US3712837A - Process for obtaining copper alloys - Google Patents

Process for obtaining copper alloys Download PDF

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Publication number
US3712837A
US3712837A US00196006A US3712837DA US3712837A US 3712837 A US3712837 A US 3712837A US 00196006 A US00196006 A US 00196006A US 3712837D A US3712837D A US 3712837DA US 3712837 A US3712837 A US 3712837A
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United States
Prior art keywords
alloy
alloys
manganese
nickel
copper
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Expired - Lifetime
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US00196006A
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English (en)
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S Shapiro
A Goldman
D Tyler
R Lanam
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Olin Corp
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Olin Corp
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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
    • C22C9/05—Alloys based on copper with manganese 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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

Definitions

  • the disclosure teaches a method of preparing copper alloy having improved toughness and stress corrosion resistance.
  • the process comprises: providing a copper alloy containing from 12.5 to 30% nickel, 12:5 to 30% manganese, balance copper; hot rolling said alloy with a starting temperature in the range of 780 to 900 0.; cold rolling said alloy; and annealing said alloy at a temperature of from 550 to 900 C. for at least one minute while maintaining an average grain size of less than 0.015 mm.
  • Copper base alloys which contain relatively large amounts of nickel and manganese. Alloys of this type are highly desirable since they are capable of obtaining yield strengths in excess of 200K s.i. upon aging. In addition, these alloys appear to have reasonable processing and in particular are not quench sensitive.
  • the presence of a marked aging response to obtain high strengths in copper-nicked manganese alloys is known. It has been found that different types of precipitation reactions may occur in this alloy system, depending on the aging temperature. For example, aging at a low temperature, such as 350 C., yield a cellular precipitate which nucleates at the grain boundaries and with time grows throughout the entire grain. The cellular precipitate consists of adjacent lamellae of a manganese-nickel rich phase and the copper-rich solid solution. Aging at higher temperatures, such as 450 C., yields mainly finely dispersed, spherical precipitates of the manganese-nickel rich phase within the grains and only a small amount of the cellular precipitate at the grain boundaries.
  • the process of the present invention comprises: providing a copper base alloy containing from 12.5 to 30% nickel, from 12.5 to 30% manganese, balance copper, wherein the nickel to manganese ratio is at least 0.75 and preferably 1.0 or higher; hot rolling said alloy with a starting hot rolling temperature in the range of 780 to 900 C., cold rolling said alloy, and annealing said alloy at a temperature of from 550 to 900 C. for at least one minute while maintaining an average grain size of less than 0.015 mm.
  • the alloys which are obtained in accordance with the present invention are excellent lower priced replacements for beryllium-copper, with increased fracture toughness.
  • the alloys achieve levels of fracture toughness approaching high alloy steels which are limited in applicability by poor corrosion resistance.
  • the alloys are superior to maraging steels in marine environments since the alloys obtained in accordance with the present invention are not susceptible to hydrogen embrittlement.
  • the alloys provided pursuant to the instant process are characterized by excellent stress corrosion resistance.
  • the starting alloys contain from 12.5 to 30% nickel, and from 12.5
  • both the nickel and manganese contents should range from 15 to 25%.
  • the nickel to manganese ratio must be at least 0.75 and preferably 1.0 or higher.
  • the nickel and manganese contents have an affect on aging response, yield strength and workability of the alloys.
  • increasing the amount Olf nickel and manganese has deleterious effects on the workability of the alloys during processing, especially over 30% each of nickel and manganese.
  • the preferred nickel to manganese ratio is 1.0 or higher.
  • the maximum aging response is obtained for a given amount of nickel and manganese when the nickel to manganese ratio is about 1.0. If the ratio is less than 1.0, an excess of manganese exists which can have adverse effects on the stress corrosion resistance of the alloy. A ratio greater than about 1.5 does not give improved results over a ratio of about 1.0 and is more expensive due to the high cost of the nickel.
  • the starting alloys contain certain alloying additions. These alloying additions will be described hereinbelow and they may be present either separately or in combination.
  • the alloy contain a material selected from the group consisting of aluminum in an amount from 0.01 to 5.0%, magnesium from 0.01 to 5.0%, boron from 0.001 to 0.1% and mixtures thereof.
  • Aluminum is the preferred addition since it tends to form a protective oxide coating during melting.
  • the aluminum should be added in an amount from 0.01 to 0.75%.
  • magnesium should be used in an amount from 0.01 to 0.75% as a deoxidant.
  • the aluminum and magnesium may be used as advantageous alloying additions in amounts greater than 0.6% for increased corrosion resistance and fracture toughness. The aluminum when used at the higher levels, also tends to modify the cellular precipitate at the grain boundaries.
  • a zinc component may be present in an amount from 0.1 to 3.5% and preferably from 1 to 3%. Increased amounts of zinc give rise to a decrease in the stress corrosion resistance and fracture toughness.
  • the zinc addition controls the grain size, reduces the cellular precipitate at the grain boundaries, changes the morphology of the inclusions, promotes sound castings and increases the aging response of the alloy.
  • Tin is also a particularly desirable additive in an amount from 0.01 to 2% and preferably from 0.5 to 1.0%. Tin tends to alter the morphology of the cellular precipitate at the grain boundary.
  • zirconium and/or titanium are preferred alloying additions in amounts 0.01 to 2.0% each, and preferably from 0.15 to 0.30% each. These materials tend to desirably change morphology and chemistry of inclusions and desirably change morphology of cellular precipitate at grain boundaries.
  • chromium is a desirable addition in an amount from 0.01 to 1.0%, and preferably from 0.15 to 0.30%. Chromium tends to control the grain size and change the morphology and chemistry of inclusion.
  • Additional desirable alloying additions are cobalt and/ or iron in amounts from 0.05 to 1.0% each, and preferably from 0.2 to 0.5% each. These materials also tend to control the grain size.
  • the alloys desirably utilize a material selected from the group consisting of aluminum, magnesium, boron, zinc, tin, zirconium, titanium, chromium, cobalt, iron and mixtures thereof, all in the amounts listed hereinabove.
  • the casting of the alloy of the present invention is not particularly significant. Any convenient method of casting may be employed. Pouring temperatures in the range of about 1000 to 1200 C. are preferably employed, with an optimum pouring temperature in the range of 1050 to 1100 C.
  • the alloy of the present invention is processed by breakdown of ingot into strip using a hot rolling operation followed by cold rolling and annealing cycles to reach final gage.
  • Preferred properties are obtained using an aging treatment.
  • the starting hot rolling temperature should be in the range of 700 to 900 C., and preferably 780 to 900 C.
  • the cooling rate from hot rolling should preferably be in excess of 25 C. per hour down to 300 C. in order to avoid precipitation of manganese-nickel rich phases.
  • the cooling rate after 300 C. is not significant.
  • the alloy is capable of cold rolling reductions in excess of 90%, but the cold rolling reduction should preferably be between 30 and 80% in order to control the grain size.
  • an average grain size less than 0.015 mm. is required to give the optimum fracture toughness.
  • An average grain size of this order can be obtained by control of the cold rolling reduction, annealing times and annealing temperatures. In general, annealtemperatures in the range of 550 to 900 C. for at least one minute can give the required grain size, with 10* hours being the practical upper limit and 2 hours being the preferred upper limit. It is preferred to anneal for from five minutes to 2 hours.
  • the material After annealing, the material is cooled in excess of 25 C. per hour down to 300 C., as indicated above, and the cold rolling and annealing cycles repeated as desired depending on gage requirements. Generally, from two to four cycles of cold rolling and annealing are preferred.
  • the alloy of the present invention may be aged in the range of 250 to 475 C., with temperatures of 380 to 460 C. being preferred. Aging times of 30 minutes to 10 hours, with preferred times of 1 to 6 hours, are used to obtain the desired properties.
  • controlling the amount of cold work prior to aging has an effect on fracture toughness and aging response. In particular, it has been observed that the cold work gives rise to increased nucleation sites for the intragranular precipitation of the discrete manganese-nickel rich particles.
  • the amount of cold rolling can vary from 10 to 50% with from 15 to 45% yielding the optimum fracture toughness.
  • EXAMPLE I The Durville method was used to cast the various alloys listed in Table I. The copper and nickel were melted under a charcoal cover. Aluminum was added to deoxidize the melt. Following the removal of the charcoal cover, the manganese and zinc additions were made. The slag was removed and the melt was poured from approximately 1080 C.
  • Example I TABLE L--COMPOSITION, WEIGHT PERCENT
  • Alloys A and B were homogenized at 840 C. for about 2 hours, followed by hot rolling from 1.500 inches to 0.418 inch and water quenching. The alloys were cold rolled 60% to 0.167 inch. Alloys A and B were then annealed at 600 C. for about 30 minutes and water quenched. The alloys were cold rolled 60% to 0.067 inch and annealed and quenched again in the same manner. Subsequent to the water quench, the alloys were cold rolled 25% to 0.050 inch and aged at 450 C. for various times.
  • Alloys C and D were homogenized at 840 C. for about 2 hours, followed by hot rolling from 1.500 inches to 0.320 inch and water quenching. The alloys were cold rolled 62.5% to 0.120 inch. Alloys C and D were then annealed at 650 C. for about 60 minutes. The alloys were cold rolled 44% to 0.067 inch and were again annealed at 650 C. for about 60 minutes. Subsequent to the water quench, the alloys were cold rolled 25% to 0.050 inch and aged at 450 C. for various times.
  • Alloys A and B had an average grain diameter of 0.005 to 0.010 mm.
  • Alloy C had an average grain diameter of 0.024 mm, and Alloy D 0.022 mm.
  • the resulting properties longitudinal to the rolling direction upon aging at 450 C. are presented in Table 11.
  • the data are presented in graphical form in FIG. 1.
  • the UPE is plotted as a function of yield strength for Alloys A, B, C and D.
  • yield strength For a given yield strength, the superiority of the fine grained material processed in accordance with the present invention is quite graphic.
  • a method of preparing copper base alloys having improved toughness and stress corrosion resistance which comprises:
  • said copper base alloy contains a material selected from the group consisting of: aluminum from 0.01 to 5%; magnesium from 0.01 to 5 boron from 0.001 to 0.1%; zinc from 0.1 to 3.5%; tin from 0.01 to 2% zirconium from 0.01 to 2%; titanium from 0.01 to 2%; chromium from 0.01 to 1%; iron from 0.05 to 1%; cobalt from 0.05 to 1%; and mixtures thereof.
  • a method according to claim 5 wherein said annealing time is from 5 minutes to 2 hours.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
  • Conductive Materials (AREA)
US00196006A 1971-11-05 1971-11-05 Process for obtaining copper alloys Expired - Lifetime US3712837A (en)

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US19600671A 1971-11-05 1971-11-05

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US (1) US3712837A (de)
JP (1) JPS545370B2 (de)
AU (1) AU461925B2 (de)
CA (1) CA975584A (de)
CH (1) CH592155A5 (de)
DE (1) DE2247333A1 (de)
FR (1) FR2159942A5 (de)
GB (1) GB1399293A (de)
IT (1) IT1000020B (de)
SE (1) SE397106B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985589A (en) * 1974-11-01 1976-10-12 Olin Corporation Processing copper base alloys
WO1994001591A1 (en) * 1992-07-01 1994-01-20 Olin Corporation Machinable copper alloys having reduced lead content
CN100537803C (zh) * 2007-01-29 2009-09-09 中南大学 炭/炭复合材料与铜连接用合金及其制备工艺
WO2020078380A1 (zh) * 2018-10-16 2020-04-23 比亚迪股份有限公司 压铸铜合金及其制备方法以及压铸铜合金复合塑料产品
CN114959356A (zh) * 2022-06-23 2022-08-30 厦门火炬特种金属材料有限公司 一种新型高电阻率、低温漂的铜基精密电阻合金及其制备方法
CN117926049A (zh) * 2024-01-26 2024-04-26 昆明理工大学 一种超高强高弹性细晶Cu-Ni-Mn合金及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5319131A (en) * 1976-08-06 1978-02-22 Mitsubishi Metal Corp Cu alloy for base material of composite electric contact
JPS56142626U (de) * 1980-03-28 1981-10-28

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985589A (en) * 1974-11-01 1976-10-12 Olin Corporation Processing copper base alloys
US5409552A (en) * 1991-03-01 1995-04-25 Olin Corporation Machinable copper alloys having reduced lead content
WO1994001591A1 (en) * 1992-07-01 1994-01-20 Olin Corporation Machinable copper alloys having reduced lead content
CN100537803C (zh) * 2007-01-29 2009-09-09 中南大学 炭/炭复合材料与铜连接用合金及其制备工艺
WO2020078380A1 (zh) * 2018-10-16 2020-04-23 比亚迪股份有限公司 压铸铜合金及其制备方法以及压铸铜合金复合塑料产品
CN111057901A (zh) * 2018-10-16 2020-04-24 比亚迪股份有限公司 压铸铜合金及其制备方法和应用以及压铸铜合金复合塑料产品
CN111057901B (zh) * 2018-10-16 2021-09-03 比亚迪股份有限公司 压铸铜合金及其制备方法和应用以及压铸铜合金复合塑料产品
CN114959356A (zh) * 2022-06-23 2022-08-30 厦门火炬特种金属材料有限公司 一种新型高电阻率、低温漂的铜基精密电阻合金及其制备方法
CN114959356B (zh) * 2022-06-23 2023-08-22 有研金属复材(忻州)有限公司 一种高电阻率、低温漂的铜基精密电阻合金及其制备方法
CN117926049A (zh) * 2024-01-26 2024-04-26 昆明理工大学 一种超高强高弹性细晶Cu-Ni-Mn合金及其制备方法

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Publication number Publication date
JPS4853926A (de) 1973-07-28
AU461925B2 (en) 1975-06-12
CH592155A5 (de) 1977-10-14
AU4685972A (en) 1974-03-28
SE397106B (sv) 1977-10-17
FR2159942A5 (de) 1973-06-22
CA975584A (en) 1975-10-07
DE2247333A1 (de) 1973-05-10
JPS545370B2 (de) 1979-03-16
GB1399293A (en) 1975-07-02
IT1000020B (it) 1976-03-30

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