR3060022A1 (fr) * 2016-12-13 2018-06-15 Nexans Materiau composite aluminium-alumine et son procede de preparation
US10465270B1 (en) * 2017-01-30 2019-11-05 General Cable Technologies Corporation Cables having conductive elements formed from aluminum alloys processed with high shear deformation processes
DE102017105411A1 (de) * 2017-03-14 2018-09-20 Viktor Alexandrovich Fokin Stahl-Aluminium-Leitzung und Verfahren zu ihrer Herstellung
BE1025729B1 (nl) * 2017-11-21 2019-06-24 Lamifil N.V. Stille geleider
RU2696794C1 (ru) * 2018-11-14 2019-08-06 Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") Способ получения катанки из термостойкого алюминиевого сплава
CN111292876B (zh) * 2020-02-21 2021-08-10 上海崇明特种电磁线厂 一种180级聚氨酯漆包铜圆线及其生产工艺

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US4402763A (en) * 1980-04-14 1983-09-06 Sumitomo Electric Industries, Ltd. High conductive heat-resistant aluminum alloy
EP0254698A1 (de) * 1986-06-20 1988-01-27 A/S Raufoss Ammunisjonsfabrikker Aluminiumlegierung, Verfahren zu ihrer Herstellung und Verwendung dieser Legierung
EP0787811A1 (de) 1996-01-30 1997-08-06 Sumitomo Electric Industries, Ltd. Hochfeste und wärmebeständige Aluminium-Legierung, leitfähiger Draht, Oberleitung und Verfahren zur Herstellung der Aluminium-Legierung
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AU2013336455B2 (en) 2017-06-08
WO2014064370A1 (fr) 2014-05-01
AU2013336455A1 (en) 2015-05-14
EP2909842A1 (de) 2015-08-26
EP2909842B1 (de) 2019-07-17
BR112015008375A2 (pt) 2017-07-04
FR2996951B1 (fr) 2015-11-27
ES2869297T3 (es) 2021-10-25
EP3540745B1 (de) 2021-03-03
US20150279518A1 (en) 2015-10-01
FR2996951A1 (fr) 2014-04-18
US10600535B2 (en) 2020-03-24

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