EP0756289B1 - Aluminiumleiter mit verbesserten elektrischen Kontakteigenschaften und Verfahren zur Herstellung desselben - Google Patents

Aluminiumleiter mit verbesserten elektrischen Kontakteigenschaften und Verfahren zur Herstellung desselben Download PDF

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Publication number
EP0756289B1
EP0756289B1 EP19960420254 EP96420254A EP0756289B1 EP 0756289 B1 EP0756289 B1 EP 0756289B1 EP 19960420254 EP19960420254 EP 19960420254 EP 96420254 A EP96420254 A EP 96420254A EP 0756289 B1 EP0756289 B1 EP 0756289B1
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European Patent Office
Prior art keywords
conductor
treatment
process according
electrochemical treatment
aluminum
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Application number
EP19960420254
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English (en)
French (fr)
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EP0756289A1 (de
Inventor
Richard Marsolais
Gabriel Colombier
Bernard Loreau
Didier Albert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto France SAS
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Aluminium Pechiney SA
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Publication of EP0756289A1 publication Critical patent/EP0756289A1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon

Definitions

  • the invention relates to the field of aluminum electrical conductors and all particularly solid or wired electrical wires and flats, and their aluminum connection devices.
  • the invention also relates to surface treatments of these conductors.
  • the Applicant has sought aluminum conductors which have the sought-after properties which can be produced at competitive costs.
  • the subject of the invention is an electrical conductor made of aluminum alloy containing intermetallic phases with iron characterized in that its surface contains little particles of iron intermetallic phases with equivalent diameter greater than 0.8 ⁇ m.
  • the electrical conductor in aluminum alloy according to the invention is characterized in that said alloy contains at least 98.5% aluminum and between 0 and 1.5% iron by weight, and in that less than 2% of the particles of intermetallic phases with iron at the surface of the conductor have an equivalent diameter greater than 0.8 ⁇ m.
  • the equivalent diameter corresponds to the diameter of a surface circle equivalent to the visible section of the particle.
  • the number and size of the phase particles Intermetallic iron can be measured by analytical techniques well known surfaces, such as scanning electron microscopy (SEM) to low energy with atomic number contrast combined with a device image analysis.
  • the particles of surface iron intermetallic phases include, as illustrated in FIG. 1, all the binary, ternary or other intermetallic particles, such as Al 3 Fe alone or in combination with Mn, Cu, Si, Ni, ..., which are not entirely immersed in the aluminum matrix or which, while being immersed in said matrix, approach within 0.2 ⁇ m of the surface of said matrix.
  • the proportion of iron by weight is between 0.05% and 1.0%.
  • a proportion of iron less than 0.05 leads to prohibitive manufacturing costs and generally reduces the mechanical characteristics of the conductor.
  • a proportion iron greater than 1.0% leads to an electrical resistivity of the conductor which exceeds the tolerances normally allowed.
  • Said alloy optionally contains other elements in solid solution or precipitates in simple or intermetallic phase, such as Si, Cu, Mg, ...
  • Said alloy is advantageously chosen from alloys of the AA1000 and AA6000 series, such than AA1110 (equivalent to AP 131050), AA1370, AA6101 and AA6201.
  • the conductor according to the invention can be obtained by spinning and / or drawing or molding according to known methods.
  • the conductors in the form of wires are preferably obtained by the CLC process (continuous casting and rolling) followed of a wire drawing according to known methods.
  • the conductor can be in any metallurgical state compatible with the application.
  • the electrical resistivity of the conductor is preferably less than 3.5 ⁇ .cm, and preferably still less than 3.0 ⁇ .cm.
  • the conductor according to the invention is used in the form solid core wire, that is to say it is formed of a single conductive strand possibly coated with an insulating sheath, or with a wired core, that is to say it is formed of a set of elementary strands, generally twisted and possibly coated with an insulating sheath.
  • the conductor according to the invention is also advantageously used in electrical connection devices.
  • the conductor according to the invention is advantageously obtained by a process comprising a surface treatment according to the second object of the invention.
  • Said process optionally includes drawing operations which are carried out before and / or after surface treatment.
  • the conductor aluminum is treated on parade or, in particular in the case of single pieces, by immersion in a succession of tanks.
  • Figure 2a the most advantageous configuration for treatment with parade is that of Figure 2a. But it is also possible to use a configuration where the two successive treatments are clearly separated as shown in Figure 2b. These two configurations correspond to a socket liquid current: current is transmitted by an electrode to the electrolyte which in turn transmits to the conductor to be processed. You can also use a plug direct current which allows good control of the voltage applied to the conductor but poses problems of driver deterioration.
  • Figures 3a and 3b represent two configurations in direct connection: the current is transmitted directly to the conductor to be treated by mechanical contact.
  • the first treatment is carried out in a very alkaline medium with a pH> 8.
  • a very alkaline medium with a pH> 8.
  • Different electrolytes meeting this criterion can be used, but due to their low cost and their high chemical stability, it is particularly advantageous to use caustic soda (NaOH) or potash (KOH), concentration between 10 and 100 g / l.
  • Treatment is carried out at a temperature between 40 ° C and 100 ° C, under an applied voltage between 2 and 10 V. Below 2 V the scrolling speeds are too low ( ⁇ 10 m / min). Above 10 V the treatment leaves a significant residual oxide layer (> 100 ⁇ ) and leads to too high contact resistances.
  • the second treatment is carried out in a weakly acidic medium (pH between 4 and 7).
  • a weakly acidic medium pH between 4 and 7
  • Different electrolytes may be suitable such as boric acid, acid phosphoric, tartaric acid.
  • This treatment is carried out at a temperature ambient which depends on the electrolyte, but which is generally between ambient and 60 ° C.
  • Tartaric acid combined with ammonia to give ammonium tartrate is a particularly suitable electrolyte because it gives good results at room temperature.
  • the applied voltage is included between 1V and 5V. Below 1V the treatment gives a too thin layer and leads to poor behavior over time of contact resistances and corrosion resistance. Above 5V the oxide layer formed is thick and leads to high contact resistances.
  • the immersion time or the scrolling speed and the various parameters of the treatments especially the applied voltage.
  • each of the treatment tanks one can add to the electrolyte, according to a known technique, detergents or emulsifiers intended to limit the pollution of the bath, electrodes and mechanisms by greases.
  • Figure 1 shows a schematic cross section of a conductor in aluminum according to the invention.
  • the conductor consists of a matrix (1), of particles of iron intermetallic phases (2, 3, 4), possibly of particles of iron-free intermetallic phases (5) and possibly of elements in solution solid.
  • Surface particles include particles touching the surface (2) and particles immersed in the aluminum matrix and approaching the surface with a distance P less than 0.2 ⁇ m, such as the particle (3).
  • FIG. 2a represents the preferred configuration of the invention with taking of liquid stream.
  • the conductor (10) circulates continuously in the treatment tanks (13, 14 and 15) using, in the case of a thread, an unwinder (11) and a reel (12).
  • an alternating voltage (18) induces a current alternating in the conductor (10) using the electrodes (19 and 20).
  • a direct voltage (17) induces a direct current in the conductor (10) at using the electrodes (20 and 21), the conductor (10) being in anodic polarization in the tank (15).
  • FIG. 2b shows another configuration with a liquid outlet.
  • a tank (16) and an electrode additional (22) have been added to separate the two treatments, while now the principle of the liquid outlet.
  • FIGs 3a and 3b show two other configurations with direct connection to the driver (30 and 31).
  • Figure 4 is a diagram of the contact resistance measurement method.
  • Figure 5 is a diagram of the test loop for the thermal cycling test.
  • Six junction fittings (50) are joined together by the conductors under test (51), one of which is used as a reference (52).
  • the conductor temperature of reference (52) is measured in the middle using a thermocouple (53).
  • Of voltage drop measurement points (54) are arranged at a distance (L) of on either side of the center of each junction fitting (50).
  • Two points of measurement of the voltage drop (55) separated by a distance (Lo) are also fitted on the reference conductor (52).
  • the test loop is connected to an electrical supply (60) which delivers either an alternating current, for the thermal cycling, i.e. direct current for resistance measurements of fittings and reference conductor.
  • Figure 6 shows the distribution of phase particle sizes intermetallic to iron of an aluminum alloy conductor AA 1370 according to art anterior (a, b) and according to the invention (c, d).
  • the ordinate gives the frequency appearance of particles.
  • the distributions a and c correspond to the diameter equivalent of particles; the distributions b and d correspond to the dimension maximum.
  • Figure 7 shows the distribution of phase particle sizes intermetallic to iron of an aluminum alloy conductor AP 131050 according to the prior art (a, b) and according to the invention (c, d).
  • the ordinate gives the frequency appearance of particles.
  • the distributions a and c correspond to the diameter equivalent of particles; the distributions b and d correspond to the dimension maximum.
  • Examples 1 to 4 relate to conductors in the form of wires. In these examples, drivers have undergone the following tests:
  • the quality of the contact was expressed in terms of the average value of the 10 best values, Rc.
  • the measurement was made under a force (F) of 5 newtons, for ⁇ 0.8 and 3 newtons for ⁇ 0.5, an intensity of 100 mA and a voltage in 20 mV open circuit.
  • the test loop was subjected to 200 thermal cycles by passing an overcurrent which brought the reference conductors to 120 ° C. Each cycle included a 15 minute warm up period and a 15 minute natural cool down period.
  • the evaluation of the contact resistance was carried out using the measurement of the junction resistance. For this we imposed an intensity (Io) in the loop and we measured the voltage drop (Uo) between two points each located at a distance (L) and on either side of the center of the fitting, the conductors being naked in these places.
  • the change in the junction resistance of all the fittings was given by the change in the ratio (K) between the start and the end of the test, which change was expressed as a percentage.
  • the distance (L) was 125 mm, the length (Lo) 254 mm and the intensity (Io) of 1A.
  • the wires treated according to the invention were exposed to salt spray (5% NaCl) for 96 hours. At the end of this period, a new measurement of the contact resistance was carried out using the cross-thread method.
  • Lot A came from a reel raw wire.
  • Lot B has undergone a surface treatment according to the invention, by scrolling in successive tanks: the AC treatment has been carried out in a bath at 60 ° C. containing 50 g / l of 98% pure NaOH and under a voltage of 5 V, the running speed being 12 m / min; treatment in direct current was carried out in a bath containing 30 g / l of tartaric acid, of which the pH had been adjusted to 5 using ammonia, and under a voltage of 1 V.
  • Lot A came from of a spool of raw wire.
  • Lot B has undergone a surface treatment according to the invention, by scrolling through successive tanks, with a neutralization phase intermediate: the AC treatment was carried out in a 62 ° bath ° C containing 50 g / l of 98% pure NaOH and at a voltage of 6 V, the speed of scrolling being 24 m / min; dc processing was performed in a bath containing 30 g / l of tartaric acid, the pH of which had been adjusted to 5 using of ammonia, and at a voltage of 1 V; neutralization treatment intermediate was carried out in a 69% nitric acid bath.
  • Lot A came from a coil of nickel-plated wire (obtained from the Company Wire drawing and rolling mills of the Mediterranean (TLM), of the ALCATEL group CABLE).
  • Lot B came from a spool of raw, unshaven wire and has been kept without treatment.
  • Batches C, D and E come from a spool of thread having undergone a shaving phase during drawing. Lot C was kept without treatment.
  • the lot D has undergone the anodizing treatment of the prior art, in a bath containing 100 g / l of phosphoric acid, at an alternating voltage of 5 V, at a temperature of 75 ° C and at a running speed of 60 m / min.
  • Lot E has suffered a surface treatment according to the invention, with a neutralization phase intermediate, by scrolling in successive tanks: current treatment alternative was carried out in a bath at 65 ° C containing 50 g / l of 98% pure NaOH and under a voltage of 7.5 V, the running speed being 48 m / min; the DC treatment was carried out in a bath containing 30 g / l of acid tartaric, the pH of which had been adjusted to 5.5 using ammonia, and under a 1.5 V voltage; the intermediate neutralization treatment was carried out in a 69% nitric acid bath.
  • the corrosion pits observed on the wires of lot B are much less deeper than those observed on the wires of lot A.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)

Claims (16)

  1. Elektrischer Leiter aus einer Aluminiumlegierung, dadurch gekennzeichnet, daß die Legierung mindestens 98,5 Masse-% Aluminium und 0 bis 1,5 Masse-% Eisen enthält und daß weniger als 2 % der intermetallischen Eisen-Phasenteilchen auf der Oberfläche des Leiters einen Äquivalentdurchmesser haben, der größer als 0,8 µm ist.
  2. Leiter nach Anspruch 1, dadurch gekennzeichnet, daß der Eisenanteil an der Masse zwischen 0,05 und 1,0 % liegt.
  3. Leiter nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Legierung aus den Legierungen der Serien AA1000 und AA6000 gewählt wird.
  4. Leiter nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß er einen spezifischen elektrischen Widerstand besitzt, der kleiner als 3,5 µΩ·cm ist.
  5. Verfahren zur Herstellung des Leiters nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet. daß es eine Oberflächenbehandlung umfaßt, bei der aufeinanderfolgend eine erste elektrochemische Behandlung mit Wechselstrom in einem stark alkalischen Medium mit einem pH-Wert von größer als 8 und dann eine zweite elektrochemische Behandlung mit Gleichstrom in einem leicht sauren Medium mit einem pH-Wert von 4 bis 7 durchgeführt wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Oberflächenbehandlung im Anschluß an die elektrochemische Behandlung mit Wechselstrom eine chemische Neutralisationsbehandlung in einem Salpetersäure enthaltenden Bad umfaßt.
  7. Verfahren nach einem der Ansprüche 5 und 6, dadurch gekennzeichnet, daß das Bad zur elektrochemischen Behandlung mit Wechselstrom aus Natrium- oder Kaliumhydroxid besteht und der Gehalt an Natriumhydroxid des Bades für die erste Behandlung zwischen 10 g/l und 100 g/l liegt.
  8. Verfahren nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß die elektrochemische Behandlung mit Wechselstrom bei einer Spannung von 2 bis 10 V erfolgt und daß das Bad für die erste Behandlung auf einer Temperatur zwischen 40°C und 100°C gehalten wird.
  9. Verfahren nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß das Bad für die elektrochemische Behandlung mit Gleichstrom aus Ammoniumtartrat besteht.
  10. Verfahren nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß die elektrochemische Behandlung mit Gleichstrom bei einer Spannung von 1 bis 5 V erfolgt.
  11. Verfahren nach einem der Ansprüche 5 bis 10, dadurch gekennzeichnet, daß der zu behandelnde Leiter zuerst mechanisch geschabt wird.
  12. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß es eine Strangguß- und Walzphase umfaßt, an die sich ein Drahtziehen mit beliebigen bekannten Mitteln anschließt.
  13. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß es eine Strangpreßphase umfaßt.
  14. Draht mit massiver Seele. die blank oder mit einer Isolierhülle versehen ist, dadurch gekennzeichnet. daß er einen Leiter nach einem der Ansprüche 1 bis 4 aufweist.
  15. Draht mit verseilter Seele, die blank oder mit einer Isolierhülle versehen ist, dadurch gekennzeichnet, daß er Leiter nach einem der Ansprüche 1 bis 4 aufweist.
  16. Anschlußvorrichtung, dadurch gekennzeichnet, daß sie einen Leiter nach einem der Ansprüche 1 bis 4 aufweist.
EP19960420254 1995-07-27 1996-07-25 Aluminiumleiter mit verbesserten elektrischen Kontakteigenschaften und Verfahren zur Herstellung desselben Expired - Lifetime EP0756289B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9509382A FR2737336B1 (fr) 1995-07-27 1995-07-27 Procede de traitement de surface de fils electriques en aluminium
FR9509382 1995-07-27

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EP0756289A1 EP0756289A1 (de) 1997-01-29
EP0756289B1 true EP0756289B1 (de) 1999-03-24

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EP19960420254 Expired - Lifetime EP0756289B1 (de) 1995-07-27 1996-07-25 Aluminiumleiter mit verbesserten elektrischen Kontakteigenschaften und Verfahren zur Herstellung desselben

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EP (1) EP0756289B1 (de)
DE (1) DE69601837T2 (de)
FR (1) FR2737336B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9859038B2 (en) 2012-08-10 2018-01-02 General Cable Technologies Corporation Surface modified overhead conductor
US10957468B2 (en) 2013-02-26 2021-03-23 General Cable Technologies Corporation Coated overhead conductors and methods
BR112018001195B1 (pt) 2015-07-21 2022-08-09 General Cable Technologies Corp Acessórios elétricos para sistemas de transmissão de potência e métodos para preparar tais acessórios elétricos

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3827917A (en) * 1969-06-18 1974-08-06 Kaiser Aluminium Chem Corp Aluminum electrical conductor and process for making the same
FR2179515A1 (en) * 1972-04-11 1973-11-23 Pechiney Aluminium Aluminium-based electrical conductor - by drawing and heat treating alloy contg magnesium, silicon and iron
FR2298619A1 (fr) * 1975-01-22 1976-08-20 Pechiney Aluminium Procede et traitement superficiel d'un fil en aluminium a usage electrique
BR8103057A (pt) * 1981-05-18 1982-12-21 Pirelli Sa Liga de aluminio para condutores eletricos e processo para a sua obtencao

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FR2737336B1 (fr) 1997-09-05
DE69601837D1 (de) 1999-04-29
EP0756289A1 (de) 1997-01-29
FR2737336A1 (fr) 1997-01-31
DE69601837T2 (de) 1999-08-12

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