US20040238086A1 - Processing copper-magnesium alloys and improved copper alloy wire - Google Patents

Processing copper-magnesium alloys and improved copper alloy wire Download PDF

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Publication number
US20040238086A1
US20040238086A1 US10/445,717 US44571703A US2004238086A1 US 20040238086 A1 US20040238086 A1 US 20040238086A1 US 44571703 A US44571703 A US 44571703A US 2004238086 A1 US2004238086 A1 US 2004238086A1
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Prior art keywords
copper alloy
wire
copper
magnesium
alloy wire
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Abandoned
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US10/445,717
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English (en)
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Joseph Saleh
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Fisk Alloy Wire Inc
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Fisk Alloy Wire Inc
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Priority to US10/445,717 priority Critical patent/US20040238086A1/en
Assigned to FISK ALLOY WIRE, INC. reassignment FISK ALLOY WIRE, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SALEH, JOSEPH
Priority to EP20030292667 priority patent/EP1482063A1/en
Priority to JP2004105908A priority patent/JP2004353081A/ja
Priority to CN200410047605.2A priority patent/CN1574107A/zh
Publication of US20040238086A1 publication Critical patent/US20040238086A1/en
Priority to JP2007289672A priority patent/JP2008095202A/ja
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • 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

Definitions

  • the present invention relates to high strength, high conductivity copper alloy wire and a method for manufacturing same, wherein the copper alloy wire is a copper-magnesium based system optionally with one or more additional elements.
  • Copper is the natural choice for conductor wire due to its high electrical conductivity.
  • High performance copper alloys are required where the mechanical properties of copper are not sufficient for a particular application.
  • these copper alloys must also meet a combination of often conflicting properties. These properties may include strength, ductility, softening resistance and flex life. Indeed, ASTM B105 and B624 describe the requirements for hard drawn and high strength, high conductivity copper alloy wire for electrical applications.
  • Cadmium copper (alloy C162) is a copper alloy containing 1% nominal cadmium with unique combination of properties. It has an electrical conductivity greater than 80% IACS and when hard can attain a tensile strength in excess of 100 ksi. These properties make the alloy very useful for high strength conductor applications, such as trolley wire or airframe wiring. In addition, this alloy exhibits unusually long flex life as evidenced by the number of cycles it can bend back and forth over a mandrel before fracture. Consequently, it is used in many other high flex conductor applications, such as those in antilock braking harnesses, audio speaker and headset or telephone connecting wire.
  • Cadmium has been known to be a health hazard and attempts are being made to replace materials containing this element.
  • Cadmium appears on the list of bio-accumulative and toxic (PBT) chemicals compiled by the Environmental Protection Agency (EPA). The EPA considers cadmium as a possible human carcinogen.
  • PBT bio-accumulative and toxic
  • EPA Environmental Protection Agency
  • cadmium as a possible human carcinogen.
  • Various proposals have been made in different countries to ban or restrict the use of this element. Therefore it is very beneficial to provide alternative alloys to Cu—Cd alloys.
  • Cu—Mg alloy base systems offer equally attractive properties.
  • Alloy C18661 with 0.1-0.7 percent Mg is a Cu—Mg alloy listed by Copper Development Association (CDA).
  • Alloy C18665 is another listed alloy with 0.4-0.9% Mg. These alloys may also contain a small amount of residual P which is typically used as a de-oxidant.
  • CDA does not list the applications of these alloys, typical applications are as trolley wire or connectors. These alloys are cast and drawn to finish size without any anneal to obtain the highest strength possible.
  • the present invention provides a process for manufacturing a copper alloy wire having a high strength and high conductivity.
  • the process broadly comprises the steps of providing a base material formed from a copper alloy containing from 0.05 to 0.9 wt % magnesium and more than 15 ppm total impurities, cold working the base material into a wire having at least a 40% reduction in original cross section area, performing a restructuring anneal after the cold working step, and drawing the annealed material into a wire having a final gage size of 0.010′′ maximum.
  • the magnesium content of the copper alloy is from 0.1 to 0.4 wt %.
  • the restructuring annealing step is performed at a temperature in the range of 650 to 1050° F. for a time period in the range of 1 to 5 hours, preferably 2-3 hours.
  • the copper alloy contains one or more additional alloying ingredients, as
  • the present invention also provides an improved copper alloy wire having high strength and high conductivity which broadly comprises a copper alloy containing from 0.05 to 0.9 wt % magnesium and more than 15 ppm impurities, which wire has a single end diameter less than or equal to 0.010 inches, a tensile strength of at least 100 ksi, and an electrical conductivity greater than 60% IACS.
  • FIG. 1 is a graph of tensile strength versus percent reduction in cross sectional area for a copper-0.12% magnesium alloy processed in accordance with the present and the same alloy processed conventionally;
  • FIG. 2 is a graph similar to FIG. 1 for a copper alloy containing 0.15% magnesium and 0.1% tin;
  • FIG. 3 is a graph of tensile strength versus wire diameter for a copper alloy containing 0.15% magnesium and 0.1% tin processed in accordance with the present invention and the same alloy processed conventionally.
  • the copper alloy wire contains from 0.05 to 0.9 wt % magnesium, preferably from 0.1 to 0.4 wt %. Increasing the amount of magnesium will increase the strength while reducing the electrical conductivity. This allows the alloy to be tailored to a desired set of properties.
  • Additional alloying elements may be added to improve strength or other properties of the alloy.
  • phosphorous is an element that can be added to increase the strength through precipitation of magnesium phosphide (Mg 3 P 2 ).
  • the amount of phosphorus added to the alloy should not exceed that needed to form the magnesium phosphide, or phosphides of other elements when present. Therefore, the phosphorus should be in an amount less than the amount of magnesium present and generally from 0.01 to 0.3 wt % and preferably from 0.02-0.15 wt %.
  • the composition, casting procedure and heat treatment must ensure that the majority of the phosphide particles are sub-micron size to provide high drawability and improved performance at small wire diameters.
  • Iron is another beneficial element that may be added to the alloy.
  • copper-magnesium alloys with iron and phosphorus present will form phosphides of magnesium and iron, which are quite beneficial.
  • the amount of iron should vary between 0.01 to 1 wt %, and preferably less than 0.5 wt %.
  • Small amounts of tin are also beneficial and serve to slightly improve the strength of the alloy.
  • the amount of tin should desirably vary from 0.01 to 0.2 wt % and preferably less than 0.1 wt %. Very small amounts of tin may be considered as a beneficial impurity. However, larger amounts of tin tend to reduce the electrical conductivity of the alloy.
  • alloying additions and conventional impurities greater than 15 ppm in total may be present.
  • small amounts of silver will improve the performance of the alloy without adversely impacting electrical conductivity.
  • Silver, when present, should be in the range of 0.01 to 0.2 wt %.
  • Other alloying additions for effecting specific objectives may include nickel in amount from 0.01 to 0.5 wt % and/or zinc in an amount from 0.01 to 0.5 wt %.
  • the present invention provides non-cadmium containing copper alloy conductors containing magnesium which can readily be used as a replacement for copper-cadmium alloys and in similar applications.
  • the processing of the copper-magnesium alloys to desired final gage wire incorporates at least one restructuring anneal before being drawn to the finish size wire required to manufacture the desired conductor.
  • the resultant wire is characterized by a good combination of strength and conductivity, as well as other desirable properties, such as good flex life and resistance to thermal softening.
  • the copper alloy wire of the present invention may be manufactured by the process of providing a base material formed from a copper alloy containing from 0.05 to 0.9 wt % magnesium, cold working the base material into a wire having at least a 40% reduction in original cross section area, performing an anneal, and drawing said material into a wire having a single end final gage of 0.010 inches maximum, preferably the final gage is more than 0.002 inches but less than 0.010 inches.
  • the copper alloy may also contain one or more of the additional elements discussed above and the annealing step may be performed after the base material has been cold worked into a wire having at least a 70% reduction in the original cross section area.
  • the restructuring anneal may be performed at a temperature in the range of 650 to 1050° F. for a time period in the range of 1 to 5 hours, preferably at a temperature in the range of 750 to 900° F. for a time period in the range of 2 to 3 hours.
  • the cold working step may be performed by any suitable technique known in the art including, but not limited to, rolling and/or drawing.
  • Copper alloy wires formed in accordance with the present invention exhibit a tensile strength of at least 100 ksi, preferably at least 110 ksi, and an electrical conductivity at room temperature of 68° F. greater than 60% IACS, and preferably greater than 70% IACS. This is an unusual set of properties for copper alloy wire products having a single end diameter less than 0.010 inches.
  • a copper-magnesium alloy was processed to wire incorporating a restructuring anneal prior to being drawn to finish gage, and for comparison without the anneal.
  • the copper alloy contained 0.12% magnesium. It was surprisingly found that the incorporation of a restructuring anneal in the processing improved the rate of work hardening and provided a stronger wire. Work hardening is the increase in strength of an alloy due to plastic deformation.
  • the alloy was cast to 21 mm (0.827 inch) diameter rod and rolled from the 21 mm diameter rod to 7.4 mm (0.291 inch) modified square cross-section.
  • the cross-section is equivalent to 0.312 inch round diameter.
  • the processing of the present invention then provided an anneal at 700-850° F. for 1-5 hours, and generally 750-800° F. for 2-3 hours, followed by drawing to desired finish gage.
  • the same alloy was drawn to finish gage directly from the 7.4 mm rod using conventional processing which does not employ any annealing.
  • FIG. 1 illustrates the tensile strength of the Cu—Mg alloys processed as aforesaid as a function of cold reduction. It can be readily seen that those alloys given the restructuring anneal obtained an increase of 10 ksi over those not given the anneal. This is a significant increase. It was also found that these alloys could be readily drawn to small diameter wire required for conductor applications, typically less than 0.010 inch diameter.
  • FIG. 2 illustrates the tensile strength of the Cu—Mg—Sn alloys processed as aforesaid as a function of percent reduction in area
  • FIG. 3 illustrates tensile strength as a function of wire diameter
  • a copper alloy containing 0.15% magnesium was processed in a manner after Example 1.
  • the alloy was given a restructuring anneal following rod rolling.
  • the annealed wire was then drawn to 0.004 inch diameter in several steps.
  • the resultant properties are shown in Table 1, below.
  • Table 1 clearly shows that not only can the alloy be drawn to small diameters, but also that the obtained tensile strength at 0.004 inch diameter exceeds 120 ksi. The properties are quite attractive and compare favorably with those of copper-cadmium alloy C162.
  • ASTM B470-95 paragraph 6 describes the test procedures for the flex test. In this test, the conductor is initially hung in a vertical position with a defined weight and is repeatedly flexed back and forth over a pair of standard steel mandrels held in a horizontal position. Flexing of the conductor is repeated until fracture. The number of cycles to fracture defines the flex life.
  • Conductors with 19 ends of 38 AWG construction as in Example 4 were prepared using the copper-0.15% magnesium-0.1% tin alloy of Example 2. Two conductors were prepared, one utilizing the no anneal condition and the second utilizing the rod rolled and annealed condition of the wire outlined in Example 1. The conductors were tested for flex life according to ASTM B470 and the results are shown in Table 3, below. TABLE 3 Annealed after No Anneal Initial Rolling Condition Break Load, lb 29.0 27.3 Single End Size, inch 0.0041 0.0041 Flex Life 34998 28137
  • the 160 ksi tensile strength is very high for a copper alloy with an electrical conductivity of greater than 60% IACS. Indeed, this represents a unique combination of tensile strength and electrical conductivity for a copper alloy. Although the electrical conductivity of this alloy is less than that of copper-cadmium, the combination of properties is excellent and is quite useful.
  • a copper-0.12% magnesium-0.1% tin-0.02% phosphorus was given a restructuring anneal of the present invention in accordance with the procedure of Example 1.
  • the alloy was annealed following initial rod rolling, the annealed wire was then drawn to a 0.004 inch diameter in several steps and the resultant properties shown in Table 5, below.
US10/445,717 2003-05-27 2003-05-27 Processing copper-magnesium alloys and improved copper alloy wire Abandoned US20040238086A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US10/445,717 US20040238086A1 (en) 2003-05-27 2003-05-27 Processing copper-magnesium alloys and improved copper alloy wire
EP20030292667 EP1482063A1 (en) 2003-05-27 2003-10-24 Processing copper-magnesium alloys and improved copper alloy wire
JP2004105908A JP2004353081A (ja) 2003-05-27 2004-03-31 銅合金線材およびその製造方法
CN200410047605.2A CN1574107A (zh) 2003-05-27 2004-05-27 加工铜镁合金的方法及改良的铜合金导线
JP2007289672A JP2008095202A (ja) 2003-05-27 2007-11-07 銅合金線材およびその製造方法

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EP (1) EP1482063A1 (ja)
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US20090311127A1 (en) * 2008-06-11 2009-12-17 Chuankai Xu Lead-free free-cutting magnesium brass alloy and its manufacturing method
CN102941417A (zh) * 2012-11-14 2013-02-27 四川大西洋焊接材料股份有限公司 一种锡青铜焊丝及其制备方法
CN104046831A (zh) * 2014-06-05 2014-09-17 锐展(铜陵)科技有限公司 一种汽车用铜合金电线的制备方法
CN104046832A (zh) * 2014-06-05 2014-09-17 锐展(铜陵)科技有限公司 一种汽车发电机用高导电铜合金线的制备方法
CN104212996A (zh) * 2013-05-30 2014-12-17 株式会社藤仓 拉丝线材的制造方法
KR20150034678A (ko) * 2012-07-02 2015-04-03 후루카와 덴키 고교 가부시키가이샤 구리합금 선재 및 그의 제조방법
CN104795123A (zh) * 2014-01-21 2015-07-22 余姚市宏达电子材料厂 镍层镀锡铜包钢线
CN105818713A (zh) * 2016-03-26 2016-08-03 无锡超洲科技有限公司 一种用于电气化铁路接触网的吊弦线及其加工工艺
US20170309369A1 (en) * 2016-04-25 2017-10-26 Yazaki Corporation Highly bendable insulated electric wire and wire harness
US20180114610A1 (en) * 2016-03-31 2018-04-26 Autonetworks Technologies, Ltd. Communication cable
US9972411B2 (en) 2013-02-14 2018-05-15 Sumitomo Electric Industries, Ltd. Copper alloy wire, copper alloy stranded wire, covered electric wire, and terminal-fitted electric wire
EP3348658A4 (en) * 2015-09-09 2019-04-10 Mitsubishi Materials Corporation COPPER ALLOY FOR ELECTRONIC / ELECTRICAL DEVICE, ELEMENT FOR PLASTIC DEFORMABLE COPPER ALLOY FOR ELECTRONIC / ELECTRICAL DEVICE, COMPONENT FOR ELECTRONIC / ELECTRICAL DEVICE, END UNIT AND BUSBAR
US10446293B2 (en) 2016-03-31 2019-10-15 Autonetworks Technologies, Ltd. Shielded communication cable
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US20190355492A1 (en) * 2017-02-01 2019-11-21 Autonetworks Technologies, Ltd. Communication cable
US10676803B2 (en) 2015-09-09 2020-06-09 Mitsubishi Materials Corporation Copper alloy for electronic/electrical device, copper alloy plastically-worked material for electronic/electrical device, component for electronic/electrical device, terminal, and busbar
US11069459B2 (en) * 2017-07-14 2021-07-20 Autonetworks Technologies, Ltd. Covered electrical wire and terminal-equipped electrical wire
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US20090311130A1 (en) * 2008-06-11 2009-12-17 Chuankai Xu Tin-free, lead-free free-cutting magnesium brass alloy and its manufacturing method
US20090311127A1 (en) * 2008-06-11 2009-12-17 Chuankai Xu Lead-free free-cutting magnesium brass alloy and its manufacturing method
KR101719889B1 (ko) 2012-07-02 2017-03-24 후루카와 덴키 고교 가부시키가이샤 구리합금 선재 및 그의 제조방법
KR20150034678A (ko) * 2012-07-02 2015-04-03 후루카와 덴키 고교 가부시키가이샤 구리합금 선재 및 그의 제조방법
EP2868758A4 (en) * 2012-07-02 2016-05-25 Furukawa Electric Co Ltd COPPER ALLOY ROLL WIRE AND MANUFACTURING METHOD THEREFOR
CN102941417A (zh) * 2012-11-14 2013-02-27 四川大西洋焊接材料股份有限公司 一种锡青铜焊丝及其制备方法
US9972411B2 (en) 2013-02-14 2018-05-15 Sumitomo Electric Industries, Ltd. Copper alloy wire, copper alloy stranded wire, covered electric wire, and terminal-fitted electric wire
CN104212996A (zh) * 2013-05-30 2014-12-17 株式会社藤仓 拉丝线材的制造方法
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JP2004353081A (ja) 2004-12-16

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