EP1647996B1 - Copper plated aluminum stranded cable and its fabrication method - Google Patents

Copper plated aluminum stranded cable and its fabrication method Download PDF

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Publication number
EP1647996B1
EP1647996B1 EP05356180A EP05356180A EP1647996B1 EP 1647996 B1 EP1647996 B1 EP 1647996B1 EP 05356180 A EP05356180 A EP 05356180A EP 05356180 A EP05356180 A EP 05356180A EP 1647996 B1 EP1647996 B1 EP 1647996B1
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Prior art keywords
nickel
wire
copper
wires
conductor
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German (de)
French (fr)
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EP1647996B2 (en
EP1647996A9 (en
EP1647996B9 (en
EP1647996A1 (en
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épouse Allaire Isabelle Michel
Louis Salvat
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Fsp - One
F S P One
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Fsp - One
F S P One
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Priority to PL05356180T priority Critical patent/PL1647996T3/en
Priority to DE602005005598.3T priority patent/DE602005005598T3/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023Alloys based on aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026Alloys based on copper
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0006Apparatus or processes specially adapted for manufacturing conductors or cables for reducing the size of conductors or cables
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/02Stranding-up
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00Power cables
    • H01B9/008Power cables for overhead application

Definitions

  • the present invention relates to conductors made of aluminum or copper-plated and nickel-plated aluminum alloy. It relates more particularly to electrical cables comprising at least one core conductor made of aluminum or aluminum alloy covered with a layer of copper itself covered with a layer of nickel.
  • the word “aluminum” broadly designates aluminum and its alloys.
  • the word “conductor” refers to an elongated electrically conductive body, the length of which is large relative to its cross-section, and which is generally in the form of a wire.
  • Aluminum-based electrical conductors are widely used in the transportation of electrical energy.
  • Aluminum-core electrical wires and cables may include a coating of insulating material, and single wires or strands may be assembled to form the conductive core of a cable.
  • aluminum conductors can be used in the raw state, that is to say without special treatment of the conductor surface.
  • Nickel plated aluminum wire strand electrical cables have already been used for example in aeronautical applications. There are more than one hundred kilometers of such cables in some current airliners.
  • aluminum has the advantage of reducing weight: for the same electrical resistance, an aluminum conductor weighs about half the weight of a copper conductor.
  • the document DE 196 33 615 A1 discloses the use of an aluminum wire having a copper coating on which is applied an outer layer of nickel.
  • the document FR 2,083,323 discloses an aircraft cable having copper coated aluminum wires itself coated with a nickel layer. Each conductor is isolated by one or more layers of plastic material.
  • the object of the invention is to propose a new structure of stranded cable for conduction of electric current having both a low electrical resistivity, good flexibility, a sufficiently large breaking load, good electrical contact properties, good anticorrosive properties for long-term use in aggressive conditions, and good capacities to absorb mechanical tightenings of electrical connection.
  • a problem is in particular to provide a protective nickel surface layer which has a satisfactory quality, both in sealing and in adhesion on the lower layer of the conductor, but which does not substantially disturb the other properties of the conductor such as electrical conductance , flexibility, weight, load at break.
  • the invention proposes an electric conductor of the aluminum cable type comprising at least one strand based on conducting wires having an aluminum core covered with an intermediate layer of copper, the intermediate layer of copper being itself covered with a surface layer of nickel.
  • the invention provides such a surface layer of nickel in a thickness of between about 1.3 ⁇ m and 3.0 ⁇ m, this superficial layer of nickel having sufficient continuity to withstand a polysulfide bath continuity test for at least 30 seconds without showing visible copper etching areas at 10x magnification.
  • the polysulfide bath continuity test is defined by the ASTM B298 standard established by the American Society for Testing Materials.
  • the thickness of the nickel surface layer is between about 2 ⁇ m and 3 ⁇ m.
  • it may be a cable comprising a strand of 37 son of 0.32 or 0.25 mm in diameter.
  • the cable may comprise a strand of 19 son of 0.30 or 0.25 or 0.20 mm in diameter.
  • nickel-plated copper alloy core wire surrounded by six nickel-plated copper aluminum wires of about 0.25 or 0.20 mm in diameter.
  • the cable can be stranded according to one or more concentric strands or concentric strands, or concentric unilay.
  • the strand or strands and / or the cable may then be covered with an insulating layer of polyimide, and an outer layer of polytetrafluoroethylene.
  • This method makes it possible in particular to avoid the appearance of oxides at the interfaces between the layers, in particular under the nickel layer, which oxides may then cause, during the drawing, discontinuities in the nickel surface layer, and thus reduce the protective and contact properties of this layer.
  • the neutral gas may advantageously be nitrogen.
  • the temperature can be about 250 ° C. for a period of at least about two hours.
  • Step d) is particularly critical.
  • the temperature of the electrolysis bath can be maintained between about 55 ° C and 65 ° C
  • the pH of the electrolysis bath can be maintained between about 2.3 and 3.0
  • the current density can be between 10 and 16 amperes per square decimetre (A / dm 2 )
  • the nickel concentration can be kept below about 140 grams per liter in the electrolysis bath. This makes it possible to more surely achieve a conductor that satisfies the optical polysulfide bath protection test mentioned above.
  • step d it is possible to predict that the temperature of the electrolysis bath is about 60 ° C., that the pH of the electrolysis bath is about 2.4, that the density current is about 15 to 16 amperes per square decimetre (A / dm 2 ).
  • the method may comprise a step prior to o ) calibrating the copper-plated aluminum roughing wire in size and hardness.
  • the copper-plated aluminum roughing wire may have, for example, a load at break less than or equal to 20 decaNewtons per square millimeter (daN / mm 2 ) approximately, and an elongation of between 2 and about 3%. In this way, it is still avoided, during drawing, the appearance of gaps or discontinuities in the surface layer of nickel.
  • the sulfamic acid bath may advantageously have a concentration of about 40 grams per liter.
  • the initial diameter of the copper-plated aluminum roughing wire may be between about 1.2 and 0.8 mm.
  • the nickel deposit is then carried out in a thickness of about 10 to 15 ⁇ m.
  • the final diameter of the coppered and nickel-plated aluminum wire is between 0.51 mm and 0.20 mm.
  • the stranding step g) is preferably carried out before the annealing step h).
  • the annealing step h) is preferably carried out before the stranding step g).
  • FIG. 1 illustrates the structure of a conductor wire 1 according to one embodiment of the invention.
  • a core 2 of aluminum covered with an intermediate layer 3 of copper, itself covered with a surface layer 4 of nickel.
  • the aluminum constituting the core 2 may be pure aluminum or an aluminum alloy.
  • a 99.5% aluminum alloy having at most 0.10% silicon and at most 0.40% iron may be preferred.
  • the wire may have a final total diameter D F of between about 0.51 mm and 0.20 mm. Other diameter values may however be used, depending on the characteristics sought.
  • the copper of the intermediate layer 3 may advantageously represent 15% by volume of the wire. This leads to a wire having the following characteristics: a density at 20 ° C of about 3.60 kilograms per cubic decimeter, a resistivity of 2.78 ⁇ 10 -8 ohms per meter, a conductivity of 60% to 64% IACS, typically 62% IACS, a breaking load of 138 Newtons per square millimeter and a minimum elongation of 6%.
  • the above son are stranded together by the usual techniques of forming cables.
  • a strand 5 of 19 wires, such as wire 1 in a concentric strand structure, the layers being of alternate directions.
  • a strand 6 of 19 wires, such as the wire 1 was made according to a strand structure unilay, the layers being of the same direction.
  • Smaller section structures may comprise seven-stranded strands 7 having a central strand 7a and six peripheral strands 7b-7g, as illustrated in FIG. figure 4 .
  • the central strand 7a may be made of nickel-plated copper alloy
  • the peripheral strands 7b-7g are made of copper-plated and nickel-plated aluminum like the wire 1 of the figure 1 .
  • Mixed strands 7 are thus produced in which the load at break is increased by this structure and the conductivity is reduced simultaneously, to the detriment of the weight.
  • the thickness E of the surface layer 4 of nickel must be greater than 1.3 ⁇ m, failing which it is found that the surface layer 4 of nickel is not sufficiently continuous to provide a effective protection of the intermediate layer 3 of copper. It is not advantageous to make a nickel layer whose thickness is greater than about 3 ⁇ m, since this adversely affects the other properties of the conductor such as electrical conductance, flexibility, load at break, and this reduces substantially the speed of manufacture of the driver.
  • the thickness E of the surface layer 4 of nickel will be between about 2 ⁇ m and 3 ⁇ m, and a good compromise is obtained with a surface layer 4 whose thickness E is equal to about 2.3 ⁇ m.
  • cables will be made with different numbers of wires and strands depending on the range.
  • a cable may comprise 7 strands of 10 or 15 wires each, the wires having a unit diameter of about 0.51 mm.
  • a cable is formed comprising seven strands of 19 son each, the son having a unit diameter of about 0.275 mm.
  • a cable is formed comprising a strand of 61 wires of about 0.32 mm in diameter.
  • the cable comprises a strand of 37 wires of about 0.32 or 0.25 mm.
  • the cable comprises a strand of 19 wires of about 0.30 or 0.25 or 0.20 mm, in a structure of Figures 2 or 3 .
  • the cables with smaller section will consist of a nickel-plated copper alloy core wire 7a, surrounded by six son 7b-7g of copper-plated and nickel-plated aluminum of 0.25 or 0.20 mm in diameter.
  • the strands can then be covered with an insulating layer of polyimide and an outer layer of polytetrafluoroethylene.
  • the roughing wire 8 was processed by an illustrated method on the figures 6 and 7 .
  • the roughing wire 8 consisted of an aluminum core 8a, covered with a copper surface layer 8b, the copper representing 15% by volume of the assembly.
  • FIG. 6 schematically illustrates the general structure of a device for manufacturing a wire according to a method of the invention.
  • the roughing wire 8 passes firstly into an ultrasound device 9, which performs a first degreasing.
  • the wire then passes into an anode degreasing tank 10, which performs anodic degreasing in a bath 11 which may for example contain sodium hydroxide and surfactants.
  • a bath 11 which may for example contain sodium hydroxide and surfactants.
  • the wire then passes into a rinsing device 12, producing a rinsing of the wire with demineralised water.
  • the yarn then passes into a tray 13 containing a sulfamic acid bath 14.
  • the sulfamic acid concentration may advantageously be about 40 grams per liter. This provides a surface treatment of the copper layer, facilitating the subsequent adhesion of nickel.
  • the wire then passes into an electrolytic nickel deposition device 15, which provides a suitable deposition of a surface layer of nickel.
  • the device will be described in more detail in relation to the figure 7 .
  • the wire then passes into a second rinsing device 16, which rinses the wire with demineralised water.
  • the wire then passes into a wire drawing device 17, in which a complete oil drawing is carried out to the final diameter, that is to say in the range of about 0.51 - 0.20 mm in diameter.
  • wire drawing takes place at a different speed than previous treatments. It is therefore necessary to provide an intermediate step during which the wire is packaged in a coil after the rinsing step in the rinsing device 16, and the wire is coated with a film of whole oil which protects it until to a subsequent drawing treatment.
  • the wire passes through an oven 18 associated with a source of neutral gas 19 such as nitrogen, in which the wire is annealed under nitrogen at about 240 ° C. for about two hours. This gives a wire 1 output, as illustrated on the figure 1 .
  • a source of neutral gas 19 such as nitrogen
  • the result obtained by this method may depend on the size and the structure of the blank wire 8.
  • a roughing wire having a breaking load of less than or equal to about 20 daN per mm 2 , and an elongation of between about 2 and 3%, with a constant dimension selected from the range of diameters between three and a half. times and five times the desired final diameter of the wire.
  • the device comprises an internal overflow tank 20, containing the electrolysis bath 21 which discharges, as indicated by the arrow 22, into an external tank 23 which contains the internal tank 20.
  • the liquid collected in the outer tank 23 is sent by pipes 24 in a storage tank 25, from which the liquid is returned to the inner tank 20 by a pump 26 and a pipe 27.
  • a nickel metal reserve 28 is housed in the inner tank 20, inside the electrolysis bath 21.
  • the blank wire 8 is moved and guided through the inner tank 20, in several passages, and comes out after depositing a layer of nickel on its surface.
  • the nickel reserve 28 is electrically connected to the positive pole of an electric generator 29 whose negative pole is connected to the wire 8.
  • the electrolysis bath 21 contains nickel sulphamate in aqueous solution. Good results require permanent control of the concentration of the electrolysis bath 21. This is done by connecting the storage tank 25 to a water supply 30, to a purge line 31, to a source of sulfamic acid 32 The pH of the electrolysis bath 21 is controlled by a pH sensor 33 acting on a regulator which controls the operation of the corresponding valves to withdraw a quantity of liquid from the electrolysis bath 21 via the purge pipe 31, to add water by the water supply 30, and to add sulfamic acid by the sulfamic acid source 32.
  • the pH of the electrolysis bath was advantageously maintained between about 2.3 and 3.0, preferably close to 2.4.
  • the temperature of the electrolysis bath 21 was also regulated, by means of a temperature sensor 34 and heating means 35, so that the electrolysis bath was for example at a temperature of approximately 60 ° C.
  • the nickel sulfamate concentration in the electrolysis bath 21 was kept low, for example less than 140 grams per liter of nickel. Otherwise, the superficial layer of nickel would have been too hard, and would have poorly supported the subsequent drawing.
  • the electric generator 29 is adapted to regulate the electrolysis current density.
  • the electrolysis current density has advantageously been maintained within a range of values of between 10 and 16 A / dm 2 ; preferably between 15 and 16 A / dm 2 .
  • a difficulty has been in determining the good, acceptable or poor quality of the nickel coating produced by the process.
  • a polysulfide bath test according to ASTM B298 has been successfully used, with a specific optical examination, which provides an overall result of quality control of the coating, highlighting any gaps or microcracks in the nickel coating.
  • a sample of yarn 1 is first defatted by immersion in a suitable organic solvent such as benzene, trichlorethylene or a mixture of ether and alcohol for at least 3 minutes. It is then removed and dried by wiping with a soft, clean cloth. The wire sample 1 should be held in the tissue until the test is complete, and should not be touched by hand.
  • a suitable organic solvent such as benzene, trichlorethylene or a mixture of ether and alcohol
  • a concentrated solution of polysulfide is prepared by dissolving sodium sulphide crystals in deionized water until saturation at about 21 ° C and adding enough sulfur flower to obtain complete saturation, which can be controlled by the presence of an excess of sulfur when the solution has sat for at least 24 hours.
  • the test solution was made by diluting a portion of the concentrated solution with deionized water to a specific gravity of 1.142 at 15.6 ° C.
  • the sodium polysulfide test solution should have sufficient strength to fully blacken a section of copper wire within 5 seconds. The test solution will not be considered exhausted as long as it can blacken a piece of copper.
  • a solution of hydrochloric acid is prepared simultaneously by diluting the commercial hydrochloric acid with distilled water to a density of 1.088 measured at 15.6 ° C. A portion of the acid solution hydrochloric acid with a volume of 180 milliliters will be considered exhausted if it can not suppress in 45 seconds the silver discoloration due to immersion in the polysulfide.
  • the sample of yarn 1 having a length of at least 114 mm was immersed for 30 seconds in a polysulfide bath 37 containing the above-described solution of sodium polysulfide maintained at a temperature of between 15.degree. 6 ° C and 21 ° C.
  • wire sample 1 is rinsed with deionized water 38, and dried with a soft, clean cloth.
  • the sample of yarn 1 was immediately immersed for 15 seconds in a hydrochloric acid solution described above, then washed thoroughly with deionized water and dried with a clean, soft cloth.
  • the sample of wire 1 is examined, for example using a binocular loupe 41 in magnification x 10. No attention will be paid to the end zones of the wire sample. 1, that is, the areas within 12.7 mm of each end.
  • a sample of yarn 1 taken from a thread of good quality, illustrated in the photograph of the figure 9 does not show a visible mark of attack of the lower layer of copper by the polysulfide bath. It is estimated that an attack mark is visible when it has an area of at least 0.02 mm 2 in magnification x 10 (corresponding to a spot of 0.01 mm side at magnification 1).
  • the electrical conductors according to the present invention may advantageously be used in all types of applications requiring a good compromise between conductivity, load at break, flexibility, weight, and long-term protection, especially in the aeronautics, in the automobile, and generally in all types of mobiles.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Non-Insulated Conductors (AREA)
  • Insulated Conductors (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Conductive Materials (AREA)
  • Processes Specially Adapted For Manufacturing Cables (AREA)
  • Wire Processing (AREA)
  • Ropes Or Cables (AREA)

Abstract

An aluminium cable electric conductor, incorporating at least one strand with a base of conducting wires (1) with a core (2) of aluminium coated with an intermediate layer (3) of copper which is coated with a superficial layer (4) of nickel, has the following characteristics : (A) the superficial layer of nickel has a thickness (E) of between 1.3 mu m and 3 mu m; (B) the superficial layer of nickel has sufficient continuity to resist a continuity test in a bath of polysulphur for at least 30 seconds without the appearance of zones of attack of the copper, visible at an enlargement of times ten. An independent claim is also included for the production of this conductor.

Description

La présente invention concerne les conducteurs en aluminium ou en alliage d'aluminium cuivré et nickelé. Elle concerne plus spécialement les câbles électriques comprenant au moins un conducteur à âme en aluminium ou en alliage d'aluminium recouverte d'une couche de cuivre elle-même recouverte d'une couche de nickel.The present invention relates to conductors made of aluminum or copper-plated and nickel-plated aluminum alloy. It relates more particularly to electrical cables comprising at least one core conductor made of aluminum or aluminum alloy covered with a layer of copper itself covered with a layer of nickel.

Dans la description et les revendications qui suivent, le mot "aluminium" désigne au sens large l'aluminium et ses alliages. Le mot "conducteur" désigne un corps électriquement conducteur de forme allongée, dont la longueur est grande par rapport à sa section transversale, et qui est généralement sous forme d'un fil.In the description and the claims which follow, the word "aluminum" broadly designates aluminum and its alloys. The word "conductor" refers to an elongated electrically conductive body, the length of which is large relative to its cross-section, and which is generally in the form of a wire.

Les conducteurs électriques à base d'aluminium sont largement utilisés dans le transport de l'énergie électrique. Des fils et câbles électriques à âme en aluminium peuvent comprendre un revêtement en matériau isolant, et des fils ou brins unitaires peuvent être assemblés pour former l'âme conductrice d'un câble.Aluminum-based electrical conductors are widely used in the transportation of electrical energy. Aluminum-core electrical wires and cables may include a coating of insulating material, and single wires or strands may be assembled to form the conductive core of a cable.

Dans le transport et la distribution d'énergie électrique, des conducteurs en aluminium peuvent être utilisés à l'état brut, c'est-à-dire sans traitement particulier de la surface du conducteur. Toutefois, on a déjà prévu de revêtir le conducteur en aluminium d'une couche de nickel, de manière à améliorer les propriétés de contact électrique.In the transport and distribution of electrical energy, aluminum conductors can be used in the raw state, that is to say without special treatment of the conductor surface. However, it has already been planned to coat the aluminum conductor with a layer of nickel, so as to improve the electrical contact properties.

Des câbles électriques à torons de fils en aluminium revêtus de nickel ont déjà été utilisés par exemple dans les applications de l'aéronautique. On trouve plus de cent kilomètres de tels câbles dans certains avions de ligne actuels.Nickel plated aluminum wire strand electrical cables have already been used for example in aeronautical applications. There are more than one hundred kilometers of such cables in some current airliners.

Par rapport à la solution traditionnelle de câbles à âme en cuivre, l'aluminium présente l'avantage d'une réduction du poids : pour la même résistance électrique, un conducteur en aluminium pèse environ la moitié du poids d'un conducteur en cuivre.Compared to the traditional copper core cable solution, aluminum has the advantage of reducing weight: for the same electrical resistance, an aluminum conductor weighs about half the weight of a copper conductor.

Malgré le gain de poids, les applications des conducteurs en aluminium dans l'industrie aéronautique sont toutefois restées minoritaires, notamment à cause d'une plus faible conductivité, d'une plus faible charge à la rupture, de moins bonnes performances de flexibilité, de la présence d'oxydes non conducteurs en superficie du conducteur, et des difficultés d'industrialisation.Despite the weight gain, the applications of aluminum conductors in the aerospace industry have, however, remained in the minority, mainly because of lower conductivity, lower load at break, poorer performance in terms of flexibility, the presence of non-conductive oxides in the driver's area, and industrialization difficulties.

Ainsi, le document DE 196 33 615 A1 décrit l'utilisation d'un fil d'aluminium ayant un revêtement de cuivre sur lequel est appliquée une couche externe de nickel.Thus, the document DE 196 33 615 A1 discloses the use of an aluminum wire having a copper coating on which is applied an outer layer of nickel.

Le document FR 2 083 323 décrit un câble pour aéronef, ayant des fils d'aluminium à revêtement de cuivre lui-même recouvert d'une couche de nickel. Chaque conducteur est isolé par une ou plusieurs couches de matière plastique.The document FR 2,083,323 discloses an aircraft cable having copper coated aluminum wires itself coated with a nickel layer. Each conductor is isolated by one or more layers of plastic material.

Les documents ci-dessus ne précisent pas l'épaisseur et la résistance de la couche de nickel, ni l'intérêt et les moyens pour garantir à la fois une conductivité suffisante, une charge à la rupture suffisante, et une flexibilité suffisante pour une utilisation en conditions difficiles et atmosphère agressive.The above documents do not specify the thickness and strength of the nickel layer, nor the interest and means to ensure both sufficient conductivity, sufficient breaking load, and sufficient flexibility for use. in difficult conditions and aggressive atmosphere.

Le document US 3,915,667 A enseigne de revêtir un conducteur en aluminium avec un revêtement interne d'étain ou de zinc, puis avec une couche à base de cuivre, puis avec un revêtement de nickel, puis enfin avec une couche externe d'étain ou d'argent. La couche intermédiaire de nickel a une épaisseur comprise entre environ 2,5 µm et 12,7 µm. Il n'est pas précisé l'intérêt d'une couche superficielle résistante de nickel, ni les moyens pour la réaliser.The document US 3,915,667 A teaches to coat an aluminum conductor with an inner coating of tin or zinc, then with a copper-based layer, then with a nickel coating, and finally with an outer layer of tin or silver. The nickel interlayer has a thickness of between about 2.5 μm and 12.7 μm. It is not specified the interest of a resistant surface layer of nickel, nor the means to achieve it.

Dans le domaine des câbles de petit diamètre, il y a un besoin d'améliorer le compromis entre la conductivité du câble, sa charge à la rupture, et sa flexibilité, de façon à satisfaire les conditions d'usage des câbles qui doivent être passés dans des gaines non linéaires et relativement longues, sans risque de détérioration ou de blocage. En outre, il y a un besoin de protection à long terme de tels câbles contre l'apparition d'oxydes non conducteurs en surface, dans des conditions d'usage sévères, par exemple des écarts de température importants et répétés, des atmosphères agressives. Egalement, il y a un besoin d'assurer une bonne connexion électrique des conducteurs sans détériorer leur structure par serrage mécanique.In the field of small diameter cables, there is a need to improve the compromise between the conductivity of the cable, its load at break, and its flexibility, so as to satisfy the conditions of use of the cables that must be passed in nonlinear sheaths and relatively long, without risk of deterioration or blockage. In addition, there is a need for long-term protection of such cables against the appearance of non-conductive oxides on the surface, under severe conditions of use, for example large and repeated temperature differences, aggressive atmospheres. Also, there is a need to ensure a good electrical connection of the conductors without damaging their structure by mechanical clamping.

Le but de l'invention est de proposer une nouvelle structure de câble multibrins pour conduction de courant électrique présentant à la fois une faible résistivité électrique, une bonne flexibilité, une charge à la rupture suffisamment grande, de bonnes propriétés de contact électrique, de bonnes propriétés anticorrosion pour un usage à long terme en conditions agressives, et de bonnes capacités pour absorber les serrages mécaniques de connexion électrique.The object of the invention is to propose a new structure of stranded cable for conduction of electric current having both a low electrical resistivity, good flexibility, a sufficiently large breaking load, good electrical contact properties, good anticorrosive properties for long-term use in aggressive conditions, and good capacities to absorb mechanical tightenings of electrical connection.

Un problème est en particulier de réaliser une couche superficielle protectrice de nickel qui présente une qualité satisfaisante, à la fois en étanchéité et en adhérence sur la couche inférieure du conducteur, mais qui ne perturbe pas sensiblement les autres propriétés du conducteur telles que la conductance électrique, la flexibilité, le poids, la charge à la rupture.A problem is in particular to provide a protective nickel surface layer which has a satisfactory quality, both in sealing and in adhesion on the lower layer of the conductor, but which does not substantially disturb the other properties of the conductor such as electrical conductance , flexibility, weight, load at break.

Pour cela, l'invention propose un conducteur électrique de type câble aluminium comprenant au moins un toron à base de fils conducteurs ayant une âme en aluminium recouverte d'une couche intermédiaire de cuivre, la couche intermédiaire de cuivre étant elle-même recouverte d'une couche superficielle de nickel. L'invention prévoit une telle couche superficielle de nickel selon une épaisseur comprise entre 1,3 µm et 3,0 µm environ, cette couche superficielle de nickel présentant une continuité suffisante pour résister à un test de continuité par bain de polysulfure pendant au moins 30 secondes sans laisser apparaître de zones d'attaque du cuivre visibles selon un grossissement x 10.For this purpose, the invention proposes an electric conductor of the aluminum cable type comprising at least one strand based on conducting wires having an aluminum core covered with an intermediate layer of copper, the intermediate layer of copper being itself covered with a surface layer of nickel. The invention provides such a surface layer of nickel in a thickness of between about 1.3 μm and 3.0 μm, this superficial layer of nickel having sufficient continuity to withstand a polysulfide bath continuity test for at least 30 seconds without showing visible copper etching areas at 10x magnification.

Le test de continuité par bain de polysulfure est défini par la norme ASTM B298 établie par l'organisme American Society for Testing and Materials.The polysulfide bath continuity test is defined by the ASTM B298 standard established by the American Society for Testing Materials.

Le détail de ce test de continuité par bain de polysulfure est donné dans la description qui suit.The details of this continuity test by polysulphide bath is given in the description which follows.

De préférence, l'épaisseur de la couche superficielle de nickel est comprise entre 2 µm et 3 µm environ.Preferably, the thickness of the nickel surface layer is between about 2 μm and 3 μm.

De bons résultats peuvent être obtenus avec une couche superficielle de nickel dont l'épaisseur est de 2,3 µm environ.Good results can be obtained with a surface layer of nickel whose thickness is about 2.3 microns.

On pourra ainsi constituer un câble de sept torons de 10 ou 15 fils chacun, les fils ayant un diamètre unitaire de 0,51 mm environ.It will thus be possible to form a cable of seven strands of 10 or 15 wires each, the wires having a unit diameter of about 0.51 mm.

Selon une autre application, on pourra constituer un câble comprenant sept torons de 19 fils chacun, les fils ayant un diamètre unitaire de 0,275 mm environ.According to another application, it will be possible to constitute a cable comprising seven strands of 19 wires each, the wires having a unit diameter of about 0.275 mm.

Selon une autre application, on pourra constituer un câble comprenant un toron de 61 fils ayant chacun un diamètre de 0,32 mm environ.According to another application, it will be possible to form a cable comprising a strand of 61 wires each having a diameter of about 0.32 mm.

Selon une autre application, on pourra constituer un câble comprenant un toron de 37 fils de 0,32 ou 0,25 mm de diamètre environ.According to another application, it may be a cable comprising a strand of 37 son of 0.32 or 0.25 mm in diameter.

Selon une autre application, le câble pourra comporter un toron de 19 fils de 0,30 ou 0,25 ou 0,20 mm de diamètre environ.According to another application, the cable may comprise a strand of 19 son of 0.30 or 0.25 or 0.20 mm in diameter.

Pour augmenter la résistance mécanique du câble, dans les petits diamètres, on pourra avantageusement prévoir un fil central d'alliage de cuivre nickelé, entouré de six fils d'aluminium cuivré nickelé de 0,25 ou 0,20 mm de diamètre environ.To increase the mechanical resistance of the cable, in small diameters, it is advantageous to provide a nickel-plated copper alloy core wire, surrounded by six nickel-plated copper aluminum wires of about 0.25 or 0.20 mm in diameter.

Le câble peut être toronné selon un ou plusieurs fils ou torons concentriques vrais, ou concentriques unilay. Le ou les torons et/ou le câble peuvent ensuite être recouverts d'une couche isolante en polyimide, et d'une couche externe en polytétrafluoroéthylène.The cable can be stranded according to one or more concentric strands or concentric strands, or concentric unilay. The strand or strands and / or the cable may then be covered with an insulating layer of polyimide, and an outer layer of polytetrafluoroethylene.

Une difficulté est de réaliser industriellement, à faible coût, la couche de nickel continue, adhérente et étanche. Pour cela, l'invention propose une procédure de fabrication de fil cuivré et nickelé comportant les étapes suivantes :

  1. a) prévoir un fil d'ébauche à âme en aluminium recouverte d'une couche de cuivre représentant 10 % à 20 % en volume, de diamètre compris entre 2 fois et 5 fois le diamètre final désiré du fil,
  2. b) dégraisser le fil d'ébauche,
  3. c) procéder à un mordançage du fil d'ébauche à l'acide sulfamique,
  4. d) déposer sur le fil d'ébauche une couche de nickel par électrolyse dans un bain d'électrolyse au sulfamate de nickel aqueux,
  5. e) rincer le fil obtenu à l'eau déminéralisée,
  6. f) tréfiler le fil obtenu en huile entière jusqu'au diamètre final,
  7. g) toronner plusieurs fils ainsi obtenus en faisceaux de fils,
  8. h) procéder à un recuit sous gaz neutre.
A difficulty is to achieve industrially, at low cost, the continuous layer of nickel, adherent and sealed. For this, the invention proposes a procedure for manufacturing copper-plated and nickel-plated wire comprising the following steps:
  1. a) providing an aluminum core preform coated with a copper layer of 10% to 20% by volume, with a diameter of between 2 and 5 times the desired final diameter of the wire,
  2. b) degrease the roughing wire,
  3. c) etching the sulfamic acid strand,
  4. d) depositing on the wire a nickel layer by electrolysis in an aqueous nickel sulfamate electrolysis bath,
  5. e) rinse the wire obtained with demineralized water,
  6. f) drawing the obtained wire into whole oil up to the final diameter,
  7. g) stranding several yarns thus obtained in bundles of yarns,
  8. h) annealing under a neutral gas.

Ce procédé permet notamment d'éviter l'apparition d'oxydes aux interfaces entre les couches, notamment sous la couche de nickel, oxydes susceptibles ensuite de provoquer, pendant le tréfilage, des discontinuités dans la couche superficielle de nickel, et de réduire ainsi les propriétés protectrices et de contact de cette couche.This method makes it possible in particular to avoid the appearance of oxides at the interfaces between the layers, in particular under the nickel layer, which oxides may then cause, during the drawing, discontinuities in the nickel surface layer, and thus reduce the protective and contact properties of this layer.

Lors de l'étape h) de recuit sous gaz neutre, le gaz neutre peut avantageusement être l'azote.During step h) of annealing under neutral gas, the neutral gas may advantageously be nitrogen.

Et en complément, lors de l'étape h) de recuit sous gaz neutre, la température peut être d'environ 250°C pendant une durée d'au moins environ deux heures.And in addition, during the neutral gas annealing step h), the temperature can be about 250 ° C. for a period of at least about two hours.

L'étape d) est particulièrement critique. Pendant cette étape, la température du bain d'électrolyse peut être maintenue entre 55°C et 65°C environ, le pH du bain d'électrolyse peut être maintenu entre 2,3 et 3,0 environ, la densité de courant peut être comprise entre 10 et 16 Ampères par décimètre carré (A/dm2), et la concentration de nickel peut être maintenue inférieure à 140 grammes par litre environ dans le bain d'électrolyse. Cela permet de réaliser de manière plus certaine un conducteur qui satisfait le test de protection au bain de polysulfure à examen optique mentionné ci-dessus.Step d) is particularly critical. During this step, the temperature of the electrolysis bath can be maintained between about 55 ° C and 65 ° C, the pH of the electrolysis bath can be maintained between about 2.3 and 3.0, the current density can be between 10 and 16 amperes per square decimetre (A / dm 2 ), and the nickel concentration can be kept below about 140 grams per liter in the electrolysis bath. This makes it possible to more surely achieve a conductor that satisfies the optical polysulfide bath protection test mentioned above.

Pour optimiser le processus, pendant l'étape d), on peut prévoir que la température du bain d'électrolyse est d'environ 60°C, que le pH du bain d'électrolyse est d'environ 2,4, que la densité de courant est d'environ 15 à 16 Ampères par décimètre carré (A/dm2).To optimize the process, during step d), it is possible to predict that the temperature of the electrolysis bath is about 60 ° C., that the pH of the electrolysis bath is about 2.4, that the density current is about 15 to 16 amperes per square decimetre (A / dm 2 ).

De préférence, le procédé peut comprendre une étape préalable ao) de calibrage du fil d'ébauche en aluminium cuivré, en dimension et en dureté.Preferably, the method may comprise a step prior to o ) calibrating the copper-plated aluminum roughing wire in size and hardness.

Après une telle étape de calibrage ao), le fil d'ébauche en aluminium cuivré peut présenter par exemple une charge à la rupture inférieure ou égale à 20 décaNewtons par millimètre carré (daN/mm2) environ, et un allongement compris entre 2 et 3 % environ. De la sorte, on évite encore, pendant le tréfilage, l'apparition de lacunes ou discontinuités dans la couche superficielle de nickel.After such a calibration step a o ), the copper-plated aluminum roughing wire may have, for example, a load at break less than or equal to 20 decaNewtons per square millimeter (daN / mm 2 ) approximately, and an elongation of between 2 and about 3%. In this way, it is still avoided, during drawing, the appearance of gaps or discontinuities in the surface layer of nickel.

Pendant l'étape c), le bain d'acide sulfamique peut avantageusement avoir une concentration d'environ 40 grammes par litre.During step c), the sulfamic acid bath may advantageously have a concentration of about 40 grams per liter.

Le diamètre initial du fil d'ébauche en aluminium cuivré peut être compris entre 1,2 et 0,8 mm environ. Le dépôt de nickel s'effectue alors selon une épaisseur de 10 à 15 µm environ. Et le diamètre final du fil en aluminium cuivré et nickelé est compris entre 0,51 mm et 0,20 mm environ.The initial diameter of the copper-plated aluminum roughing wire may be between about 1.2 and 0.8 mm. The nickel deposit is then carried out in a thickness of about 10 to 15 μm. And the final diameter of the coppered and nickel-plated aluminum wire is between 0.51 mm and 0.20 mm.

De préférence, l'étape b) de dégraissage du fil peut comprendre les étapes :

  1. b1) dégraisser le fil d'ébauche par ultrasons,
  2. b2) procéder à un dégraissage anodique du fil d'ébauche dans un bain contenant de la soude et des tensioactifs,
  3. b3) rincer le fil d'ébauche à l'eau déminéralisée.
Preferably, step b) of degreasing the wire may comprise the steps:
  1. b1) degreasing the roughing wire by ultrasound,
  2. b2) anodic degreasing of the blank wire in a bath containing sodium hydroxide and surfactants,
  3. b3) rinse the roughing wire with deionized water.

Pour les fils de diamètre inférieur ou égal à 0,25 mm, on réalise de préférence l'étape g) de toronnage avant l'étape h) de recuit. Par contre, pour les fils de diamètre supérieur, on réalise de préférence l'étape h) de recuit avant l'étape g) de toronnage.For wires of diameter less than or equal to 0.25 mm, the stranding step g) is preferably carried out before the annealing step h). On the other hand, for the wires of greater diameter, the annealing step h) is preferably carried out before the stranding step g).

D'autres objets, caractéristiques et avantages de la présente invention ressortiront de la description suivante de modes de réalisation particuliers, faite en relation avec les figures jointes, parmi lesquelles :

  • la figure 1 est une vue en perspective en coupe transversale d'un fil à âme en aluminium selon un mode de réalisation de la présente invention ;
  • la figure 2 est une coupe transversale d'un toron à 19 fils de type concentrique vrai ;
  • la figure 3 est une coupe transversale d'un toron à 19 fils de type concentrique unilay ;
  • la figure 4 est une coupe transversale d'un toron à 7 fils ;
  • la figure 5 est une vue en perspective en coupe transversale d'une ébauche de fil en aluminium cuivré à partir duquel on réalise le fil selon l'invention ;
  • la figure 6 est une vue schématique générale d'un dispositif pour la fabrication du fil de la figure 1 selon un mode de réalisation de l'invention ;
  • la figure 7 est une vue schématique du poste de nickelage dans l'installation de la figure 6 ;
  • la figure 8 illustre les deux étapes d'un processus de test permettant de contrôler la qualité du fil obtenu ;
  • la figure 9 est une vue d'un fil de bonne qualité ayant subi le test ; et
  • la figure 10 est une vue d'un fil de mauvaise qualité ayant subi le test.
Other objects, features and advantages of the present invention will become apparent from the following description of particular embodiments, with reference to the accompanying figures, in which:
  • the figure 1 is a cross-sectional perspective view of an aluminum core wire according to an embodiment of the present invention;
  • the figure 2 is a cross-section of a 19-wire strand of true concentric type;
  • the figure 3 is a cross-section of a 19-wire strand of concentric type unilay;
  • the figure 4 is a cross section of a 7-wire strand;
  • the figure 5 is a cross-sectional perspective view of a blank of copper-plated aluminum wire from which the yarn according to the invention is made;
  • the figure 6 is a general schematic view of a device for the manufacture of the wire of the figure 1 according to one embodiment of the invention;
  • the figure 7 is a schematic view of the nickel plating station in the installation of the figure 6 ;
  • the figure 8 illustrates the two steps of a test process to control the quality of the wire obtained;
  • the figure 9 is a view of a good quality thread that has been tested; and
  • the figure 10 is a view of a poor quality wire that has been tested.

On considère tout d'abord la figure 1, qui illustre la structure d'un fil 1 conducteur selon un mode de réalisation de l'invention. On distingue une âme 2 en aluminium, recouverte d'une couche intermédiaire 3 en cuivre, elle-même recouverte d'une couche superficielle 4 en nickel.We first consider the figure 1 , which illustrates the structure of a conductor wire 1 according to one embodiment of the invention. There is a core 2 of aluminum, covered with an intermediate layer 3 of copper, itself covered with a surface layer 4 of nickel.

L'aluminium constituant l'âme 2 peut être de l'aluminium pur ou un alliage d'aluminium. On pourra préférer un alliage à 99,5 % d'aluminium ayant au plus 0,10 % de silicium et au plus 0,40 % de fer.The aluminum constituting the core 2 may be pure aluminum or an aluminum alloy. A 99.5% aluminum alloy having at most 0.10% silicon and at most 0.40% iron may be preferred.

Dans les applications pour l'industrie aéronautique ou l'industrie automobile, le fil peut avoir un diamètre total final DF compris entre environ 0,51 mm et 0,20 mm. D'autres valeurs de diamètre pourront toutefois être utilisées, en fonction des caractéristiques recherchées.In applications for the aviation industry or the automotive industry, the wire may have a final total diameter D F of between about 0.51 mm and 0.20 mm. Other diameter values may however be used, depending on the characteristics sought.

Le cuivre de la couche intermédiaire 3 peut représenter avantageusement 15 % en volume du fil. Cela conduit à un fil ayant les caractéristiques suivantes : une densité à 20°C d'environ 3,60 kilogrammes par décimètre cube, une résistivité de 2,78 10-8 ohms par mètre, une conductivité de 60 % à 64% IACS, généralement de 62 % IACS, une charge à la rupture de 138 Newtons par millimètre carré et un allongement minimum de 6 %.The copper of the intermediate layer 3 may advantageously represent 15% by volume of the wire. This leads to a wire having the following characteristics: a density at 20 ° C of about 3.60 kilograms per cubic decimeter, a resistivity of 2.78 × 10 -8 ohms per meter, a conductivity of 60% to 64% IACS, typically 62% IACS, a breaking load of 138 Newtons per square millimeter and a minimum elongation of 6%.

Pour réaliser à la fois une flexibilité satisfaisante, et une conductivité suffisante grâce à une grande section transversale, les fils ci-dessus sont assemblés en toron par les techniques habituelles de formation de câbles.To achieve both satisfactory flexibility, and sufficient conductivity through a large cross section, the above son are stranded together by the usual techniques of forming cables.

Par exemple, comme illustré sur la figure 2, on peut réaliser un toron 5 de 19 fils tels que le fil 1, selon une structure de toron concentrique, les couches étant de sens alternés. Selon un autre exemple, sur la figure 3, on a réalisé un toron 6 de 19 fils tels que le fil 1, selon une structure de toron unilay, les couches étant de même sens.For example, as shown on the figure 2 it is possible to produce a strand 5 of 19 wires, such as wire 1, in a concentric strand structure, the layers being of alternate directions. In another example, on the figure 3 a strand 6 of 19 wires, such as the wire 1, was made according to a strand structure unilay, the layers being of the same direction.

Par contre, on évitera une structure de type toron unilay hexagonal, qui peut rendre plus difficile ou défectueuse la connexion électrique en bout de câble.On the other hand, one will avoid a structure of the type strand unilay hexagonal, which can make more difficult or defective the electrical connection at the end of cable.

Des structures de section plus petite peuvent comprendre des torons 7 à sept brins, ayant un brin central 7a et six brins périphériques 7b-7g, comme illustré sur la figure 4. Le brin central 7a peut être en alliage de cuivre nickelé, tandis que les brins périphériques 7b-7g sont en aluminium cuivré et nickelé comme le fil 1 de la figure 1. On réalise ainsi des torons mixtes 7, dans lesquels on augmente par cette structure la charge à la rupture et on réduit simultanément la conductivité, au détriment du poids.Smaller section structures may comprise seven-stranded strands 7 having a central strand 7a and six peripheral strands 7b-7g, as illustrated in FIG. figure 4 . The central strand 7a may be made of nickel-plated copper alloy, whereas the peripheral strands 7b-7g are made of copper-plated and nickel-plated aluminum like the wire 1 of the figure 1 . Mixed strands 7 are thus produced in which the load at break is increased by this structure and the conductivity is reduced simultaneously, to the detriment of the weight.

Dans le fil de la figure 1, l'épaisseur E de la couche superficielle 4 de nickel doit être supérieure à 1,3 µm, à défaut de quoi on constate que la couche superficielle 4 de nickel n'est pas suffisamment continue pour assurer une protection efficace de la couche intermédiaire 3 de cuivre. Il n'est pas avantageux de réaliser une couche de nickel dont l'épaisseur est supérieure à 3 µm environ, car cela affecte défavorablement les autres propriétés du conducteur telles que la conductance électrique, la flexibilité, la charge à la rupture, et cela réduit sensiblement la vitesse de fabrication du conducteur. De préférence, l'épaisseur E de la couche superficielle 4 de nickel sera comprise entre 2 µm et 3 µm environ, et un bon compromis est obtenu avec une couche superficielle 4 dont l'épaisseur E est égale à 2,3 µm environ.In the wire of the figure 1 , the thickness E of the surface layer 4 of nickel must be greater than 1.3 μm, failing which it is found that the surface layer 4 of nickel is not sufficiently continuous to provide a effective protection of the intermediate layer 3 of copper. It is not advantageous to make a nickel layer whose thickness is greater than about 3 μm, since this adversely affects the other properties of the conductor such as electrical conductance, flexibility, load at break, and this reduces substantially the speed of manufacture of the driver. Preferably, the thickness E of the surface layer 4 of nickel will be between about 2 μm and 3 μm, and a good compromise is obtained with a surface layer 4 whose thickness E is equal to about 2.3 μm.

En pratique, on constituera des câbles ayant des nombres de fils et de torons différents en fonction de la gamme.In practice, cables will be made with different numbers of wires and strands depending on the range.

Selon un premier exemple, un câble peut comprendre 7 torons de 10 ou 15 fils chacun, les fils ayant un diamètre unitaire de 0,51 mm environ.According to a first example, a cable may comprise 7 strands of 10 or 15 wires each, the wires having a unit diameter of about 0.51 mm.

Selon un second exemple, on constitue un câble comprenant sept torons de 19 fils chacun, les fils ayant un diamètre unitaire de 0,275 mm environ.In a second example, a cable is formed comprising seven strands of 19 son each, the son having a unit diameter of about 0.275 mm.

Selon un troisième exemple, on constitue un câble comprenant un toron de 61 fils de 0,32 mm de diamètre environ.According to a third example, a cable is formed comprising a strand of 61 wires of about 0.32 mm in diameter.

Selon un autre exemple, le câble comprend un toron de 37 fils de 0,32 ou 0,25 mm environ.In another example, the cable comprises a strand of 37 wires of about 0.32 or 0.25 mm.

Selon un autre exemple, le câble comprend un toron de 19 fils de 0,30 ou 0,25 ou 0,20 mm environ, selon une structure des figures 2 ou 3.In another example, the cable comprises a strand of 19 wires of about 0.30 or 0.25 or 0.20 mm, in a structure of Figures 2 or 3 .

Enfin, les câbles à plus faible section seront constitués d'un fil central 7a d'alliage de cuivre nickelé, entouré de six fils 7b-7g d'aluminium cuivré et nickelé de 0,25 ou 0,20 mm de diamètre.Finally, the cables with smaller section will consist of a nickel-plated copper alloy core wire 7a, surrounded by six son 7b-7g of copper-plated and nickel-plated aluminum of 0.25 or 0.20 mm in diameter.

Les torons pourront ensuite être recouverts d'une couche isolante en polyimide et d'une couche externe en polytétrafluoroéthylène.The strands can then be covered with an insulating layer of polyimide and an outer layer of polytetrafluoroethylene.

Pour la réalisation d'un fil 1 tel qu'illustré sur la figure 1, on est parti d'un fil d'ébauche 8 en aluminium cuivré de plus grand diamètre Dl tel qu'illustré sur la figure 5, le diamètre Dl de fil d'ébauche 8 étant compris entre 2 et 5 fois le diamètre final DF désiré du fil, par exemple de 0,8 à 1,2 millimètres environ. Cela a permis un traitement rapide, industriellement économique.For the realization of a thread 1 as illustrated on the figure 1 , we started from a copper-plated aluminum blank wire 8 of larger diameter D l as illustrated on the figure 5 , the diameter D 1 of blank wire 8 being between 2 and 5 times the desired final diameter D F of the wire, for example from 0.8 to 1.2 millimeters approximately. This allowed a fast, industrially economical treatment.

On a traité le fil d'ébauche 8 par un procédé illustré sur les figures 6 et 7.The roughing wire 8 was processed by an illustrated method on the figures 6 and 7 .

Le fil d'ébauche 8 était constitué d'une âme 8a en aluminium, recouverte d'une couche superficielle 8b en cuivre, le cuivre représentant 15 % en volume de l'ensemble.The roughing wire 8 consisted of an aluminum core 8a, covered with a copper surface layer 8b, the copper representing 15% by volume of the assembly.

On considère maintenant la figure 6, qui illustre schématiquement la structure générale d'un dispositif pour la fabrication d'un fil selon un procédé de l'invention.We now consider the figure 6 , which schematically illustrates the general structure of a device for manufacturing a wire according to a method of the invention.

Le fil d'ébauche 8 passe tout d'abord dans un dispositif à ultrasons 9, qui réalise un premier dégraissage. Le fil passe ensuite dans un bac de dégraissage anodique 10, qui réalise un dégraissage anodique dans un bain 11 pouvant par exemple contenir de la soude et des tensio actifs. De la sorte, on s'assure que la surface du fil est dépourvue d'oxydes. La présence de tels oxydes serait défavorable au tréfilage ultérieur.The roughing wire 8 passes firstly into an ultrasound device 9, which performs a first degreasing. The wire then passes into an anode degreasing tank 10, which performs anodic degreasing in a bath 11 which may for example contain sodium hydroxide and surfactants. In this way, it is ensured that the surface of the wire is free of oxides. The presence of such oxides would be unfavorable to subsequent drawing.

Le fil passe ensuite dans un dispositif de rinçage 12, produisant un rinçage du fil à l'eau déminéralisée.The wire then passes into a rinsing device 12, producing a rinsing of the wire with demineralised water.

Le fil passe ensuite dans un bac 13 contenant un bain d'acide sulfamique 14. La concentration d'acide sulfamique peut avantageusement être d'environ 40 grammes par litre. On réalise ainsi un traitement de surface de la couche en cuivre, facilitant l'adhérence ultérieure du nickel.The yarn then passes into a tray 13 containing a sulfamic acid bath 14. The sulfamic acid concentration may advantageously be about 40 grams per liter. This provides a surface treatment of the copper layer, facilitating the subsequent adhesion of nickel.

Le fil passe ensuite dans un dispositif de dépôt électrolytique de nickel 15, qui réalise un dépôt approprié d'une couche superficielle de nickel. Le dispositif sera décrit plus en détail en relation avec la figure 7. Le fil passe ensuite dans un second dispositif de rinçage 16, qui rince le fil à l'eau déminéralisée.The wire then passes into an electrolytic nickel deposition device 15, which provides a suitable deposition of a surface layer of nickel. The device will be described in more detail in relation to the figure 7 . The wire then passes into a second rinsing device 16, which rinses the wire with demineralised water.

Le fil passe ensuite dans un dispositif de tréfilage 17, dans lequel on réalise un tréfilage en huile entière jusqu'au diamètre final, c'est-à-dire dans la gamme de 0,51 - 0,20 mm de diamètre environ.The wire then passes into a wire drawing device 17, in which a complete oil drawing is carried out to the final diameter, that is to say in the range of about 0.51 - 0.20 mm in diameter.

Généralement, le tréfilage s'effectue à une vitesse différente des traitements précédents. Il est donc nécessaire alors de prévoir une étape intermédiaire au cours de laquelle le fil est conditionné en bobine après l'étape de rinçage dans le dispositif de rinçage 16, et on enduit le fil d'un film d'huile entière qui le protège jusqu'à un traitement de tréfilage ultérieur.Generally, wire drawing takes place at a different speed than previous treatments. It is therefore necessary to provide an intermediate step during which the wire is packaged in a coil after the rinsing step in the rinsing device 16, and the wire is coated with a film of whole oil which protects it until to a subsequent drawing treatment.

En sortie du dispositif de tréfilage 17, le fil passe dans un four 18 associé à une source de gaz neutre 19 tel que l'azote, dans lequel le fil subit un recuit sous azote à 240°C environ pendant deux heures environ. On obtient ainsi un fil 1 en sortie, tel qu'illustré sur la figure 1.At the output of the wire drawing device 17, the wire passes through an oven 18 associated with a source of neutral gas 19 such as nitrogen, in which the wire is annealed under nitrogen at about 240 ° C. for about two hours. This gives a wire 1 output, as illustrated on the figure 1 .

Le résultat obtenu par ce procédé peut dépendre de la dimension et de la structure du fil d'ébauche 8. Pour s'affranchir des éventuelles dispersions de dimension et de structure, on peut avantageusement procéder à une étape préalable de calibrage du fil d'ébauche 8, pour lui donner une dimension et une dureté appropriées et constantes. On pourra avantageusement préférer un fil d'ébauche ayant une charge à la rupture inférieure ou égale à 20 daN par mm2 environ, et un allongement compris entre 2 et 3 % environ, avec une dimension constante choisie dans la gamme des diamètres compris entre trois fois et cinq fois le diamètre final désiré du fil.The result obtained by this method may depend on the size and the structure of the blank wire 8. In order to overcome any size and structure dispersions, it is advantageous to carry out a preliminary step of calibrating the blank wire. 8, to give it a dimension and a hardness appropriate and constant. It is preferable to prefer a roughing wire having a breaking load of less than or equal to about 20 daN per mm 2 , and an elongation of between about 2 and 3%, with a constant dimension selected from the range of diameters between three and a half. times and five times the desired final diameter of the wire.

On considère maintenant la figure 7, pour la description du dispositif 15 réalisant l'étape de dépôt de la couche de nickel par électrolyse.We now consider the figure 7 , for the description of the device 15 carrying out the step of depositing the nickel layer by electrolysis.

Le dispositif comprend un bac interne 20 à débordement, contenant le bain d'électrolyse 21 qui se déverse, comme indiqué par la flèche 22, dans un bac externe 23 qui contient le bac interne 20. Le liquide recueilli dans le bac externe 23 est envoyé par des canalisations 24 dans une cuve de stockage 25, de laquelle le liquide est renvoyé dans le bac interne 20 par une pompe 26 et une canalisation 27. Une réserve de nickel métallique 28 est logée dans le bac interne 20, à l'intérieur du bain d'électrolyse 21. Le fil d'ébauche 8 est déplacé et guidé à travers le bac interne 20, en plusieurs passages, et ressort après dépôt d'une couche de nickel sur sa surface. La réserve de nickel 28 est connectée électriquement au pôle positif d'un générateur électrique 29 dont le pôle négatif est connecté au fil 8.The device comprises an internal overflow tank 20, containing the electrolysis bath 21 which discharges, as indicated by the arrow 22, into an external tank 23 which contains the internal tank 20. The liquid collected in the outer tank 23 is sent by pipes 24 in a storage tank 25, from which the liquid is returned to the inner tank 20 by a pump 26 and a pipe 27. A nickel metal reserve 28 is housed in the inner tank 20, inside the electrolysis bath 21. The blank wire 8 is moved and guided through the inner tank 20, in several passages, and comes out after depositing a layer of nickel on its surface. The nickel reserve 28 is electrically connected to the positive pole of an electric generator 29 whose negative pole is connected to the wire 8.

Le bain d'électrolyse 21 contient du sulfamate de nickel en solution aqueuse. De bons résultats nécessitent de contrôler en permanence la concentration du bain d'électrolyse 21. On prévoit pour cela de raccorder la cuve de stockage 25 à une alimentation en eau 30, à une canalisation de purge 31, à une source d'acide sulfamique 32. On contrôle le pH du bain d'électrolyse 21 par un capteur de pH 33 agissant sur un régulateur qui commande la manoeuvre des vannes correspondantes pour soutirer une quantité de liquide du bain d'électrolyse 21 par la canalisation de purge 31, pour ajouter de l'eau par l'alimentation en eau 30, et pour ajouter de l'acide sulfamique par la source d'acide sulfamique 32.The electrolysis bath 21 contains nickel sulphamate in aqueous solution. Good results require permanent control of the concentration of the electrolysis bath 21. This is done by connecting the storage tank 25 to a water supply 30, to a purge line 31, to a source of sulfamic acid 32 The pH of the electrolysis bath 21 is controlled by a pH sensor 33 acting on a regulator which controls the operation of the corresponding valves to withdraw a quantity of liquid from the electrolysis bath 21 via the purge pipe 31, to add water by the water supply 30, and to add sulfamic acid by the sulfamic acid source 32.

Dans les essais réalisés, le pH du bain d'électrolyse a été avantageusement maintenu entre 2,3 et 3,0 environ, de préférence voisin de 2,4.In the tests carried out, the pH of the electrolysis bath was advantageously maintained between about 2.3 and 3.0, preferably close to 2.4.

On a également régulé la température du bain d'électrolyse 21, au moyen d'un capteur de température 34 et de moyens de chauffe 35, afin que le bain d'électrolyse soit par exemple à une température d'environ 60°C.The temperature of the electrolysis bath 21 was also regulated, by means of a temperature sensor 34 and heating means 35, so that the electrolysis bath was for example at a temperature of approximately 60 ° C.

La concentration en sulfamate de nickel dans le bain d'électrolyse 21 a été maintenue à un niveau bas, par exemple inférieur à 140 grammes par litre de nickel. A défaut, la couche superficielle de nickel aurait été trop dure, et aurait mal supporté le tréfilage ultérieur.The nickel sulfamate concentration in the electrolysis bath 21 was kept low, for example less than 140 grams per liter of nickel. Otherwise, the superficial layer of nickel would have been too hard, and would have poorly supported the subsequent drawing.

Le générateur électrique 29 est adapté pour réguler la densité de courant d'électrolyse. Dans les essais réalisés, la densité de courant d'électrolyse a été avantageusement maintenue dans une fourchette de valeurs comprise entre 10 et 16 A/dm2 ; de préférence comprise entre 15 et 16 A/dm2.The electric generator 29 is adapted to regulate the electrolysis current density. In the tests carried out, the electrolysis current density has advantageously been maintained within a range of values of between 10 and 16 A / dm 2 ; preferably between 15 and 16 A / dm 2 .

A titre d'exemple, on donne ci-après des résultats de quelques essais qui ont été effectués avec des conditions différentes de dépôt électrolytique, et on indique la qualité satisfaisante ou non du fil obtenu, j étant la densité de courant : Echantillons j pH Résultat 1 14 2,5 bon 2 14 2,95 acceptable 3 14 3,2 mauvais 4 14 3,55 mauvais 5 20 2,5 mauvais 6 22 2,5 mauvais 7 17 2,5 mauvais 8 11,2 2,5 acceptable 9 8,4 2,5 mauvais By way of example, the following are the results of some tests which have been carried out with different conditions of electrolytic deposition, and the satisfactory or unsatisfactory quality of the wire obtained is indicated, j being the current density: Samples j pH Result 1 14 2.5 Well 2 14 2.95 acceptable 3 14 3.2 bad 4 14 3.55 bad 5 20 2.5 bad 6 22 2.5 bad 7 17 2.5 bad 8 11.2 2.5 acceptable 9 8.4 2.5 bad

Une difficulté a été de déterminer la qualité bonne, acceptable ou mauvaise du revêtement de nickel réalisé par le procédé.A difficulty has been in determining the good, acceptable or poor quality of the nickel coating produced by the process.

On a utilisé avec succès un test au bain de polysulfure selon la norme ASTM B298, avec un examen optique spécifique, qui procure un résultat global de contrôle de la qualité du revêtement, en mettant en évidence les lacunes ou microfissures éventuelles du revêtement de nickel.A polysulfide bath test according to ASTM B298 has been successfully used, with a specific optical examination, which provides an overall result of quality control of the coating, highlighting any gaps or microcracks in the nickel coating.

Comme illustré sur la figure 8, un échantillon de fil 1 est tout d'abord dégraissé par immersion dans un solvant organique approprié 36 tel que le benzène, le trichloréthylène ou un mélange d'éther et d'alcool, pendant au moins 3 minutes. Il est ensuite retiré et séché par essuyage à l'aide d'un tissu doux et propre. On doit tenir l'échantillon de fil 1 dans le tissu jusqu'à la suite du test, et l'on doit éviter de le toucher à la main.As illustrated on the figure 8 a sample of yarn 1 is first defatted by immersion in a suitable organic solvent such as benzene, trichlorethylene or a mixture of ether and alcohol for at least 3 minutes. It is then removed and dried by wiping with a soft, clean cloth. The wire sample 1 should be held in the tissue until the test is complete, and should not be touched by hand.

On prépare une solution concentrée de polysulfure en dissolvant des cristaux de sulfure de sodium dans de l'eau déminéralisée jusqu'à saturation à environ 21 °C et en ajoutant suffisamment de fleur de souffre pour obtenir la saturation complète, que l'on peut contrôler par la présence d'un excès de souffre lorsque la solution a reposé pendant au moins 24 heures. On réalise la solution de test en diluant une portion de la solution concentrée avec de l'eau déminéralisée jusqu'à une densité spécifique de 1,142 à 15,6°C. La solution de test de polysulfure de sodium doit avoir une force suffisante pour noircir entièrement un tronçon de fil de cuivre en 5 secondes. La solution de test ne sera pas considérée comme épuisée tant qu'elle pourra noircir une pièce de cuivre.A concentrated solution of polysulfide is prepared by dissolving sodium sulphide crystals in deionized water until saturation at about 21 ° C and adding enough sulfur flower to obtain complete saturation, which can be controlled by the presence of an excess of sulfur when the solution has sat for at least 24 hours. The test solution was made by diluting a portion of the concentrated solution with deionized water to a specific gravity of 1.142 at 15.6 ° C. The sodium polysulfide test solution should have sufficient strength to fully blacken a section of copper wire within 5 seconds. The test solution will not be considered exhausted as long as it can blacken a piece of copper.

On prépare simultanément une solution d'acide chlorhydrique, en diluant l'acide chlorhydrique commercial avec de l'eau distillée jusqu'à atteindre une densité de 1,088 mesurée à 15,6°C. Une portion de la solution d'acide chlorhydrique ayant un volume de 180 millilitres sera considérée comme épuisée si elle ne peut pas supprimer en 45 secondes la décoloration de l'argent due à l'immersion dans le polysulfure.A solution of hydrochloric acid is prepared simultaneously by diluting the commercial hydrochloric acid with distilled water to a density of 1.088 measured at 15.6 ° C. A portion of the acid solution hydrochloric acid with a volume of 180 milliliters will be considered exhausted if it can not suppress in 45 seconds the silver discoloration due to immersion in the polysulfide.

Pour tester le fil, on immerge l'échantillon de fil 1 ayant une longueur d'au moins 114 mm pendant 30 secondes dans un bain de polysulfure 37 contenant la solution de polysulfure de sodium décrite ci-dessus maintenue à une température comprise entre 15,6°C et 21 °C.To test the yarn, the sample of yarn 1 having a length of at least 114 mm was immersed for 30 seconds in a polysulfide bath 37 containing the above-described solution of sodium polysulfide maintained at a temperature of between 15.degree. 6 ° C and 21 ° C.

Ensuite on rince l'échantillon de fil 1 à l'eau déminéralisée 38, et on le sèche avec un tissu doux et propre.Then the wire sample 1 is rinsed with deionized water 38, and dried with a soft, clean cloth.

On immerge immédiatement l'échantillon de fil 1 pendant 15 secondes dans une solution 39 d'acide chlorhydrique décrite ci-dessus, puis on le lave entièrement à l'eau déminéralisée 40 et on le sèche avec un tissu doux et propre.The sample of yarn 1 was immediately immersed for 15 seconds in a hydrochloric acid solution described above, then washed thoroughly with deionized water and dried with a clean, soft cloth.

Moins de deux heures après ce traitement, on examine l'échantillon de fil 1, par exemple à l'aide d'une loupe binoculaire 41 en grossissement x 10. On ne portera pas attention aux zones d'extrémité de l'échantillon de fil 1, c'est-à-dire les zones à moins de 12,7 mm de chaque extrémité.Less than two hours after this treatment, the sample of wire 1 is examined, for example using a binocular loupe 41 in magnification x 10. No attention will be paid to the end zones of the wire sample. 1, that is, the areas within 12.7 mm of each end.

Un échantillon de fil 1 prélevé sur un fil de bonne qualité, illustré sur la photographie de la figure 9, ne présente pas de marque visible d'attaque de la couche inférieure de cuivre par le bain de polysulfure. On estime qu'une marque d'attaque est visible lorsqu'elle présente une surface d'au moins 0,02 mm2 en grossissement x 10 (correspondant à un spot de 0,01 mm de côté au grossissement 1).A sample of yarn 1 taken from a thread of good quality, illustrated in the photograph of the figure 9 does not show a visible mark of attack of the lower layer of copper by the polysulfide bath. It is estimated that an attack mark is visible when it has an area of at least 0.02 mm 2 in magnification x 10 (corresponding to a spot of 0.01 mm side at magnification 1).

Par contre, un échantillon de fil prélevé sur un fil défectueux, tel qu'illustré sur la photographie de la figure 10, présente des zones sombres 42 qui sont la preuve d'un défaut d'étanchéité de la couche superficielle de nickel, laissant se produire une attaque du cuivre sous-jacent par le bain de polysulfure. C'est de cette façon qu'ont été examinés les fils des échantillons du tableau ci-dessus.On the other hand, a sample of wire taken from a defective wire, as illustrated in the photograph of the figure 10 , has dark areas 42 which are evidence of a lack of sealing of the nickel surface layer, leaving an attack of the underlying copper by the polysulfide bath. This is how the threads of the samples in the table above were examined.

Les conducteurs électriques selon la présente invention pourront avantageusement être utilisés dans tous types d'applications requérant un bon compromis entre la conductivité, la charge à la rupture, la flexibilité, le poids, et la protection à long terme, notamment dans l'aéronautique, dans l'automobile, et de façon générale dans tous types de mobiles.The electrical conductors according to the present invention may advantageously be used in all types of applications requiring a good compromise between conductivity, load at break, flexibility, weight, and long-term protection, especially in the aeronautics, in the automobile, and generally in all types of mobiles.

La présente invention n'est pas limitée aux modes de réalisation qui ont été explicitement décrits, mais elle en inclut les diverses variantes et généralisations contenues dans le domaine des revendications ci-après.The present invention is not limited to the embodiments which have been explicitly described, but it includes the various variants and generalizations thereof within the scope of the claims below.

Claims (21)

  1. Aluminum cable type electrical conductor comprising at least one stranded conductor based on conductive wires (1) with an aluminum core (2) coated with an intermediate layer (3) of copper itself coated by a surface layer (4) of nickel, characterized in that :
    - the surface layer (4) of nickel has a thickness (E) from about 1,3 µm to about 3 µm,
    - the surface layer (4) of nickel has sufficient continuity to resist a polysulfide bath (37) continuity test for at least 30 seconds without visible traces of attack (42) of the copper appearing at x10 magnification.
  2. Conductor according to claim 1, characterized in that the thickness (E) of the surface layer (4) of nickel is from about 2 µm to about 3 µm.
  3. Conductor according to claim 2, characterized in that the thickness (E) of the surface layer (4) of nickel is about 2,3 µm.
  4. Conductor according to any one of claims 1 to 3, characterized in that it consists of a cable comprising seven stranded conductors each of 10 or 15 wires having an individual diameter of about 0,51 mm.
  5. Conductor according to any one of claims 1 to 3, characterized in that it consists of a cable with seven stranded conductors each of 19 wires having an individual diameter of about 0,275 mm.
  6. Conductor according to any one of claims 1 to 3, characterized in that it consists of a cable with stranded conductor of 61 wires having a diameter of about 0,32 mm.
  7. Conductor according to any one of claims 1 to 3, characterized in that it consists of a cable with one stranded conductor of 37 wires having a diameter of about 0,32 mm or about 0,25 mm.
  8. Conductor according to any one of claims 1 to 3, characterized in that it consists of a cable comprising one stranded conductor (5, 6) of 19 wires of about 0,30 mm or about 0,25 mm or about 0,20 mm.
  9. Conductor according to any one of claims 1 to 3, characterized in that it comprises a central wire (7a) of nickel-plated copper alloy surrounded by six wires (7b-7g) of nickel-plated copper-plated aluminum with a diameter of about 0,25 mm or about 0,20 mm.
  10. Conductor according to any one of claims 1 to 9, characterized in that the cable is stranded with one or more true concentric or unilay concentric wires or stranded conductors.
  11. Conductor according to any one of claims 1 to 10, characterized in that the stranded conductor(s) and/or the cable are coated with an insulative layer of polyimide and an external layer of polytetrafluoroethylene.
  12. Method for producing a conductor according to any one of claims 1 to 11, in which is provided a copper-plated and nickel-plated aluminum wire fabrication procedure including the following steps :
    a) providing a wire blank (8) with an aluminum core (8a) coated with a layer of copper (8b) representing 10% to 20% by volume, of diameter (Dl) from twice to five times the required final diameter (DF) of the wire,
    b) degreasing the wire blank (8),
    c) etching the wire blank (8) using sulfamic acid (14),
    d) depositing on the wire blank (8) a layer of nickel by electrolysis in an electrolysis bath (21) containing aqueous nickel sulfamate, the temperature of the electrolysis bath (21) being maintained from about 55°C to about 65°C, the pH of the electrolysis bath (21) being maintained from about 2,3 to about 3,0, the current density (j) being from 10 A/dm2 to 16 A/dm2, the concentration of nickel being maintained at less than 140 grams per liter approximately in the electrolysis bath (21),
    e) rinsing the wire obtained with demineralized water,
    f) drawing the wire obtained in whole oil to the final diameter,
    g) stranding a plurality of the wires obtained in this way into bundles of wires,
    h) annealing in a neutral gas.
  13. Method according to claim 12, characterized in that, in the neutral gas annealing step h), the neutral gas is nitrogen.
  14. Method according to any of claim 12 or claim 13, characterized in that, in the neutral gas annealing step h), the temperature is maintained at about 250°C for at least about two hours.
  15. Method according to any one of claims 12 to 14, characterized in that, in the step d), the temperature of the electrolysis bath (21) is about 60°C, the pH of the electrolysis bath (21) is about 2,4, and the current density is about 15 to 16 A/dm2.
  16. Method according to any one of claims 12 to 15, characterized in that it comprises a prior step ao) of calibrating the copper-plated aluminum wire blank (8) in terms of dimensions and hardness.
  17. Method according to any one of claims 12 to 16, characterized in that, after a calibration step ao), when effected, the copper-plated aluminum wire blank (8) has a yield point less than or equal to about 20 daN/mm2 and an elongation from about 2% to about 3%.
  18. Method according to any one of claims 12 to 17, characterized in that, in the step c), the sulfamic acid bath has a concentration of about 40 grams per liter.
  19. Method according to any one of claims 12 to 18, characterized in that the initial diameter (Dl) of the wire blank (8) of copper-plated aluminum is from about 1,2 mm to about 0,8 mm, the nickel is deposited to a thickness from about 10 µm to about 15 µm, and the final diameter of the copper-plated and nickel-plated aluminum wire (1) is from about 0,51 mm to about 0,20 mm.
  20. Method according to any one of claims 12 to 19, characterized in that the step b) of degreasing the wire comprises :
    b1) degreasing the wire blank (8) by ultrasound,
    b2) anodically degreasing the wire blank (8) in a bath (11) containing soda and surfactants,
    b3) rinsing the wire blank (8) with demineralized water.
  21. Method according to any one of claims 12 to 20, characterized in that, for wires of diameter less than or equal to 0,25 mm, the stranding step g) is carried out before the annealing step h), whereas for wires of greater diameter the annealing step h) is carried out before the stranding step g).
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DE05356180T1 (en) 2006-10-12
ATE390694T1 (en) 2008-04-15
EP1647996B2 (en) 2016-11-16
TW200626746A (en) 2006-08-01
EP1647996A9 (en) 2006-07-05
EP1647996B9 (en) 2008-08-13
DE602005005598T2 (en) 2009-04-30
PL1647996T3 (en) 2008-09-30
CN1760993B (en) 2011-05-11
ES2259944T1 (en) 2006-11-01
FR2876493A1 (en) 2006-04-14
EP1647996A1 (en) 2006-04-19
DE602005005598T3 (en) 2017-04-06
US20060102368A1 (en) 2006-05-18
FR2876493B1 (en) 2007-01-12
DE602005005598D1 (en) 2008-05-08
US7105740B2 (en) 2006-09-12
TWI391525B (en) 2013-04-01
CN1760993A (en) 2006-04-19

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