EP0408469B1 - Kupfer-Eisen-Kobalt-Titanlegierung mit guten mechanischen und elektrischen Eigenschaften und Verfahren zu ihrer Herstellung - Google Patents

Kupfer-Eisen-Kobalt-Titanlegierung mit guten mechanischen und elektrischen Eigenschaften und Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0408469B1
EP0408469B1 EP90420315A EP90420315A EP0408469B1 EP 0408469 B1 EP0408469 B1 EP 0408469B1 EP 90420315 A EP90420315 A EP 90420315A EP 90420315 A EP90420315 A EP 90420315A EP 0408469 B1 EP0408469 B1 EP 0408469B1
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European Patent Office
Prior art keywords
alloy
content
temperature
process according
conductivity
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EP90420315A
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English (en)
French (fr)
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EP0408469A1 (de
Inventor
Christian Gandossi
Alain Picault
Laurent Mineau
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Trefimetaux SAS
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Trefimetaux SAS
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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
    • H01B1/026—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent

Definitions

  • the present invention relates to a copper-iron-cobalt-titanium alloy, its process for manufacturing it, as well as its field of use.
  • the electrical interconnection is evolving rapidly. Whether in the field of electronics (component support grids, contacts), or in the field of connectors (clips, lugs, connectors), the size of the parts carrying the electric current is constantly decreasing. On the other hand, the complexity of the form of these contacts is only increasing.
  • the manufacturer of copper alloys and semi-finished products is therefore subject to the following challenge: increase the electrical and thermal conductivity of traditional alloys to limit the heating of connectors and maintain or improve the level of mechanical properties. The improvement of these mechanical properties must obviously include the ability of the alloy to be deformed in the directions parallel and perpendicular to the rolling direction.
  • a ternary copper alloy with 2% nickel and 0.5% silicon has been known for a long time which has good mechanical properties (mechanical resistance 600 MPa); however, such an alloy has an electrical conductivity limited to 60% IACS because of the solubility of the Ni2Si precipitate.
  • US Pat. No. 4,559,200 shows the improvements brought about by small additions of magnesium or nickel to a CuFeTi alloy. More recently, a copper-iron-cobalt-titanium alloy described in Polish patent No. 115185 has been proposed covering a wide range of compositions. These alloys can reach 85% IACS conductivity for a tensile strength of 440 MPa. However, these properties to be achieved require two heat treatments.
  • Example 1 shows that this ratio is highly significant for expressing the variability of the electrical conductivity. In the field where Co / Fe is between 0.1 and 0.9 and more particularly between 0.15 and 0.45 the electrical conductivity is particularly high. It should be noted that the electrical conductivity values of Example 1 are to be considered in a relative and not absolute manner, these tests being selection tests in the laboratory, which do not necessarily reproduce exactly all the means that can be used industrially, which influences on absolute conductivity values.
  • the compositions of iron, cobalt, titanium are respectively between 0.1 and 1%, between 0.05 and 0.4 and between 0.035 and 0.6%, as for the residual oxygen content it is preferably less than 20 ppm.
  • Obtaining high-performance alloys requires deoxidation of the bath of the liquid alloy, in particular to have control over the composition of the bath and to prevent the addition elements, titanium in particular, from playing the role of deoxidation and are not eliminated.
  • the composition is also well controlled by preparation under vacuum, the oxygen content then being very low, generally less than 0.0005%. But due to the high cost, the Applicant preferred a conventional fusion, with deoxidation of the bath.
  • the Applicant has thus carried out semi-industrial tests with deoxidation of the Cu Fe Co Ti alloy bath of composition according to the invention. She observed that phosphorus, a deoxidizing agent often used in the prior art, did not lead to a very efficient alloy, so she studied and compared several deoxidizing agents (see example 2): phosphorus, magnesium and boron. The Applicant has surprisingly found that boron leads to more efficient alloys than those obtained with phosphorus or magnesium although the latter is, on the basis of thermodynamic data, the most powerful deoxidizing agent of the three.
  • boron makes it possible to obtain a bath of low residual oxygen content, and, on the other hand, the boron oxide formed is easily removed from the bath, unlike the other oxides, which, among other consequences, avoids the hard spots of the alloy during cutting at high speed, and finally that the residual boron content in the alloy is very low, generally less than 0.0005%, (but nevertheless detectable); the consequence is a high level of conductivity and a relatively low temperature TM, TM being the temperature of the precipitation treatment which leads to the maximum conductivity (see FIG. 3 of Example 2); finally, note the greater fineness of dispersion of the precipitates in the case of deoxidation with boron.
  • the precipitation treatment is part of the transformation phase of the alloy which, after the casting of the alloy, includes its homogenization between 800 ° C and 1000 ° C for a time between 0.1 and 10 hours, its hot rolling up to 650 ° C followed by a possible quenching which can vary from 20 ° C / min to 2000 ° C / min , its cold rolling with one or more intermediate anneals; however, the excellent cold deformability of the alloy according to the invention generally allows it to be shaped with only a thermal precipitation treatment, which constitutes an economic range.
  • the properties of the semi-finished products obtained, whether electrical conductivity or mechanical characteristics, also depend on the transformation phase and in particular on the thermal precipitation treatment. With regard to the conductivity, FIG.
  • the precipitation treatment takes place at a temperature between TM and Tm and preferably close to Tm to obtain "balanced" properties according to the invention:% IACS> 80 and Rm> 500 MPa.
  • Tm will be, at most, 80 ° C lower than TM; another method to define Tm is to consider the slope of the% IACS curve as a function of the temperature: Tm corresponds to the temperature where the slope begins to increase appreciably and reaches for example the value of 0.3% IACS / ° C.
  • the slope change area is preferred.
  • Example 3 clearly shows that only the alloy according to the invention (test C ′) exhibits high properties both in conductivity and mechanical properties, but it is however necessary to note the advantage of this type of treatment for greatly increasing the characteristics. mechanics of other alloys (tests A 'and B') when average conductivities (around 70% IACS) are sufficient.
  • a precipitation treatment "at low temperature”, between 350 ° and 550 ° C will give maximum mechanical resistance (tests A 'and B') while a treatment at "high temperature” between 450 ° and 650 ° C will rather lead to maximum conductivity, the common domain between 450 ° and 550 ° being that in which the mechanical and conductivity properties are "balanced".
  • the duration of the precipitation treatments varies according to the technology used: from 1 hour to 10 hours in a static oven and from 10 seconds to 30 minutes in a passing oven.
  • the alloy according to the invention it is possible to reinforce the mechanical properties by adding elements such as aluminum, tin, zinc, nickel, silver, chromium to the basic composition. , beryllium, rare earths.
  • the total sum of these elements must be less than 1.5% if one wants to keep sufficient conductivity: these additions of elements generally reducing the electrical conductivity constitute only a secondary form of the invention.
  • the invention shows that only the combination of particular means that are the composition of the alloy with a ratio Co Fe precise, the particular choice of a deoxidizing agent and a temperature range for the precipitation treatment, makes it possible to obtain both a high electrical conductivity and a high mechanical resistance.
  • Example 4 illustrates well the "classic" properties of alloys of the prior art: when they have a high electrical conductivity their mechanical resistance is low and vice versa. It clearly shows the advantageous performances of the product obtained according to the invention.
  • the range of production of the alloys according to the invention is particularly economical since high work hardening rates can be achieved with a single heat treatment: the precipitation heat treatment.
  • the alloys of the invention are suitable for applications requiring simultaneously high conductivity and mechanical resistance, they are recommended for the manufacture of conductive elements for electronics and in connection and in particular for applications such as leadframes, springs contact, connections.
  • FIG. 1 illustrates, on a diagram having the ratio Ti / (Fe + Co) on the abscissa and the electrical conductivity in% IACS on the ordinate, the results obtained for the 7 tests denoted R1 to R7, described in Example 1.
  • FIG. 2 illustrates, on a diagram having the Co / Fe ratio on the abscissa and the electrical conductivity in% IACS on the ordinate, the results obtained for the 7 tests, denoted R1 to R7, described in Example 1, which allow the plotting of a curve.
  • FIG. 3 illustrates, on a diagram having the temperature in ° C on the abscissa and the electrical conductivity in% IACS on the ordinate, the variations in electrical conductivity as a function of the precipitation treatment temperature for each of the three deoxidizing agents studied in Example 2 magnesium (curve A), phosphorus (curve B), boron (curve C).
  • FIG. 4 illustrates, on a diagram having on the abscissa the mechanical resistance in MPa, and on the order of the electrical conductivity in% IACS, the performances of the alloy obtained according to the invention (C '), according to Polish patent n ° 115185 , (D and F) and according to American patent n ° 4559200 (E), as indicated in example 4.
  • the zone (III) where the alloy obtained according to the invention is found is that of the alloys having at the same time mechanical characteristics and electrical conductivity high.
  • Table 2 which follows indicates the conductivity of each alloy expressed in% IACS measured at room temperature, as a function of the precipitation temperature:
  • Table 2 shows that the maximum conductivity values, expressed in% IACS and underlined in this table, are obtained for a precipitation temperature close to 560 ° C and that these maximum values are very dispersed.
  • Ti / (Fe + Co) ratio of Polish patent n ° 115185 shows that, on the one hand in the range 0.25 - 1 for Ti / (Fe + Co) claimed for this report, the conductivity varies a lot for similar values (comparison of tests R1, R2, R3, R4 between them and tests R5, R6, R7 between them) and that, on the other hand this ratio Ti / (Fe + Co) does not make it possible to determine the favorable domain of high conductivities since the 7 representative points do not make it possible to draw a curve having an indisputable maximum (see FIG.
  • This example illustrates a modality of the shaping of alloys produced in all points as in example 2 (test A 'of example 3 corresponds to test A of example 2, likewise for B 'and C')), except that the precipitation treatment takes place at a lower temperature (505 ° C for A ', 485 ° C for B', 475 ° C for C ') for 4 hours and the final rolling corresponds at a thickness reduction of 29%:
  • the following properties are obtained:
  • These alloys exhibit a hardness greater than 130 HV after 30 minutes at 450 ° C., which illustrates their excellent resistance to softening.
  • FIG. 4 situates these tests in a plane having the mechanical resistance on the abscissa and the electrical conductivity on the ordinate and clearly illustrates the advantage of the invention.
  • the non-comparative test F is given for information: it corresponds to test D but with a transformation range comprising two heat treatments instead of one.

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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)
  • Manufacture And Refinement Of Metals (AREA)

Claims (11)

  1. Verfahren zur Herstellung einer Cu-Fe-Co-Ti-Legierung mit enem Schritt zur Erzeugung der Legierung und einem Schritt zur Umwandlung der Legierung, der eine Ausscheidungswärmebehandlung aufweist, dadurch gekennzeichnet, daß
    a) man eine Legierung erzeugt, deren Zusammensetzung den folgenden Bedingungen genügt (Gewichtszusammensetzungen):
    - Co/Fe-Verhältnis zwischen 0,10 und 0,90
    - Ti/(Fe + Co)-Verhältnis zwischen 0,30 und 1
    - Eisengehalt im Bereich von 0,030 bis 2 %
    - Kobaltgehalt im Bereich von 0,025 bis 1,8 %
    - Titangehalt im Bereich von 0,025 bis 4 %
    - Sauerstoffgehalt unter 50 ppm
    - Gesamtgehalt an anderen eventuellen Zusätzen unter 1,5 %
    - Gehalt an metallischen Verunreinigungen unter 0,1 % bei jeder davon unter 0,015 %
    - Rest Kupfer,
    b) man das Bad der flüssigen Legierung desoxidiert, indem man Bor in das Bad einführt und daraus das gebildete Boroxid entfernt, und
    c) man die kaltverformte Legierung einer Ausscheidungswärmebehandlung bei einer Temperatur von höchstens 80°C unter der Temperatur TM unterwirft, die zur maximalen elektrischen Leitfähigkeit führt.
  2. Verfahren nach dem Anspruch 1, bei dem das Verhältnis Co/Fe im Bereich von 0,15 bis 0,45 liegt.
  3. Verfahren nach dem Anspruch 2, bei dem der Sauerstoffgehalt unter 20 ppm ist.
  4. Verfahren nach dem Anspruch 2, bei dem der Eisengehalt im Bereich von 0,1 bis 1 % liegt.
  5. Verfahren nach dem Anspruch 2, bei dem der Kobaltgehalt im Bereich von 0,05 bis 0,4 % liegt.
  6. Verfahren nach dem Anspruch 2, bei dem der Titangehalt im Bereich von 0,035 bis 0,6 % liegt.
  7. Verfahren nach dem Anspruch 2, bei dem man das Titan in Form einer Vorlegierung nach Einführung des Bors derart einführt, um Titanverluste zu vermeiden und um ein Schmelzen und ein Gießen unter Vakuum zu vermeiden.
  8. Verfahren nach dem Anspruch 2, bei dem die Ausscheidungswärmebehandlung bei einer unter der Temperatur TM liegenden Temperatur durchgeführt wird, für die die Neigung der elektrischen Leitfähigkeitskurve in % IACS als Funktion der Temperatur im Bereich von 0,1 bis 0,3 % IACS/°C liegt.
  9. Nach irgendeinem der Ansprüche 1 bis 8 erhaltene Legierung.
  10. Legierung nach dem Anspruch 9,
    dadurch gekennzeichnet, daß
    sie weniger als 10 ppm Bor enthält.
  11. Verwendung der Legierung nach irgendeinem der Ansprüche 9 und 10 zur Herstellung leitender Elemente für die Elektronik und die Anschlußtechnik und insbesondere Trägergitter von Bauteilen, die Kontaktfedern, die Verbindungen.
EP90420315A 1989-07-07 1990-07-04 Kupfer-Eisen-Kobalt-Titanlegierung mit guten mechanischen und elektrischen Eigenschaften und Verfahren zu ihrer Herstellung Expired - Lifetime EP0408469B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8909906A FR2649418B1 (fr) 1989-07-07 1989-07-07 Alliage de cuivre-fer-cobalt-titane a hautes caracteristiques mecaniques et electriques et son procede de fabrication
FR8909906 1989-07-07

Publications (2)

Publication Number Publication Date
EP0408469A1 EP0408469A1 (de) 1991-01-16
EP0408469B1 true EP0408469B1 (de) 1993-11-24

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EP90420315A Expired - Lifetime EP0408469B1 (de) 1989-07-07 1990-07-04 Kupfer-Eisen-Kobalt-Titanlegierung mit guten mechanischen und elektrischen Eigenschaften und Verfahren zu ihrer Herstellung

Country Status (8)

Country Link
US (1) US5026434A (de)
EP (1) EP0408469B1 (de)
JP (1) JPH0694578B2 (de)
KR (1) KR940002684B1 (de)
DE (1) DE69004756T2 (de)
ES (1) ES2046754T3 (de)
FI (1) FI95815C (de)
FR (1) FR2649418B1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6282064B1 (en) * 1994-03-15 2001-08-28 International Business Machines Corporation Head gimbal assembly with integrated electrical conductors
US6539609B2 (en) 1994-07-05 2003-04-01 International Business Machines Corporation Method of forming a head gimbal assembly
FR2809626B1 (fr) * 2000-05-30 2003-03-07 Poudres & Explosifs Ste Nale Seringue sans aiguille avec membrane d'isolation d'un ejecteur multiconduit
CN113265558B (zh) * 2021-03-22 2022-10-14 江西省科学院应用物理研究所 一种抗弯折性能优异的铜铁合金及其加工方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783143A (en) * 1954-06-24 1957-02-26 Driver Co Wilbur B Age-hardenable, copper-base alloy
US4047980A (en) * 1976-10-04 1977-09-13 Olin Corporation Processing chromium-containing precipitation hardenable copper base alloys
JPS6039139A (ja) * 1983-08-12 1985-02-28 Mitsui Mining & Smelting Co Ltd 耐軟化高伝導性銅合金
DE3511999A1 (de) * 1985-04-02 1986-10-02 Wieland-Werke Ag, 7900 Ulm Verwendung einer kupfer-titan-kobalt-legierung als werkstoff fuer elektronische bauteile
JPS6250426A (ja) * 1985-08-29 1987-03-05 Furukawa Electric Co Ltd:The 電子機器用銅合金
JPH0788545B2 (ja) * 1987-04-28 1995-09-27 三菱マテリアル株式会社 特性異方性の少ない高強度高靭性Ｃｕ合金

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DE69004756T2 (de) 1994-05-05
KR940002684B1 (ko) 1994-03-30
KR910003132A (ko) 1991-02-27
FR2649418B1 (fr) 1991-09-20
EP0408469A1 (de) 1991-01-16
JPH0353036A (ja) 1991-03-07
FI903449A0 (fi) 1990-07-06
ES2046754T3 (es) 1994-02-01
FI95815C (fi) 1996-03-25
JPH0694578B2 (ja) 1994-11-24
FR2649418A1 (fr) 1991-01-11
DE69004756D1 (de) 1994-01-05
FI95815B (fi) 1995-12-15
US5026434A (en) 1991-06-25

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