EP2887361A1 - Rust-resistant, elongate, electrically conductive member - Google Patents

Abstract

The invention relates to an elongated electrically conductive element comprising a core made of copper or copper alloy and at least one layer of white bronze surrounding said copper or copper alloy core, characterized in that said white-bronze layer is the layer the outermost of the elongated electrically conductive element

Description

The present invention relates to an elongate electrically conductive member comprising a core of copper or copper alloy and at least one layer of white bronze, and to an electrical cable comprising at least one such elongated electrically conductive member.

It applies typically but not exclusively, to low voltage (especially less than 6kV) or medium voltage (especially 6 to 45-60 kV) energy cables, in the building, automotive and rail.

More particularly, the invention relates to an electric cable having a good resistance to corrosion while ensuring good mechanical and electrical properties, particularly in terms of temperature resistance and electrical conductivity.

Of the document EP 0 893 187 A1 is known a metal part (eg brass high frequency coaxial connector body), on which is deposited a copper layer, then an anti-corrosion coating comprising a layer of white bronze, a palladium layer covering said white bronze layer, and a gold layer covering said palladium layer. The white bronze is an alloy of copper and tin generally comprising between 20 and 40% by weight of tin. With this coating, said metal part is resistant to corrosion while retaining good brazeability. However, the chemical composition of the white bronze layer used is not described, the presence of a layer of palladium and / or a gold layer in said part decreases its electrical conductivity, and the presence of a layer of gold as the outermost layer of the metal part decreases its resistance to deformation. In addition, this metal part has the disadvantage of being very expensive by the use of precious metals such as palladium and gold, and by its method of preparation which requires several steps to form the different metal layers. Finally, this metal part is not used to design an electric cable.

The object of the present invention is to overcome the drawbacks of the techniques of the prior art by providing an elongate electrically conductive element comprising a core of copper or copper alloy and at least one layer of white bronze, said elongate electrically conductive element being economic and having a good resistance to corrosion while ensuring good electrical properties, especially in terms of electrical conductivity, and good mechanical properties, especially in terms of temperature resistance. In particular, during the manufacture of an electrical cable comprising one or more elongated electrically conductive elements, the elongate electrically conductive element (s) are generally isolated by means of an electrically insulating layer of plastic material such as a layer comprising polytetrafluoroethylene (PTFE) whose application (eg by extrusion) requires a heat treatment step at a temperature of about 370 ° C for 10 minutes, which requires that the electric cable can withstand such a temperature.

The present invention therefore has for its first object an elongate electrically conductive element comprising a core made of copper or copper alloy and at least one layer of white bronze surrounding said core of copper or copper alloy, characterized in that said layer of bronze white is the outermost layer of the elongated electrically conductive element.

In the invention, the term "elongated electrically conductive element" means an electrically conductive element having a longitudinal axis. In particular, the electrically conductive element is elongated because it has undergone at least one drawing step (cold deformation step, in particular through diamond dies).

In the invention, the term "white bronze layer" means a layer comprising copper and at least 20% by weight of tin.

In the invention, the expression "said white bronze layer is the outermost layer of the elongated electrically conductive element" means that the white bronze layer of the elongated electrically conductive element of the invention is not covered by any other metal layer.

In other words, the entire outer surface of the white bronze layer (i.e. the whole of the farthest surface of the elongated electrically conductive element) is not covered by any other metal layer.

For example, said white bronze layer is not covered by any layer of palladium and / or any gold layer and / or any layer of tin.

With this outermost white bronze layer of the electrically conductive element, the air oxidation of the elongate electrically conductive element of the invention is avoided both at room temperature (ie 20 ° C.), at elevated temperatures ranging from 200 ° C to 400 ° C. Furthermore, the white bronze layer used in the elongated electrically conductive element of the invention, unlike other anti-corrosion coatings of the prior art (e.g. nickel), is not toxic to the environment. Finally, the elongated electrically conductive element of the invention retains good electrical properties, especially in terms of electrical conductivity, resistivity and linear resistance, good mechanical properties, especially in terms of breaking strength, and good performance. brazing.

The white bronze layer extends in particular along the longitudinal axis of the elongated electrically conductive element.

The white bronze layer preferably has a substantially regular surface. Thus, the white bronze layer forms a continuous envelope (without irregularities or roughness) surrounding said copper core or copper alloy.

According to a particularly preferred embodiment of the invention, the white bronze layer of the elongated electrically conductive element comprises at most 57% by weight of tin, and preferably at most 40% by weight of tin.

In a particular embodiment, the white bronze layer of the elongated electrically conductive element of the invention further comprises zinc. The combination of copper, at least 20% by weight of tin and zinc provides a layer having both good temperature resistance and good corrosion resistance.

It is preferable that said white bronze layer comprises only tin (at least 20% by weight), copper and zinc. Indeed, if we add other elements in said layer, the electrical conductivity and / or the breaking strength can drop significantly, especially at high temperatures.

In a particular embodiment, the white bronze layer of the elongated electrically conductive element of the invention comprises from 40 to 55% by weight of copper, and preferably from 45 to 53% by weight of copper. If the amount of copper in the white bronze layer is greater than 55% by weight, the elongate electrically conductive member of the invention may exhibit decreased corrosion resistance. If the amount of copper is less than 40% by weight, the elongated electrically conductive element of the invention may have decreased electrical conductivity.

In a particular embodiment, the white bronze layer of the elongated electrically conductive element of the invention comprises from 30 to 57% by weight of tin, and preferably from 31 to 38% by weight of tin. . If the amount of tin is greater than 57% by weight, the elongated electrically conductive element of the invention may have a reduced temperature resistance. If the amount of tin is less than 30% by weight, the elongate electrically conductive member of the invention may exhibit low corrosion resistance.

In a preferred embodiment, the white bronze layer of the elongate electrically conductive element of the invention comprises from about 3 to about 20 weight percent zinc, and preferably from about 13 to about 18 weight percent zinc. If the amount of zinc in the white bronze layer is greater than 20% by weight, the elongated electrically conductive element of the invention may exhibit decreased corrosion resistance. If the amount of zinc is less than 3% by weight, the elongated electrically conductive member of the invention may have decreased temperature resistance and tensile strength.

The white bronze layer of the elongated electrically conductive element of the invention may have a thickness ranging from 0.1 μm to 100 μm, preferably from 2 to 10 μm, and more preferably from 3 to 7 μm.

In a particular embodiment, the elongate electrically conductive element does not comprise a layer consisting of nickel and / or copper layer, in particular surrounding the copper or copper alloy core. In particular, the presence of a nickel layer can alter the electrical conductivity properties of the elongated electrically conductive element.

In a preferred embodiment, the white bronze layer is directly in contact (i.e. in direct physical contact) with the copper or copper alloy core.

In other words, the elongated electrically conductive element of the invention does not include an intermediate layer (s) positioned between the copper or copper alloy core and the white bronze layer.

The copper or copper alloy core may have a cross section ranging from 0.3 mm ² to 85 mm ² , and preferably ranging from 0.3 mm ² to 70 mm ² .

The copper or copper alloy core preferably has a round cross-sectional shape.

Advantageously, the white bronze layer is deposited on the core of copper or copper alloy by electroplating.

The electroplating is carried out by techniques well known to those skilled in the art. Preferably, the electrodeposition is carried out in an alkaline medium (ie pH> 7), and preferably at a pH ranging from 13.1 to 13.5.

The electrodeposition can also be carried out in an acid medium (i.e. pH <7), and preferably at a pH ranging from 2 to 5.

The copper or copper alloy core may be immersed in an aqueous electrolysis bath comprising a copper precursor, a zinc precursor and a tin precursor. In the electrolysis bath, the copper precursor may be selected from copper cyanide and copper sulphate, the zinc precursor may be zinc sulphate, and the tin precursor may be tin sulphate. The copper, the zinc and the tin are then codéposés on said soul, that is to say that the tin, the zinc and the copper are alloys during their deposit on the soul of copper or alloy of copper. In this case, the electrolytic bath contains the precursors of copper, zinc and tin in the proportions chosen respectively identical to those of the alloy constituting the white bronze layer. By way of example, the bath may comprise from 10 to 15 g / l approximately copper precursor (s), from 10 to 20 g / l approximately tin precursor (s), and from 0 to 5 g / l about one precursor (s) of zinc.

In a preferred embodiment, the electrolytic parameters used during electroplating are dictated by a current density and a conductivity of the electrolysis bath. For a desired thickness on a prototype copper core, the current density is preferably set from about 0.5 to 60 A / dm ² , and more preferably from about 1 to 5 A / dm ² . The temperature of the electrolysis bath may range from 25 ° C to 65 ° C, and preferably from 55 to 65 ° C.

The electroplating method makes it possible to control and favor the formation of a continuous envelope (without irregularities or roughness) around the copper or copper alloy core.

Thus, the white bronze layer is preferably not formed around the copper or copper alloy core by diffusion by heat treatment (a step well known under the Anglicism " reflow treatment ") .

Indeed, this type of process consists in depositing on a metal part a copper layer and then a layer of tin, and in heating the assembly, in particular at a temperature of at least 150 ° C., in order to allow diffusion of the copper in the tin layer and thus form an intermetallic layer of copper alloy and tin between the copper layer and the tin layer. In this process, the copper-tin alloy layer is formed in situ and it is difficult to control its thickness and to obtain a substantially regular surface. In addition, the intermetallic layer obtained by this method is brittle or brittle, which reduces the bending strength of the electrically conductive element. Finally, this method does not make it possible to form a layer of white bronze which further comprises zinc.

The second subject of the present invention is an electrical cable comprising at least one elongated electrically conductive element as defined in the present invention, and at least one polymer layer surrounding said electrically conductive element.

In a preferred embodiment, said polymer layer is directly in contact with the white bronze layer of the elongated electrically conductive member.

The polymer layer may be an electrically insulating layer.

According to a particularly preferred embodiment of the invention, the polymer layer comprises polytetrafluoroethylene (PTFE) or a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP).

The polymeric layer is preferably an extruded layer by techniques well known to those skilled in the art.

The electrical cable of the invention is preferably a low-voltage (in particular less than 6kV) or medium voltage (in particular 6 to 45-60 kV) energy cable.

The figure 1 schematically represents a structure, in cross section, of an electric cable according to the invention.

The figure 1 shows an electrical cable comprising an elongate electrically conductive member comprising a core of copper or copper alloy (1-1) and a layer of white bronze (1-2) surrounding said core of copper or copper alloy (1- 1); and a polymer layer (2) surrounding said elongate electrically conductive member. The thickness of the white bronze layer is indicated by the arrow and the reference e.

EXAMPLES Example 1 Manufacture of an Elongated Electrically Conductive Element According to the Invention

A 5 μm thick white bronze layer was applied by electrodeposition on a 2.57 mm diameter copper wire.

The alkaline electrolysis bath prepared consisted of about 14 g / l of copper, about 55 g / l of free cyanide, about 19 g / l of free potash, about 20 g / l of tin and about 4 g / l of zinc. . The bath pH was about 13.3. The current density was about 1.5A / dm ² and the temperature of the electrolysis bath was about 62 ° C.

The composition of the white bronze layer surrounding the copper core was 51% by weight of copper, 33% by weight of tin and 16% by weight of zinc. This composition was analyzed using an EDX energy dispersion spectrometer (20 kV, x1000, ± 1% by weight) sold under the trade name 227A 1SUS by the company Noran Instruments and with the aid of a SEM scanning electron microscope sold under the trade name JSM5310 by the company JEOL.

Example 2: Corrosion resistance and temperature resistance of the elongated electrically conductive element according to the invention

The elongate electrically conductive member as prepared above in Example 1 was temperature-enhanced for 2 hours at 200 ° C, or for 10 minutes at 300 ° C, or for 10 minutes at 370 ° C.

Table 1 below indicates the chemical composition of the white bronze layer before aging and its evolution as a function of aging. <b> TABLE 1 </ b> chemical composition of the white bronze layer of the electrically conductive element of the invention Cu (% by mass) Sn (% by weight) Zn (% by weight) Before aging 51 33 16 200 ° C / 2h 51 34 15 300 ° C / 10min 53 30 17 370 ° C / 10min 48 36 16

Thus, from the results of Table 1, it is found that the white bronze layer of the invention does not see its chemical composition change, and thus has a good temperature resistance.

Furthermore, no change in color of said layer during these different temperatures has been observed, whereas when using a bare copper wire (that is to say a wire comprising only a copper core and not having a layer of white bronze), a noticeable color change was observed. In fact, the bare copper wire has turned brown when aged at 300 ° C / 10min and black when aged at 370 ° C / 10min, these colors being characteristic of its oxidation in the air, and therefore the formation of an oxide layer on the surface.

Finally, a neutral salt spray corrosion resistance test was carried out according to the ISO 9227-ASTM B117 standard on the electrically conductive element of the invention before aging using an apparatus sold under the trade name 610e / 400 by the Erichsen company. It showed an absence of corrosion after 96 hours at 35 ° C in the presence of 5% by weight of NaCl, thus showing a good resistance to corrosion.

Example 3 Mechanical and Electrical Properties of the Elongated Electrically Conductive Element According to the Invention

Table 2 below shows the electrical and mechanical characteristics of the elongated electrically conductive element as prepared above in Example 1 before aging and after temperature aging at 370 ° C. for 10 minutes, and by comparison with electrical and mechanical characteristics of a bare copper wire before aging and after temperature aging at 370 ° C for 10 minutes.

The linear resistance (RL) was measured using a resistivity bench equipped with a microohmeter sold under the trade name MGR10 by the company SEFELEC.

The electrical resistivity (in μΩ.cm) of the coated elongated electrically conductive element was calculated from the linear resistance RL, the diameter of the elongated electrically conductive element, and the length of said element.

Electrical conductivity was calculated from the electrical resistivity of the coated elongated electrically conductive member and the electrical resistivity of the copper.

The mechanical strength (Rm) or breaking strength and elongation (A) or elongation at break were measured using an apparatus sold under the trade name DY35 by the company Adamel Lhomergy. <b> TABLE 2 </ b> Bare Cu wire Soul in Cu covered with white bronze Bare Cu wire Soul Cu covered with white bronze Before aging After aging 370 ° C / 10min Diameter (mm) 0,992 0,992 0,992 0,992 Length (m) 1,000 1,000 1,000 1,000 RL (mΩ / m) 22.255 22.669 21,700 22.131 Resistivity (μΩ.cm) 1,720 1,752 1,677 1,717 Electrical conductivity (% IACS) 100.2 98.4 102.8 100.4 Rm (MPa) 430 430 230 230 AT (%) 1 1 20 20 Aspect of the thread red Grey black Grey

Thus, Table 2 shows that the presence of the white-bronze layer in the elongate electrically conductive element of the invention makes it possible to improve the resistance to corrosion (appearance of the wire) while retaining good electrical properties (electrical conductivity , linear resistance and resistivity) and mechanical (breaking strength, elongation at break) with respect to an electrically conductive element which would contain only a copper core (ie without the white bronze layer).

Example 4 Other Properties of the Elongated Electrically Conductive Element According to the Invention Wire drawing

The wire drawing process is a cold forming process that involves stretching a wire by progressively reducing its diameter through tools called dies. The diameter of the element electrically Elongated conductor as obtained above is then decreased from 2.57 mm to 1.024 mm thanks to a die sold by the Esteves Company. This simulates the compression that usually occurs during the formation of an electric cable.

It appears from the results of the drawing test that the elongated electrically conductive element according to the invention is well drawn. In other words, said white bronze layer remains on the entire surface of the copper core without discontinuities and no crack is observed, which reflects a good adhesion of said white bronze layer to the copper core. In addition, the white bronze layer has the ability to withstand the compressive force caused by cable formation.

Example 5: solderability

The elongated electrically conductive element before aging and as prepared above in Example 1, was subjected to a brazability test according to IEC-60068-2-20. The test was carried out according to 3 angles of rotation (0 °, 120 ° and 240 °) and with a temperature of 235 ° C.

The wetting time obtained was less than 1 second, indicating good solderability of the elongate electrically conductive element of the invention.

Claims (15)

An elongated electrically conductive member comprising a core of copper or copper alloy and at least one layer of white bronze surrounding said copper or copper alloy core, characterized in that said white bronze layer is the outermost layer of copper elongated electrically conductive element. An elongated electrically conductive element according to claim 1, characterized in that the white bronze layer comprises copper and at least 20% by weight of tin. An elongated electrically conductive element according to claim 1 or claim 2, characterized in that the white bronze layer is not covered by any other metal layer. Elongated electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer comprises at most 57% by weight of tin. An elongated electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer has a substantially regular surface. An elongate electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer further comprises zinc. An elongated electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer comprises from 40 to 55% by weight of copper. An elongate electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer comprises from 30 to 57% by weight of tin. An elongated electrically conductive element according to any one of claims 6 to 8, characterized in that the white bronze layer comprises from 3% to 20% by weight of zinc. Elongated electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer has a thickness ranging from 0.1 to 100 μm. Elongated electrically conductive element according to any one of the preceding claims, characterized in that the white bronze layer is in direct contact with the copper or copper alloy core. Electrical cable characterized in that it comprises at least one elongated electrically conductive element as defined in any one of the preceding claims, and at least one polymer layer surrounding said electrically conductive element. Electrical cable according to claim 12, characterized in that said polymer layer is in direct contact with the white bronze layer of the elongated electrically conductive element. Electrical cable according to Claim 12 or Claim 13, characterized in that the polymer layer comprises polytetrafluoroethylene (PTFE) or a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP). Electrical cable according to one of Claims 12 to 14, characterized in that it is a low voltage or medium voltage power cable.

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