US3017268A - Copper base alloys - Google Patents

Copper base alloys Download PDF

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Publication number
US3017268A
US3017268A US27680A US2768060A US3017268A US 3017268 A US3017268 A US 3017268A US 27680 A US27680 A US 27680A US 2768060 A US2768060 A US 2768060A US 3017268 A US3017268 A US 3017268A
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alloy
copper
alloys
hours
properties
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US27680A
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Matti J Saarivirta
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Cyprus Amax Minerals Co
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American Metal Climax Inc
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Priority to US27680A priority Critical patent/US3017268A/en
Priority to GB9049/61A priority patent/GB951121A/en
Priority to CH531461A priority patent/CH424276A/de
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    • 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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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

  • This invention vrelates to copper base alloys essentially containing titanium, tin and chromium.
  • the alloys of this invention have a minimum copper content of 90% and are age hardenable.
  • age hardenable copper base alloys containing beryllium are used quite extensively.
  • Commercie-illy available beryllium alloys containing, for example, 0.4 to 0.7% beryllium, 2.3 to 2.7% cobalt, balance copper possess attractive mechanical properties in several respects including a tensile strength of as much as 100,000 p.s.i lcombined with electrical conductivity of about 48% that of pure copper.
  • Such a combination of properties are exceedingly diicult to obtain since in the case of most copper alloys having a tensile strength of about 90,000 to 100,000 p.s.i. or higher, the electrical conductivity is rarely above 30% that of pure copper.
  • beryllium-copper alloys are satisfactory for various electrical and electronic applications with respect to meeting mechanical and physical property requirements no-t met by most other copper base alloys, such alloys have the drawback that they are rather difficult and costly to make. Furthermore, these alloys require the use of beryllium which in addition to being expensive is also an 'extremely toxic substance necessitating special precautions in the making and subsequent processing of such alloys. Then too, whereas such beryllium copper alloys are suitable for rather limited high temperature applications, extreme brittleness is encountered at temperatures in excess of about 22S-250 C. leading to failure of the alloy. Accordingly, there is an urgent need for materials which not only possess satisfactory properties at ordinary temperatures of operation but which also are capable of withstanding higher temperatures over prolonged periods of operation without excessive deterioration of the alloy by embrittlement or otherwise.
  • lt is another object of this invention to provide age hardenable copper-titanium-tin-chromium alloys that possess improved properties compared with beryllium-copper alloys especially with respect to retention of said properties under service conditions involving lelevated temperatures appreciably higher than 250 C.
  • Another object of this invention is to provide new and novel alloys that substantially meet the requirements with respect to tensile strength, electrical conductivity and other properties satisfied by heryllium-coppers without incurring the high cost Vof* production and toxicity problems associated with such beryllium-containing alloys.
  • the copper base quaternary alloys of this invention generally contain from 0.3 to 4% titanium, 0.5 to 5% tin, 0.05 to 2% chromium, the balance being copper which is present in all instances in the amount of at least with respect to the overall alloy composition.
  • Phosphorus and/or silver may be optionally included in amounts not exceeding 0.05 and 1% respectively without significantly altering the properties of the resulting alloys although the presence ofphosphorus in amounts appreciably above 0.02% does effect some reduction in the electrical conductivity of the material.
  • the preferred composition of the quaternary alloy consists of from 1 to 3% titanium, 2 to 4% tin and 0.2 to 0.8% chromium, balance copper, with the proportion of titanium to tin being in the ratio of approximately 1:1.7 respectively.
  • Optimum properties of the alloy are obtained with the use of from 1.3 to 1.7% titanium, 2.2 to 2.9% tin and 0.3 to 0.6% chromium. All of the foregoing percentages refer to the actual content of the various alloying elements in the resulting alloy product.
  • tough pitch copper may be used in makingl the alloys of the present invention, it is definitely preferred to make said alloys with initially oxygen-free copper.
  • Such coppers include electrolytic cathode copper, copper made in a reducing atmosphere such as OFHC brand copper, or copper made using an inert atmosphere, a vacuum or under a charcoal cover, Chemically deoxidized copper obtained by the treatment of oxygencontaining copper with phosphorus, lithium or other deoxidiz'ers may also be used in making said alloys.
  • the alloys can be made according to standard alloying methods such as melting the Copper in an induction furnace and adding the desired amounts of titanium, tin and chromium and possibly other ingredients such as silver and phosphorus when the melt is at a temperature of about 1300 C.
  • the alloying ingredients may be in any form suitable for a-lloying purposes such as metal sponge, master alloys, etc.
  • the chromium may be included Patented Jan. f6, 1962' in appropriate amount in the form of a copper master alloy (5% Cr) along with the copper at the time of preparing the copper melt in which event only the titanium and tin need be subsequently added.
  • phosphorusdeoxidized or phosphorized copper may be used in preparing the initial melt whereby the separate addition of phosphorus at a later time need not be made if phosphorus is to be included in the alloy.
  • the ternperature of the melt is lowered and held at about 1200" C. with the alloy being stirred and allowed to settle for about 5-10 minutes after which it is cast in accordance with conventional practices.
  • an inert protective atmophere consisting of argon, helium or other inert gas be used throughout the entire operation including the casting step.
  • non-oxidizing gases such as carbon monoxide, nitrogen or hydrogen should be avoided since such gases react in varying degrees with one or more of the alloying ingredients and especially with tit"- nium. If carried out correctly, the melting, alloying and casting procedure presents no diiculties and sound castings are readily produced using copper or any other suitable molds in casting the alloy.
  • the alloys of the present invention possess excellent hot workability upon being preheated a-t about 800 to 850 C. said hot working being effected either by hot rolling or forging as may be desired.
  • a 300 pound casting in the form of an 8 inch diameter billet was readily hot forged after preheating for one hour into square rod material of 2.5 and 1.5 inch sizes respectively with no diiii'cult'y.
  • the alloys may also be readily cold worked' to reductions un to 90% and even higher by rolling or Wire drawing without difficulty.
  • The' conventional heat treatments used to obtain age hardening in copper alloys may be satisfactorily used to harden the alloys of the present invention.
  • Solution annealing is effected by heating the alloy to temperatures gen ⁇ erally ranging from about 825 to 890 C. for from a few minutes to about an hour or so depending on the solution annealing temperature used, it being preferred, however, to utilize a temeprature between 850 and 885 C. and optimally about 875 C. for about 30 minutes after Which the alloy is quenched.
  • Age hardening for from 2 to 4 hours at temperatures generally between 400 and 475 C. and preferably at about 450 C. is conducive to development of maximum strength. If electrical conductivity of about 40 to 50% I.A.C.S.
  • the optimum combination of properties with respect to strength and conductivity are produced by extending the heat treatment period to generally Vfrom 6 to 8 hours utilizing the preferred age hardening temperature of about 450 C.
  • Cold working by wire drawing prioi to precipitation hardening of the alloy appreciably reduces the aging time required for development of optimum properties including electrical conductivities between 40 and 5 0%.
  • the cast alloy processed for example, by solution annealing at 875 C. for from 15 to 30 minutes, quenched in Water and age hardened for from 6 to 14 hours at 450 C. possesses a tensile strength ranging from 60,000 to 80,000 p.s.i., electrical conductivity of from 35 to 50% I.A.C.S. and elongation values (percent in 2 inches) up to 10%.
  • the tensile strength of the solution annealed material Prior to age hardening, generally ranges from 45,000 to 55,000 p.s.i., the electrical conductivity is only about 7% I.A.C.S. and elongation is about 40% with reference to a representative alloy of the same composition containing 1.5% titanium, 2.5% tin, 0.5% chromium, balance copper.
  • the alloys of the present invention are readily processed from cast material into Wrought products such as bar stock, wire, sheet material, etc. utilizing typical processing steps consisting of (a) preheating the cast alloy at 800 to 850 C., (b) hot working as by rolling or forging, (c) solution annealing at about 875 C. for about 30 minutes, (d) quenching, and (e) age hardening at about 450 C. for about 6 to 8 hours.
  • Cold working with intermediate annealing may be additionally included in the processing steps with the alloy being subjected to precipitation hardening either in the cold Worked state or in the solution annealed condition following quenching.
  • the FIGURE shows that maximum precipitation hardening of the alloy occurs during the second through fourth hours of heat treatment but the electrical conductivity is only 20 to 25% I.A.C.S. with such heat treatment.
  • Overaging occurs after 4 hours with some loss of tensile strength but with an increase in elongation and conductivity values with the optimum combination of properties being obtained after aging for 6 to 8 hours.
  • tensile and yield strengths of about 95,000 and 70,000 p.s.i. respectively
  • elongation of from 13 to 16% and electrical conductivity values of from 40 to 46% I.A.C.S. are characteristic properties of the alloy.
  • Hardness values of this representative alloy range from 75 VPN in the solution annealed condition to about 200 VPN after aging for 8 hours.
  • Tensile strengths appreciably abo"e 100,000 p.s.i. with electrical conductivity better than 40% are readily obtained by aging the alloy after cold working-by wire drawing.
  • the properties obtained with specimens of 0.081 inch diameter wire of typical alloy compositions consisting of 1.5% Ti, 2.5% Sn, 0.7% Cr, balance copper (Alloy A) and 1.5% Ti, 2.75% Sn, 0.7% Cr, balance copper (Alloy B) that were cold worked 64% and aged for Varying periods up to 5 hours at 425 C. are summarlzed 1n Table I.
  • ultotrr/isiie siit'engtli 34-50, 000 8800s, 000 98-116, 000 O Se 0.1'7Zo1iset lis-28,000 70-90000 944-108.000 Proportioniillimit 8-18, 000 Lits-08,000 (s0-50,000 Table II Moduius olelasiicity (p. iii-i7, 000, 000 Y Elongation(pereentin2inch 20-35 8-15 5-12 A. ALLOY GOLD WoRirED 50% (ROLLED) Dcetllty (percent reduction in 32 I Eckters h ardnes (7 P lT).
  • the alloys of the present invention exhibit good ducg' ggg 1275, ggg gg 38 40 tility and strength at elevated temperatures asv will be 42g 5 1171000 1001000 ⁇ 90 4020 apparent from; the properties listed in Table IV.
  • the 425 6 115,000 95,000 8-0 40-0 short time Ktensile properties of the 15% Ti 25% Sn 92, 00 9.0 250 40.0 45g 58,000 10.0 23e 43.0 0.5% Cr, balance Cu, alloy in the form of 0.25 inch diameter rods were determined at 300 and 425 C. after B. ALLOY COLD WORKED 66. 5% 45 solution annealing at 875 C., quenching and heat treating at 450 C. for 6 hours.
  • beryllium copper alloy having the composition 0.65% Be, 2.70% Co, balance copper, 11i the form of 0.25 inch diameter rod material processed by solution annealing at 920 C., quenching and heat treat-
  • Table III A summary of the properties of a representative alloy ing at 480 C. for 3 hours and subsequently tested yat the of the present invention is presented in Table III wherein s211110 101111101010105 possessed 1611511@ '5119119118 0f 78,000
  • the perature properties of the respective alloys are quite comproportional limit was only 18,000 p.s.1. for the beryllium- 'parable with respect to the materials (a) in solution aricopper alloy compared to the value of 32,000 p.s.i. listed iiealed condition, (b) in the solution annealed and heat above. Contrasted with the elongation and ductility treated condition and also (c) in the solution annealed, values for the new alloy listed in Table IV, the berylliumrzold Worked and heat treated condition. copper alloy specimens tested at the same temperatures were extremely brittle and the elongation and ductility values therefor were nil.
  • silver may be additionally incorporated in the quaternary alloy in amounts up to about 1% without materially effecting the properties of the resulting all-oy.
  • the foregoing alloys were all made with initially oxygen-free copper. It was found that the tensile properties of the alloy made using tough pitch copper are generally about the same as those of the corresponding alloy made with initially oxygen-free copper provided that both alloys are processed in the same manner. The electrical conductivity is somewhat lower, however, as illustrated by the alloys containing 1.5% Ti, 2.5% Sn, 0.5% Cr. Comparison of the properties of the similarly processed alloys made with initially oxygen-free and tough pitch coppers showed a depression in electrical conductivity of from 45 to 37% I.A.C.S. attributable to the presence of OJZO in the tough pitch copper. Accordingly, the use of initially oxygen-free copper is generally necessary for obtaining electrical conductivities above 40% I.A.C.S.
  • An age hardenable copper base alloy of at least copper content said alloy consisting essentially of from 0.3 to 4% titanium, 0.5 to 5% tin and 0.05 to 2% chromium, the balance being substantially all copper with incidental impurities normally associated therewith.
  • An age hardenable copper base alloy of at least 90% copper content said alloy consisting essentially of from l to 3% titanium, 2 to 4% tin and 0.2 to 0.8% chromium, the balance being copper with incidental impurities nor mally associated therewith.
  • An age hardenable copper base alloy of at least copper content said alloy consisting essentially of from 1.3 to 1.7% titanium, 2.2 to 2.9% tin and 0.3 to 0.6% chromium, the balance being copper with incidental impurities normally associated therewith.
  • An age hardenable copper base alloy of at least 95% copper content said alloy consisting essentially of from 1.3 to 1.7% titanium,V 2.2 to 2.9% tin and 0.3 to 0.6% chromium, the balance being initially oxygen-free copper, the titanium and tin being present in the alloy in the ratio of about 1:1.7 respectively.
  • An age hardenable copper base alloy of at least 90% copper content said alloy consisting essentially of from 1 to 3% titanium, 2 to 4% tin, 0.2 to 0.8% chromium and an additional alloying element selected from the group consisting of silver and phosphorus in the amounts not eX- ceexling 1% and 0.05 respectively, the balance of the alloy being substantially all copper with incidental impurities normally associated therewith.
  • An age hardenable copper base alloy consisting essentially of from 1 to 3% titanium, 2 to 4% tin, 0.2 to 0.8% chromium and the balance substantially initially oxygen-free copper with impurities normally associated with such copper.
  • An age hardened alloy consisting essentially of from about 1.3 to 1.7% titanium, about 2.2to 2.9% tin, about 0.3 to 0.6% chromium, the balance being substantially all initially oxygen-free copper with impurities normally associated with such copper, said alloy being characterized by a combination of properties including a tensile strength of at least 90,000 p.s.i. and electrical conductivity of at least 40% I.A.C.S.
  • Copper-titanium-tin-chromium alloy made with initially oxygen-free copper, the content of titanium, tin and chromium of the quaternary alloy being about 1.5, 2.5 and 0.5% respectively, said alloy in the cold Worked and aged condition being characterized by a minimum tensile strength of 110,000 p.s.i. and electrical conductivity above 40% I.A.C.S.

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US27680A 1960-05-09 1960-05-09 Copper base alloys Expired - Lifetime US3017268A (en)

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GB9049/61A GB951121A (en) 1960-05-09 1961-03-13 Copper base alloys
CH531461A CH424276A (de) 1960-05-09 1961-05-05 Kupferlegierung und Verfahren zu deren Herstellung

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3305324A (en) * 1966-05-26 1967-02-21 Mallory & Co Inc P R Tungsten powder bodies infiltrated with copper-titanium-bismuth or copper-titanium-tin
US4116688A (en) * 1975-12-24 1978-09-26 General Dynamics Corporation Alloy and structures made therefrom
US4116689A (en) * 1975-12-24 1978-09-26 General Dynamics Corporation Material and method for securing boron filaments to each other and to a substrate and cutting tools therefrom
US4244679A (en) * 1978-07-31 1981-01-13 Kabushiki Kaisha Toyoda Jidoshokki Seisakusho Swash-plate-type compressor for air-conditioning vehicles
US20130115530A1 (en) * 2011-11-07 2013-05-09 Rovcal, Inc. Copper Alloy Metal Strip For Zinc Air Anode Cans
US20190161841A1 (en) * 2016-11-28 2019-05-30 Metal Industries Research & Development Centre Copper alloy wire and manufacturing method thereof
CN119800143A (zh) * 2024-12-27 2025-04-11 烟台万隆真空冶金股份有限公司 一种钛青铜合金丝材的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2059557A (en) * 1936-03-17 1936-11-03 Union Carbide & Carbon Res Lab Copper-base alloys
US2189198A (en) * 1938-06-28 1940-02-06 Titanium Alloy Mfg Co Copper-titanium alloy
US2797300A (en) * 1955-03-03 1957-06-25 Revere Copper & Brass Inc Welding
GB812407A (en) * 1955-02-18 1959-04-22 London Electric Wire Company A Improvements relating to chromium copper alloys

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2059557A (en) * 1936-03-17 1936-11-03 Union Carbide & Carbon Res Lab Copper-base alloys
US2189198A (en) * 1938-06-28 1940-02-06 Titanium Alloy Mfg Co Copper-titanium alloy
GB812407A (en) * 1955-02-18 1959-04-22 London Electric Wire Company A Improvements relating to chromium copper alloys
US2797300A (en) * 1955-03-03 1957-06-25 Revere Copper & Brass Inc Welding

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3305324A (en) * 1966-05-26 1967-02-21 Mallory & Co Inc P R Tungsten powder bodies infiltrated with copper-titanium-bismuth or copper-titanium-tin
US4116688A (en) * 1975-12-24 1978-09-26 General Dynamics Corporation Alloy and structures made therefrom
US4116689A (en) * 1975-12-24 1978-09-26 General Dynamics Corporation Material and method for securing boron filaments to each other and to a substrate and cutting tools therefrom
US4244679A (en) * 1978-07-31 1981-01-13 Kabushiki Kaisha Toyoda Jidoshokki Seisakusho Swash-plate-type compressor for air-conditioning vehicles
US20130115530A1 (en) * 2011-11-07 2013-05-09 Rovcal, Inc. Copper Alloy Metal Strip For Zinc Air Anode Cans
US10270142B2 (en) * 2011-11-07 2019-04-23 Energizer Brands, Llc Copper alloy metal strip for zinc air anode cans
US20190161841A1 (en) * 2016-11-28 2019-05-30 Metal Industries Research & Development Centre Copper alloy wire and manufacturing method thereof
CN119800143A (zh) * 2024-12-27 2025-04-11 烟台万隆真空冶金股份有限公司 一种钛青铜合金丝材的制备方法

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CH424276A (de) 1966-11-15

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