WO1998017423A1 - Cuivre renforce par dispersion - Google Patents

Cuivre renforce par dispersion Download PDF

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Publication number
WO1998017423A1
WO1998017423A1 PCT/US1997/019443 US9719443W WO9817423A1 WO 1998017423 A1 WO1998017423 A1 WO 1998017423A1 US 9719443 W US9719443 W US 9719443W WO 9817423 A1 WO9817423 A1 WO 9817423A1
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WO
WIPO (PCT)
Prior art keywords
oxide
metal
copper
dispersion strengthened
particles
Prior art date
Application number
PCT/US1997/019443
Other languages
English (en)
Inventor
Evgueni P. DANELIA
Original Assignee
Danielia Evgueni P
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 Danielia Evgueni P filed Critical Danielia Evgueni P
Priority to AU50899/98A priority Critical patent/AU5089998A/en
Publication of WO1998017423A1 publication Critical patent/WO1998017423A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding
    • B23K35/402—Non-consumable electrodes; C-electrodes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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
    • 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

Definitions

  • the present invention relates to copper metal alloy that is dispersion strengthened with stable dispersed oxides and also to a method for making dispersion strengthened copper alloys .
  • the dispersion strengthened material hereof comprises a copper metal matrix having dispersed oxides incorporated therewithin.
  • the dispersed oxides include at least one oxide selected from the group consisting of aluminum oxide or beryllium oxide and, optionally, a second oxide selected from the group consisting titanium oxide, hafnium oxide, zirconium oxide and mixtures thereof.
  • the oxides are introduced into the dispersion strengthened material by the internal oxidization thereof.
  • the first oxide and second oxide are present in a mass ratio of greater than 4:1.
  • a method of forming the dispersion strengthened material which includes the steps of forming a copper alloy, the alloy comprising copper, at least one metal selected from the group consisting of aluminum or beryllium, forming the alloy into either powder or granulated particles, oxidizing the particles to form an oxide skin on the surface of the products, internally oxidizing the particles to form a copper matrix comprising oxides of aluminum or beryllium compacting the particles into a billet or other compact form and, thereafter, extruding the compacted particles using a drawing coefficient of at least about 12 to form a dispersion strengthened material.
  • the present process contemplates the formation of the alloy by melting the copper, preferably, as scrap in an induction heating furnace under reducing condition using a protecting flux at a temperature ranging from about 2240°F up to about 2260°F. Thereafter, and in a preferred embodiment hereof, the aluminum or beryllium is introduced into the melt in a proportion of from about 1.3 to about 1.7 times the amount required in the final alloy. Thereafter, an additional metal selected from the group consisting of titanium, hafnium or zirconium is admixed thereinto. Next, the melt is superheated and thereafter immediately cast into an ingot or gas atomized.
  • the resulting powder product can be further processed by cold isostatically pressing the powder into billets which can be emplaced in a fill can and, then, extruded into any desired product.
  • the present invention is directed to a dispersion strengthened copper material and a method therefor that includes the steps of forming a copper alloy having alloying elements capable of being oxidized and oxidizing the alloy using particular oxidation parameters to provide a final product with disperse oxide particles that preferably have an average size of about 10 nm or less.
  • the oxide particles are uniformly distributed in the bulk of the matrix metal, which give the metal improved mechanical and electrical properties over non-strengthened copper and over prior art dispersion strengthened materials.
  • the copper alloy includes at least on preferably at least two, alloying elements capable of being oxidized to form oxide particles within the copper metal matrix.
  • the copper alloy comprises at least one metal which is either aluminum or beryllium as alloying elements. Additional alloying elements which may be included therewith hafnium, titanium, zirconium or mixtures thereof.
  • the aluminum or beryllium is present in an amount from about 0.01 weight percent to about 0.8 weight percent and preferably, less than about 0.6 weight percent of the total weight alloy.
  • the titanium is present in an amount from about 0.01 weight percent to about 0.80 weight percent and, preferably, is present in an amount less than about 0.15 weight percent of the total weight of the alloy.
  • the hafnium as well as the zirconium are, likewise, present in an amount from about 0.01 weight percent to about 0.80 weight percent and, preferably, comprise less than about 0.15 weight percent of the alloy.
  • the balance of the alloy is essentially copper.
  • the weight ratio of aluminum or beryllium to the other alloys is greater than 4:1 and the total concentration of the alloying elements, preferably, does not exceed about 0.9 weight percent in the final product.
  • the copper alloy can be melted and formed into an ingot.
  • the ingot can then be dispersed into chips with a milling machine having a flake or platelet form.
  • the chips have a thickness of about 100 micrometers or less and can have a width of, for example, up to about 1 millimeter.
  • the copper alloy can be particulated by spraying molten droplets of the alloy in an inert gas to produce discrete granules.
  • the granules are, preferably, separated, such as by using a sieve, so that the granules have an average particle size of about 300 micrometers or less.
  • the dispersion strengthened material hereof is prepared by a process which includes initially forming the alloy by melting a source of copper, such as copper scrap, by induction heating under reducing conditions using a protective flux. Typically, melting occurs at a temperature ranging from about 2240°F to about 2260°F. Thereafter, the first metal, i.e. aluminum or beryllium is introduced into the melt, preferably, as large pieces thereof. Generally, the aluminum or beryllium is introduced into the melt in an amount equal to about 1.3 to about 1.7 times the quantity desired in the final alloy. Upon introduction into the melt, the temperature is raised to about 2300°F for about three to four minutes.
  • the additional metals where used, are introduced into the melt as master alloys, i.e. either copper- titanium alloy, copper-hafnium alloy or copper-zirconium alloy. Typically, they are introduced, in the order of titanium, then, hafnium and/or zirconium. Upon introduction into the melt the melt is superheated up to about 1290°C for about 1 to 2 minutes and thereafter it is immediately cast into an ingot or atomized in the powders granules.
  • master alloys i.e. either copper- titanium alloy, copper-hafnium alloy or copper-zirconium alloy.
  • they are introduced, in the order of titanium, then, hafnium and/or zirconium.
  • the melt is superheated up to about 1290°C for about 1 to 2 minutes and thereafter it is immediately cast into an ingot or atomized in the powders granules.
  • the flakes or granules (hereinafter collectively referred to as particles) of the alloy are then subjected to surface oxidation to form an oxide skin on the surface of each particle.
  • the particles are dispersed on a tray such as a stainless steel tray, to permit substantially free access of the oxidizing environment to the particles.
  • the depth of the particle layer in the tray can be up to about 5 centimeters .
  • the surface oxidation of the particles takes place at a temperature in the range of from about 250°C to about 900°C, and, preferably, in the range of from about 300°C to about
  • the particles can be exposed to air or any other atmosphere having a sufficient oxygen content.
  • over pressures of oxygen may be useful.
  • a film of copper oxide is thereby formed on the surface of substantially every particle, which serves as the oxidant for the subsequent internal oxidation of the alloying elements. Since copper oxide is formed on the surface of substantially every particle, a uniform distribution of the oxidant and thus the internal oxidation of the alloying elements can also be uniform.
  • the preferred thickness of the copper oxide film depends on the average shape and the dispersivity of the particles, as well as on the concentration of alloying elements in the alloy.
  • the internal oxidation includes the step of heating the powder particles in an inert atmosphere at a temperature of from about 850°C to about 950°C.
  • the inert atmosphere can include argon, nitrogen, or a mixture of carbon dioxide and carbon monoxide.
  • the atmosphere used should include a relatively low partial pressure of oxygen such as about 10 -7 atmospheres. Typically, in lower purity gases, there is enough residual water vapor to maintain such a low partial pressure of oxygen. The low partial pressure of oxygen will maintain the proper oxygen stoichiometry on the outside of the oxide skin on the particles, while the particles internally oxidize from the interface of the particle and the oxide skin layer.
  • the partial pressure of oxygen is therefore from about 10 "6 to 10 ⁇ 8 atmospheres.
  • the duration of the internal oxidation process depends on the shape and the size of the powder particles, on the type and concentration of the alloying elements in the alloy, as well as on the temperature.
  • the preferred time, in seconds, can be calculated, also, as described in the aforementioned application and patent.
  • the particles so produced will thus comprise a copper matrix strengthened by a dispersion of fine oxides of either aluminum oxide or beryllium oxide, optionally, with one or more of titanium oxide, hafnium oxide, zirconium oxide and mixtures thereof.
  • the oxides will have a size of less than about 10 nra as measured by electron microscopy techniques .
  • the master alloys are used to introduce the alloying elements such as titanium, hafnium or zirconium into the melt.
  • the master alloys will have a copper to other metal (s) weight ratio of from about 70:30 to about 30:70, depending on the introduced alloying elements. It is, also, desirable that the composition of the master alloys be brittle so that they break up easily to form small pieces before introducing into the melt for uniform distribution of the alloying elements in the melt.
  • the adjuvants, i.e. the master alloys, introduced into the copper melt have a melting temperature close to that of copper to prevent the oxidization of the metal.
  • the casting of the superheated melt takes place in a rapid period of time to preclude the oxidization of the alloys.
  • the products hereof will have an aluminum or beryllium to adjuvant other metal ratio of greater than 4:1.
  • the particles have an oxidized skin layer formed thereon, which particles are then heated in an inert atmosphere to dissociate oxygen from the copper oxide skin and drive the dissociated oxygen into the bulk of the particles to oxidize at least a portion of the alloying elements.
  • the dispersion strengthened particles are either briquetted (e.g., pressed) or compacted into a fill can which can then be further processed when briquetted, they are then subjected to hot extrusion.
  • a briquette is pressed at a pressure of from about 5 to about 6 metric tons per square centimeter.
  • the density of the briquette after pressing is a least about 90% or greater.
  • the briquettes are then extruded, preferably, at a temperature of from about 850°C to about 950°C, during which consolidation and diffusion welding of the particles occurs.
  • Good diffusion welding can advantageously be achieved by extruding the briquette with a drawing coefficient of at least about 12, more preferably at least about 16. That is, the cross sectional area of the briquette is preferably reduced by at least about a factor of 12 during extrusion, as described in the aforementioned application.
  • a simplification of the process and subsequent reduction of the cost of the process can be achieved if the briquetting of the powder is carried out immediately after the surface oxidation of the particles. That is, the particles having an oxide skin are briquetted prior to the internal oxidation of the alloying elements. The internal oxidation is thus carried out when the particles are in briquette form, but prior to extrusion.
  • the powders can be pressed by an isostatic process to form small compact billets which can then be loaded into a fill can and surrounded with other powders. This fill can then be extruded.
  • Products produced according to the present invention are useful in applications where the high conductivity of copper is desirable along with good hardness and strength, ductility, etc. particularly at elevated temperatures. Applications include welding electrodes, electrical contacts, heat conductors, foils, and the like.
  • EXAMPLE 1 Several alloys, as set forth in Table I, were prepared by melting copper, in an induction-heating furnace under reducing conditions using carbon flux. The copper was melted at 2250°F. Then aluminum and beryllium was added to the copper and melted in about three minutes at a temperature increasing up to 2300°F. Thereafter, a second metal was introduced, as a master alloy, and melted at the same temperature. Then, the melt was superheated for about 1.5 minutes at 2350°F and, then, gas atomized. Thereafter, the particles were surface oxidized and then internally oxidized, to form powders in accordance herewith.
  • the powder was then loaded into a rubber can using a vibration process with an apparent density in the range of 45% to 56% (45%-56% of the theoretical density) and subjected to pressing in a cold isostatic press to obtain compact billets with an apparent density of from about 75% to 85%.
  • the billets were loaded into a copper can having an internal diameter about 160mm. Additional powder was added to the can to fill it.
  • the loaded can was welded shut and extruded into bars at the temperature 1550°F (about 850°C) .
  • Alloys A, B, C below were prepared according to the described in Example 1. Final bars were cold drawn into wires of 0.05 mm diameter for alloys B and C and into a wire 0.2 mm diameter for alloy A. Alloy A could not be drawn to a diameter of less than 0.2 mm because of breakage, in comparison to alloys B and C.
  • the properties of the alloy wires after cold drawing (CD) and after the following annealing at 1832°F (1000°C) for 1 hour (A) are presented in Table III.
  • Alloys A, E and F below were prepared according to the procedure described in Example 1 for alloys E and F and by the method according to the parent application for alloy A. The final bars were hot and then cold rolled to a strip of 0.2 mm thick. Their resulting properties were determined after cold rolling, and, also, after annealing at 1832°F (1000°C) for 1 hour. The results are set forth in Table IV. TABLE IV

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

Abstract

L'invention concerne un alliage de cuivre renforcé par dispersion et un procédé de production dudit alliage. Ledit alliage comprend de préférence du béryllium ou de l'aluminium comme premier métal d'alliage et du zirconium, du titane ou de l'hafnium comme second métal d'alliage. Ces métaux sont soumis à une oxydation interne dans des conditions déterminées de façon à donner un matériau cuivre renforcé par dispersion présentant une bonne dureté et une conductivité élevée. Le matériau renforcé par dispersion peut servir à de nombreuses applications, dont des électrodes de soudage et des contacts électriques.
PCT/US1997/019443 1996-10-22 1997-10-22 Cuivre renforce par dispersion WO1998017423A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50899/98A AU5089998A (en) 1996-10-22 1997-10-22 Dispersion strengthened copper

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US73487896A 1996-10-22 1996-10-22
US08/734,878 1996-10-22

Publications (1)

Publication Number Publication Date
WO1998017423A1 true WO1998017423A1 (fr) 1998-04-30

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PCT/US1997/019443 WO1998017423A1 (fr) 1996-10-22 1997-10-22 Cuivre renforce par dispersion

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AU (1) AU5089998A (fr)
WO (1) WO1998017423A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100354999C (zh) * 2005-10-07 2007-12-12 乐清市帕特尼触头有限公司 低压电器用清洁环保型铜基触头材料及其触点制备方法
CN102489861A (zh) * 2011-12-16 2012-06-13 沈阳黎明航空发动机(集团)有限责任公司 一种氧化物弥散强化合金防震屏零件的焊接方法
WO2013037502A1 (fr) * 2011-09-15 2013-03-21 Universität Bayreuth Procédé pour la fabrication d'une matière composite à matrice métallique
CN110592419B (zh) * 2019-10-14 2020-11-03 郁杨 一种高强高导铜合金及其制备方法
CN115069977A (zh) * 2022-07-15 2022-09-20 广东省科学院佛山产业技术研究院有限公司 一种模具用铜铍钴合金板及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3026200A (en) * 1956-10-11 1962-03-20 134 Woodworth Corp Method of introducing hard phases into metallic matrices
US3179515A (en) * 1960-04-27 1965-04-20 Grant Dispersion strengthened metals
US3184835A (en) * 1961-10-02 1965-05-25 Handy & Harman Process for internally oxidationhardening alloys, and alloys and structures made therefrom
US3525609A (en) * 1966-03-07 1970-08-25 Ass Elect Ind Copper alloy material
US3615899A (en) * 1968-01-27 1971-10-26 Furukawa Electric Co Ltd Method of producing materials having a high strength a high electrical conductivity and a high heat resistance
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
US4315770A (en) * 1980-05-02 1982-02-16 Scm Corporation Dispersion strengthened metals
US4478787A (en) * 1982-06-18 1984-10-23 Scm Corporation Method of making dispersion strengthened metal bodies and product
US5004498A (en) * 1988-10-13 1991-04-02 Kabushiki Kaisha Toshiba Dispersion strengthened copper alloy and a method of manufacturing the same
US5030275A (en) * 1987-12-14 1991-07-09 Scm Metal Products, Inc. Equiaxed dispersion strengthened copper product

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3026200A (en) * 1956-10-11 1962-03-20 134 Woodworth Corp Method of introducing hard phases into metallic matrices
US3179515A (en) * 1960-04-27 1965-04-20 Grant Dispersion strengthened metals
US3184835A (en) * 1961-10-02 1965-05-25 Handy & Harman Process for internally oxidationhardening alloys, and alloys and structures made therefrom
US3525609A (en) * 1966-03-07 1970-08-25 Ass Elect Ind Copper alloy material
US3615899A (en) * 1968-01-27 1971-10-26 Furukawa Electric Co Ltd Method of producing materials having a high strength a high electrical conductivity and a high heat resistance
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
US4315770A (en) * 1980-05-02 1982-02-16 Scm Corporation Dispersion strengthened metals
US4478787A (en) * 1982-06-18 1984-10-23 Scm Corporation Method of making dispersion strengthened metal bodies and product
US5030275A (en) * 1987-12-14 1991-07-09 Scm Metal Products, Inc. Equiaxed dispersion strengthened copper product
US5004498A (en) * 1988-10-13 1991-04-02 Kabushiki Kaisha Toshiba Dispersion strengthened copper alloy and a method of manufacturing the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100354999C (zh) * 2005-10-07 2007-12-12 乐清市帕特尼触头有限公司 低压电器用清洁环保型铜基触头材料及其触点制备方法
WO2013037502A1 (fr) * 2011-09-15 2013-03-21 Universität Bayreuth Procédé pour la fabrication d'une matière composite à matrice métallique
CN102489861A (zh) * 2011-12-16 2012-06-13 沈阳黎明航空发动机(集团)有限责任公司 一种氧化物弥散强化合金防震屏零件的焊接方法
CN110592419B (zh) * 2019-10-14 2020-11-03 郁杨 一种高强高导铜合金及其制备方法
CN115069977A (zh) * 2022-07-15 2022-09-20 广东省科学院佛山产业技术研究院有限公司 一种模具用铜铍钴合金板及其制备方法

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Publication number Publication date
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