EP0225889A1 - Neue legierungen mit höheren elektrischen und mechanischen leistungsfähigkeiten, deren zubereitung und anwendungen, insbesondere in den elektrischen, elektronischen und verbindungstechnischen gebieten - Google Patents

Neue legierungen mit höheren elektrischen und mechanischen leistungsfähigkeiten, deren zubereitung und anwendungen, insbesondere in den elektrischen, elektronischen und verbindungstechnischen gebieten

Info

Publication number
EP0225889A1
EP0225889A1 EP86902844A EP86902844A EP0225889A1 EP 0225889 A1 EP0225889 A1 EP 0225889A1 EP 86902844 A EP86902844 A EP 86902844A EP 86902844 A EP86902844 A EP 86902844A EP 0225889 A1 EP0225889 A1 EP 0225889A1
Authority
EP
European Patent Office
Prior art keywords
alloys
metal
matrix
powder
alloys according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP86902844A
Other languages
English (en)
French (fr)
Inventor
Jules Caisso
Martine Cahoreau
Edmond Dedieu
Michel Grosbras
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.)
Trefimetaux SAS
Original Assignee
Trefimetaux SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Trefimetaux SAS filed Critical Trefimetaux SAS
Publication of EP0225889A1 publication Critical patent/EP0225889A1/de
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H01H1/02372—Composite material having a noble metal as the basic material and containing oxides containing as major components one or more oxides of the following elements only: Cd, Sn, Zn, In, Bi, Sb or Te
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/025—Composite material having copper as the basic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state

Definitions

  • the invention relates to new alloys with both, in particular, high electrical and mechanical performance, their manufacture and their applications, in particular, in the electrical, electronic and connector fields.
  • This phase can be formed by precipitation from a supersaturated solid solution.
  • this technique has the drawback of causing the loss of mechanical properties at high temperature as a result of the total or partial solution of the precipitates.
  • fine dispersions of hard particles are introduced directly into the metal or formed by internal oxidation of the low-alloyed metal, which leads to a high hardening which only collapses in the vicinity of the fu ⁇ if we.
  • the invention therefore aims to provide new alloys having both high conductive and mechanical properties.
  • the invention also aims to provide materials based on these alloys which can be used in particular in the electrical, electronic and connector fields, thanks in particular to their good mechanical strength and their high conductivity.
  • the alloys according to the invention which comprise a matrix based on at least one conductive metal M, are characterized in that they are formed from a homogeneous dispersion in the matrix of coherent particles stable from one or more associations of ions of type M, M ′, fJ in which M represents the metal or metals of the matrix, M ′ represents a metal different from M, capable of undergoing internal oxidation and O 2 represents oxygen.
  • coherent particles designates particles which, unlike the so-called incoherent particles present in alloys of the MM '0 type developed ⁇ according to the prior art, have a continuity of the crystalline planes at the particle-metal interface of the matrix and significant deformations in the vicinity of the interface.
  • the average size of these particles is less than approximately 20 nm, in particular of the order of 10 nm.
  • these particles are distributed uniformly in the metal matrix M, the interparticle distance being approximately 60 nm, which gives great homogeneity to the alloy.
  • coherent particles are, in fact, intimately linked to the metal matrix and during cutting of the material, unlike incoherent particles, they do not separate from the matrix and do not give rise to an abrasive action. This results, in particular, in less wear of the cutting tools.
  • the coherent particles practically do not coalesce during annealing, which gives these alloys better resistance to annealing than that of alloys based on incoherent particles.
  • the matrix is constituted by a single conductive metal M.
  • M represents copper.
  • Another suitable conductive metal is silver.
  • the matrix comprises at least one base metal M forming one or more solid solutions with one or more solutes R.
  • Preferred solid solutions of this type include a copper-based matrix containing an R element such as P, Sn or Zn as a solute.
  • the matrix is based on at least one metal M hardened by the precipitation of one or more elements A, by a phenomenon of structural hardening or even by spinodal decomposition (precipitation with ordering of the atoms of the elements of addition).
  • the matrix is based on copper, hardened by the precipitation of elements A, such as, for example, Fe, Fe and P, Ni and Si, Ni and Al, Zr, Cr, Co or Co and Si. At a content which can go up to approximately 1%.
  • elements A such as, for example, Fe, Fe and P, Ni and Si, Ni and Al, Zr, Cr, Co or Co and Si.
  • precipitation hardening alloys such as Cu-Fe, Cu-Fe-P, Cu-Ni-Si, Cu-Ni-Al, Cu-Zr, Cu-Cr, Cu-Co or Cu-Co-Si.
  • the associations of ions __ '__' £. dispersed in the metallic matrix correspond to a single type of association.
  • the alloys of the invention comprise several types of associations M, M '0, the symbols M' then having different meanings.
  • the ions _M ' more particularly represent aluminum, thorium beryllium or titanium ions, aluminum being preferred. Alloys comprising coherent particles of associations of ions (Cu, Al, 0) dispersed in a copper matrix formed from solid solutions Cu-Al at 0.25-0.30% Al by weight approximately of Al, allow a good compromise to be achieved between mechanical properties and electrical properties.
  • Alloys of this type in their raw state of manufacture are characterized by an electrical conductivity of at least 85% IACS, a breaking load greater than about 500 MPa and an elastic limit of 0.2% greater than approximately 450 MPa.
  • Alloys of particularly high electrical and mechanical performance are produced according to the internal oxidation process described below, from a powder containing the base metal M of the matrix, the metal or metals M 'susceptible to oxidize and, if necessary, the elements with hardening effect.
  • the process > according to the invention, for manufacturing the alloys defined above is characterized in that the starting alloy powder is subjected ? whose particle size is compatible with the formation of coherent particles ; to the action of an oxidant formed of a powder of granulometry in the order of m of a metal oxide capable of supplying by thermal decomposition the oxygen necessary for the internal oxidation of M, the starting alloy comprising a matrix based on at least one metal.
  • M if necessary hardened by one or more R or A elements as defined above.
  • the small particle size on the one hand of the starting bonding, on the other hand, of the oxidant leads to the obtaining of coherent particles of small size, which gives the alloy an elastic limit higher than that obtained with the alloys of the prior art.
  • the mixture of the starting alloy powder and the oxidizer is subjected to at least one densification operation.
  • the starting powder is more particularly formed of particles of particle size less than 400 ⁇ m more especially less than about 180 ⁇ m, especially from 30 to 110 ⁇ m.
  • the oxidant is preferably formed by a metal oxide in which the metal is identical to the base metal of the matrix., M.
  • the oxidant and the starting alloy in the form of powders are mixed and subjected to the internal oxidation operation.
  • the oxidation times and the oxidation temperature will be easily determined by a person skilled in the art from calibration curves giving the oxidation depth as a function of time in the base alloy used.
  • the residual oxygen is reduced by heating under a hydrogen atmosphere.
  • the material obtained is advantageously subjected to at least one densification operation, for example, to a pressure compacting step.
  • the study of the conditions for preparing composite alloys of Cu type shows that it is advantageous to use a powder of Cu-Al alloy containing from 0.10 to 1% approximately by weight. of aluminum, preferably 0.25 to 0.30% by weight approximately, which allows a good compromise to be achieved between the mechanical properties, in particular the temperature resistance and the electrical properties.
  • the particle size of the Cu-Al powder is more particularly between 30 and 10 l im.
  • the oxidizing agent is then advantageously constituted by Cu 2 O in the form of particles of particle size not exceeding 1 ⁇ m approximately.
  • the mixing of Cu-Al with Cu-0 is carried out at a rate of approximately 2 to 2.5 parts by weight of Cu_0 per 100 parts by weight of Cu-Al.
  • the Al content can advantageously be increased up to
  • the internal oxidation is carried out at a temperature of the order of 900 ° C. for approximately 30 to 45 minutes.
  • the residual copper oxide is annealed under a hydrogen atmosphere at a temperature of the order of approximately 800 ° C. for at least 2 hours.
  • a pressure of the order of 70 to 80 MPa makes it possible to obtain a material of density close to 0.8.
  • the particle sizes used make it possible to obtain only coherent particles of small size, which leads to an increase in the elastic limit compared to alloys of type M,, M 'containing incoherent particles.
  • the experimental results show that the elastic limit of the materials of the invention is approximately 7% higher than that of the alloys M, M '0 of the prior art. It is also * interesting to note that in the material thus obtained which contains essentially only coherent particles, the Young's modulus is that of the copper matrix in all the crystal whereas, in the materials with incoherent particles, the Young's modulus is different from that of copper (or M) at the location of the incoherent particles where the modulus is that of Al-0- (or M'O)
  • the tests of deformation at a set speed (cold and after annealing), the hardness tests and the measurements of the electrical conductivity of the alloys obtained made it possible to demonstrate their high mechanical properties, their maintenance after annealing at high temperature. also high electrical properties.
  • these alloys are particularly suitable for applications where good mechanical properties are required simultaneously with high electrical or thermal conductivity.
  • Electronic applications mainly include their use in the form of supports, for example, for transistors, diodes or for integrated circuits.
  • the matrix metal used in the alloys of the invention is very advantageously pure OFHC copper, or deoxidized copper with phosphorus (Cu / b), or alloys very lightly loaded copper.
  • the alloys of the invention in particular those in which the matrix forms a solid solution or is hardened by precipitation of an element are advantageously used for the development of conductive springs, the lugs and the connectors for the automotive, household appliances, electronics.
  • the material retains, in particular, its resistance after operations such as brazing.
  • FIG. 1 representing the crystal structure of the coherent particles of alloys of the invention determined by X-rays
  • the Cu-0 powder used is also subjected to prior degassing.
  • the conditioning of the mixture is followed by a compression of the aggregate of powders enclosed in the container in order to acquire a green tint sufficient to be handled without special precautions.
  • the value of the pressure used is 8 MPa.
  • the hermetic copper container containing the mixture of Cu-Al and Cu-0 powders is placed in an alumina cane placed inside an oven. After a primary vacuum, prior to the cane, a continuous sweep of argon N 55 (at 99.9995% argon) is carried out throughout the duration of the oxidation (temperature rise, holding and cooling times ). The container is cooled in the oven. At the end of the oxidation operation, the mixture is present under form of aggregate.
  • the container is opened at both ends.
  • the powder aggregate is swept by a mixture of hydrogen and nitrogen. This sweeping takes place at a temperature of 820 ° C. after a prior vacuum from the alumina cane.
  • the powder aggregate undergoes a compression treatment which is essential for the good behavior of the sheath of the container during the final densification treatment. powder.
  • the advantageously used sintering and hot extrusion process makes it possible to simultaneously compress and sinter the agglomerated powder obtained after internal oxidation.
  • the device consists of a hydraulic press and an oven si ⁇ killed nearby which allows the heating of the container before its extrusion.
  • the hydraulic press used with a capacity of 80 tons, its container is heated to 400 ⁇ C and the speed of the piston is of the order of one meter per second.
  • the container is heated in the oven with air for one hour.
  • the experiments were carried out in the temperature range 700 ° C * £. t 900 ° C (metal temperature). Dies of circular or rectangular section of various dimensions corresponding to extrusion ratios between 20 and 60 have been used.
  • the previously manufactured cylindrical bar can be subjected to a further drawing treatment.
  • the study of the intensities diffused by the crystal structure a shows that the structure of the coherent particles does not correspond to that of the oxide A1 Anlagen0, but to a cubic structure of an arrangement of ions Cu, Al and 0 .
  • FIG. 1 the structure of the coherent particles determined by X-rays is described, the size of the different types of ions or atoms being arbitrary.
  • the dimensions for oxygen and copper are as follows: (these dimensions are defined along a perpendicular axis in the plane of the figure).
  • Oxygen (largest circle), solid circle 1/8, 5/8, dotted circle 3/8, 7- / 8: copper (medium circles) ⁇ "1/2, ⁇ - 0, 1 C zl /, 3/4 and 0-0. 1/2, 1.
  • Figure 2 corresponds to an electron micrograph (230000 magnification) of the material Cu- (Cu-Al-O), at 0.3% by weight of Al. Examination of this photo reveals the coherent particles of (Cu-Al- 0) visible on the whole grain. As an indication, some of these particles have been identified by arrows.
  • the head test pieces used for the tensile tests have the respective useful length and diameter.
  • FIG. 3 The evolution of the breaking stress, of the plastic elongation as a function of the annealing temperature for an annealing duration of 2 h is shown in FIG. 3 (respectively curves j a, _b_, and of the variation of the stress imposed in MPa or elongation in% depending on the temperature in ° C). The same characteristics are reported in FIG. 4 for an annealing time equal to 10 h.
  • the samples After sintering and hot extrusion, the samples are cold spun at a drawing rate of 20%.
  • the initial bar is subjected to a chemical stripping to remove the surface layer of copper (container), then to a cold drawing to make its section homogeneous.
  • L has measured electrical conductivity is 85% IACS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
EP86902844A 1985-05-10 1986-05-05 Neue legierungen mit höheren elektrischen und mechanischen leistungsfähigkeiten, deren zubereitung und anwendungen, insbesondere in den elektrischen, elektronischen und verbindungstechnischen gebieten Ceased EP0225889A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8507157 1985-05-10
FR8507157A FR2581658B1 (fr) 1985-05-10 1985-05-10 Nouveaux alliages dotes de performances electriques et mecaniques elevees, leur fabrication et leurs applications en particulier dans les domaines electrique, electronique et connectique

Publications (1)

Publication Number Publication Date
EP0225889A1 true EP0225889A1 (de) 1987-06-24

Family

ID=9319179

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902844A Ceased EP0225889A1 (de) 1985-05-10 1986-05-05 Neue legierungen mit höheren elektrischen und mechanischen leistungsfähigkeiten, deren zubereitung und anwendungen, insbesondere in den elektrischen, elektronischen und verbindungstechnischen gebieten

Country Status (6)

Country Link
US (1) US4752333A (de)
EP (1) EP0225889A1 (de)
JP (1) JPS62502813A (de)
KR (1) KR880700441A (de)
FR (1) FR2581658B1 (de)
WO (1) WO1986006871A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2746016C1 (ru) * 2020-03-30 2021-04-05 Владимирова Юлия Олеговна, Жаропрочный и износостойкий материал на основе меди

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US5204318A (en) * 1987-03-27 1993-04-20 Massachusetts Institute Of Technology Preparation of superconducting oxides and oxide-metal composites
US5189009A (en) * 1987-03-27 1993-02-23 Massachusetts Institute Of Technology Preparation of superconducting oxides and oxide-metal composites
US4892581A (en) * 1988-12-05 1990-01-09 The United States Of America As Represented By The United States Department Of Energy Dispersion strengthened copper
JPH03188654A (ja) * 1989-12-18 1991-08-16 Nippon Steel Corp 樹脂モールド型半導体用放熱体
US5443615A (en) * 1991-02-08 1995-08-22 Honda Giken Kogyo Kabushiki Kaisha Molded ceramic articles
GB2243160B (en) * 1990-02-13 1994-08-10 Honda Motor Co Ltd A method of producing a moulded article
IT1241000B (it) * 1990-10-31 1993-12-27 Magneti Marelli Spa Dispositivo elettromagnetico di controllo dell'alimentazione di corrente al motore elettrico di avviamento di un motore a combustione interna per autoveicoli.
GB2291434B (en) * 1994-07-20 1997-12-24 Honda Motor Co Ltd Process for producing sintered aluminium products
US5580517A (en) * 1994-11-08 1996-12-03 Kyushu Ceramics Industry Co., Ltd. Method of making composites of metals and oxides
SE518515C2 (sv) * 2000-06-15 2002-10-15 Elektrokoppar Ab Förfarande för framställning av dispersionshärdade metallprodukter
US6696700B2 (en) * 2001-03-09 2004-02-24 National University Of Singapore P-type transparent copper-aluminum-oxide semiconductor
US20080142126A1 (en) * 2006-12-14 2008-06-19 General Electric Company Graded metallic structures and method of forming; and related articles

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US3787200A (en) * 1967-09-05 1974-01-22 Copper Range Co Metal powders for roll compacting
US3893844A (en) * 1972-01-13 1975-07-08 Scm Corp Dispersion strengthened metals
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
CH588152A5 (de) * 1972-12-11 1977-05-31 Siemens Ag
US4077816A (en) * 1973-07-30 1978-03-07 Scm Corporation Dispersion-strengthened metals
JPS5539617A (en) * 1978-09-14 1980-03-19 Hitachi Ltd Manufacturing of glass mold type diode
US4274873A (en) * 1979-04-09 1981-06-23 Scm Corporation Dispersion strengthened metals
US4315777A (en) * 1979-08-07 1982-02-16 Scm Corporation Metal mass adapted for internal oxidation to generate dispersion strengthening
JPS5931838A (ja) * 1982-08-18 1984-02-21 Teikoku Piston Ring Co Ltd 耐熱，導電性分散強化銅合金材料の製造方法
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JPS60131903A (ja) * 1983-12-21 1985-07-13 Nippon Gakki Seizo Kk 分散強化銅合金形成用合金粉末

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2746016C1 (ru) * 2020-03-30 2021-04-05 Владимирова Юлия Олеговна, Жаропрочный и износостойкий материал на основе меди

Also Published As

Publication number Publication date
FR2581658A1 (fr) 1986-11-14
FR2581658B1 (fr) 1987-07-17
JPS62502813A (ja) 1987-11-12
US4752333A (en) 1988-06-21
KR880700441A (ko) 1988-03-15
WO1986006871A1 (fr) 1986-11-20

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