US20040042928A1 - High strength copper alloy and manufacturing method therefor - Google Patents

High strength copper alloy and manufacturing method therefor Download PDF

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Publication number
US20040042928A1
US20040042928A1 US10/653,352 US65335203A US2004042928A1 US 20040042928 A1 US20040042928 A1 US 20040042928A1 US 65335203 A US65335203 A US 65335203A US 2004042928 A1 US2004042928 A1 US 2004042928A1
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cold rolling
copper alloy
reduction rate
additional cold
high strength
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Abandoned
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US10/653,352
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English (en)
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Fumiaki Sasaki
Yozo Tsugane
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Dowa Metanix Co Ltd
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Individual
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Assigned to YAMAHA METANIX CORPORATION reassignment YAMAHA METANIX CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SASAKI, FUMIAKI, TSUGANE, YOZO
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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
    • 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

  • This invention relates to high strength copper alloys that contain titanium (Ti) to realize high bend formability and high yield strength.
  • this invention also relates to manufacturing methods for manufacturing high strength copper alloys.
  • high strength titanium-contained copper alloy is produced as shown in FIG. 4, in which a prescribed material therefor is subjected to cold rolling and is then subjected to solution treatment upon heating to a temperature ranging from 750° C. to 950° C. for 1000 seconds and is then subjected to final cold rolling processing; thereafter, it is subjected to precipitation treatment upon heating to a temperature ranging from 300° C. to 700° C. for a prescribed time ranging from 0.5 hour to 15 hours, for example.
  • This conventional high strength copper alloy contains titanium (Ti) at 2.9-3.5 weight percent, which may be defined by Japanese Industrial Standards Code JISH3130C1990. This alloy can be used for various components and connectors of electronic devices and electric appliances.
  • t1 denotes a plate thickness of a material after cold rolling
  • t2 denotes a plate thickness of a material after final cold rolling
  • a high strength copper alloy is made of a prescribed material composed of Cu and inevitable impurities as well as titanium (Ti) at 0.1 to 4 weight percent, wherein it is possible to further include at least one of Ag, Ni, Fe, Si, Sn, Mg, Zn, Cr, and P at a prescribed weight percent ranging from 0.01 to 2 in total.
  • the material is subjected to cold rolling, precipitation treatment, and additional cold rolling sequentially, wherein the reduction rate of the additional cold rolling is set to 3% or more, and the total reduction rate of the cold rolling and the additional cold rolling ranges from 15% to 50%, so that a ratio of yield strength versus tensile strength is set to 0.9 or more.
  • FIG. 1 is a brief diagram showing a manufacturing process of a high strength copper alloy in accordance with a first embodiment of the invention
  • FIG. 2 is a brief diagram showing a manufacturing process of a high strength copper alloy in accordance with a second embodiment of the invention
  • FIG. 3 is a graph showing curves representing ratios of yield strength versus tensile strength in copper alloys produced in the present invention compared with a conventional art
  • FIG. 4 shows a manufacturing process for a conventional high strength copper alloy
  • FIG. 5 is a table showing processing conditions of samples compared with comparative samples.
  • FIG. 6 is a table showing characteristics of samples compared with comparative samples.
  • FIG. 1 shows a manufacturing process for a high strength copper alloy in accordance with a first embodiment of the present invention.
  • a copper alloy material containing titanium (Ti) at 1 to 4 weight percent is subjected to cold rolling and is then subjected to solution treatment upon heating to a temperature ranging from 750° C. to 950° C. for a prescribed time ranging from 10 seconds to 1000 seconds.
  • cold rolling is performed on the material; thereafter, precipitation treatment is performed at a temperature ranging from 300° C. to 700° C. for a prescribed time ranging from 0.5 hour to 15 hours.
  • additional cold rolling is performed on the material.
  • the aforementioned material is prepared by way of a vacuum melting furnace introducing pure copper (Cu) and pure titanium (Ti) and is then cast into an ingot having prescribed dimensions such as 50 mm thickness and 150 mm width, for example.
  • the reduction rate of the additional cold rolling is set to 3% or more, so that the total reduction rate may range from 15% to 50%.
  • the additional cold rolling reduction rate is less than 3%, it is necessary to increase the total reduction rate in order to realize a high strength for a copper alloy, which, however, results in deterioration of bend formability.
  • the reduction rate of the conventional art is substantially set to 0%, the present embodiment becomes close to the conventional art in property if the reduction rate is less than 3%, wherein in order to produce yield strength matching 90% or more of the tensile strength, it is necessary to increase the total reduction rate to be 50% or more, whereas if the total reduction rate exceeds 50%, a hardening process may be caused to occur intensely in cold rolling so that a copper alloy product must be deteriorated in bend formability.
  • the present embodiment is characterized in that the precipitation treatment is followed by the additional cold rolling; in other words, the precipitation treatment is performed before the final cold rolling (i.e., additional cold rolling).
  • the precipitation treatment is performed before the final cold rolling (i.e., additional cold rolling).
  • a dotted curve shown in FIG. 3 represents the property of a high strength copper alloy. Compared with the solid curve representing the property of the conventional copper alloy, a value of yield strength against the tensile strength is increased to be higher and is therefore improved in the copper alloy of the present embodiment at the same total reduction rate.
  • FIG. 3 noticeably shows that the present embodiment can offer a sufficient high value of yield strength matching 90% of the tensile strength at a lower-limit value of 15% of the total reduction rate.
  • a Cu-Ti alloy is produced through precipitation treatment that is performed generally at a relatively high temperature, which results in a high heat resistance.
  • the present embodiment is characterized in that the additional cold rolling is performed after the precipitation process, which may present a possibility that the heat resistance will be reduced.
  • the copper alloy of the present embodiment can demonstrate substantially the same heat resistance compared with the conventional copper alloy. This is because dislocation due to the additional cold rolling after the precipitation process may be subjected to pinning by precipitates and be avoided.
  • the present embodiment can increase the yield strength to match 90% or more of the tensile strength even when the total reduction rate is 50% or less.
  • the copper alloy of the present embodiment is compared with the conventional copper alloy at the same total reduction rate, it is possible to actualize the following advantages:
  • the present embodiment can offer a ratio of yield strength versus tensile strength at 0.9 even when the total reduction rate is set to 15%.
  • the second embodiment shown in FIG. 2 performs cold rolling, solution treatment, cold rolling before precipitation, precipitation treatment, and additional cold rolling in turn.
  • the second embodiment is characterized by performing stress relaxation annealing after the additional cold rolling, wherein an alloy coil is put into a batch type furnace in which it is heated to a temperature ranging from 200° C. to 700° C. for a prescribed time ranging from 0.5 hour to 15 hours; preferably, it is heated to a temperature of 350° C. for three hours, for example.
  • an alloy coil is put into a continuous furnace in which it is heated to a temperature ranging from 300° C. to 950° C. for 10 seconds to 1000 seconds; preferably, it is heated to a temperature of 500° C. for 30 seconds, for example.
  • the second embodiment performs stress relaxation annealing after the additional cold rolling under the aforementioned conditions, it is possible to improve spring characteristics (e.g., spring limit values), which have been slightly reduced in the additional cold rolling. Therefore, it is possible to obtain relatively high spring limit values while securing relatively high bend formability and relatively high yield strength.
  • spring characteristics e.g., spring limit values
  • the aforementioned stress relaxation annealing is performed for the purpose of improvements of spring characteristics without deteriorating the material in strength, conductivity, and bend formability.
  • the batch type furnace or continuous furnace is used to perform the stress relaxation annealing.
  • heating is performed at a temperature ranging from 200° C. to 700° C. for 0.5 hour to 15 hours. This is because it is difficult to improve spring characteristics, which have been reduced in the additional cold rolling, at a relatively low temperature less than 200° C., and yield strength must be reduced due to progress of recrystallization at a relatively high temperature higher than 700° C.
  • aging must be progressed too rapidly to realize improvement of spring characteristics so that bend formability must be deteriorated when annealing is performed for 15 hours or more.
  • heating is performed at a temperature ranging from 300° C. to 900° C. for 10 seconds to 1000 seconds. This is because when the heating temperature is less than 300° C., heating must be performed for a long time, resulting in a reduction of productivity, wherein it is difficult to improve spring characteristics, which have been reduced in the additional cold rolling, when heating temperature is very low. In addition, when heating temperature is higher than 900° C., solution treatment is progressed so rapidly that yield strength and conductivity are reduced. Furthermore, when heating is performed for a short time less than 10 seconds, the material cannot be sufficiently heated so that spring characteristics cannot be improved. When heating is performed for a long time greater than 1000 seconds, productivity must be reduced.
  • the copper alloy has a prescribed composition including titanium (Ti) at 0.1 to 4 weight percent. If the titanium content is appropriately set, it may be possible to produce a copper alloy having a high strength because the titanium content is increased so that an amount of precipitation hardening must be increased during manufacturing processes. However, conductivity and bend formability must be reduced, so that productivity must be correspondingly reduced. That is, when the titanium content is less than 0.1 weight percent, a copper alloy must be decreased in strength because of a relatively small amount of precipitation hardening. When it exceeds 4 weight percent, a copper alloy must be deteriorated in characteristics so that productivity must be decreased. Because of the aforementioned reasons, the titanium content is set in a range from 0.1 to 4 weight percent.
  • the second embodiment it is possible to selectively use at least one of Ag, Ni, Fe, Si, Sn, Mg, Zn, Cr, and P, which can be contained in the material at a ratio ranging from 0.01 to 2 weight percent in total.
  • These elements may present an improvement of the strength of Cu-Ti alloy due to precipitation hardening and solid solution hardening. When the total of these elements is less than 0.01 weight percent, it is very difficult to obtain the aforementioned effect. When it exceeds 2 weight percent, these elements must deteriorate reduction rate in production of Cu—Ti alloy, which may result in reduction of conductivity and bend formability.
  • pure Cu and pure Ti are adequately blended together and are then introduced into a vacuum melting furnace, thus producing an ingot having prescribed dimensions such as 50 mm thickness and 150 mm width.
  • the material is heated up to 900° C. and subjected to homogenization; then, the material is subjected to solution treatment upon heating to a temperature of 900° C. for 70 to 200 seconds.
  • cold rolling before precipitation is performed under prescribed conditions, which are shown in FIG. 5.
  • the material is subjected to precipitation treatment upon heating at a temperature of 450° C. for 6 hours; thereafter, the additional cold rolling after precipitation is performed under prescribed conditions shown in FIG. 5.
  • samples 1-11 are subjected to additional cold rolling to realize a plate thickness of 0.30 mm after final cold rolling.
  • comparative samples 12-22 are also produced without performing additional cold rolling, wherein each of them is subjected to cold rolling before precipitation to realize a plate thickness of 0.30 mm after final cold rolling.
  • samples 8-11 (corresponding to the embodiments) and comparative samples 19-20 are subjected to stress relaxation annealing after additional cold rolling.
  • FIG. 6 Characteristics of copper alloys that are produced as samples 1-11 and comparative samples 12-22 are shown in FIG. 6, wherein assessments using Japanese Industrial Standards (JIS) are performed with respect to tensile strength according to JIS-Z2241, yield strength according to JIS-Z2241 (allowing 0.2% offset in yield strength), elongation according to JIS-Z2241 (breaking elongation), conductivity according to JIS-H0505, spring characteristics according to JIS-H3130 (spring limit values), bend formability according to JIS-H3130 (W bending), and heat resistance according to stress relaxation characteristics, for example.
  • JIS Japanese Industrial Standards
  • the bend formability is assessed through the observation of the exterior of a bent portion upon estimation of a minimum bent radius causing no crack at a prescribed total reduction rate, as follows:
  • each sample is formed in 10 mm width and L mm length, and is wound about an instrument having a radius r, to which a certain stress is applied and which is heated to 230° C. for 1000 hours; thus, a degree of stress relaxation is expressed in percent.
  • FIG. 6 shows that each of samples 1-4 and 7-11 is superior in both tensile strength and yield strength in comparison with comparative samples at the same total reduction rate, wherein a ratio of yield strength versus tensile strength is 0.9 or more. In addition, each of them is also superior in bend formability, which is equal or high than that of the comparative sample. Furthermore, each of them is superior in heat resistance as well.
  • Each of samples 5-6 may be somewhat weak in tensile strength and yield strength because of a reduction of titanium content, wherein similar to the aforementioned samples, each of them has a relatively high ratio of yield strength versus tensile strength, which is 0.9 or more.
  • each of samples 8-11 is subjected to stress relaxation annealing; therefore, each of them is superior in spring limit value in comparison with the foregoing samples 1-7 while securing high yield strength and high bend formability.
  • Comparative sample 12 has a relatively low ratio of yield strength versus tensile strength, which is 0.88, because of a relatively low additional cold rolling reduction rate that is 2% (see FIG. 5). Comparative example 13 offers relatively low elongation and relatively low conductivity because of a relatively high total reduction rate that is 70%.
  • Each of comparative samples 14-18 substantially corresponds to the conventional alloy that is produced without performing additional cold rolling, wherein each of them is reduced in a ratio of yield strength versus tensile strength, and it offers very small elongation.
  • Comparative sample 19 cannot demonstrate improvement in spring characteristics because of a relatively low temperature in stress relaxation annealing.
  • comparative sample 20 not only has improved spring characteristics but also degraded bend formability due to progress of aging because of the relatively long time in stress relaxation annealing.
  • Comparative sample 21 is reduced in strength because of a relatively small titanium content and is also reduced in heat resistance. Comparative sample 22 is reduced in both tensile strength and yield strength because of a relatively high titanium content and is remarkably reduced in bend formability.
  • a high strength copper alloy of this invention contains titanium (Ti) at 0.4 to 4 weight percent, wherein it is basically composed of copper (Cu) and inevitable impurities. That is, a prescribed material is subjected to cold rolling and precipitation treatment, and is then subjected to additional cold rolling.
  • the reduction rate of the additional cold rolling is set to 3% or more, and the total reduction rate for the cold rolling and additional cold rolling is set in a range from 15% to 50%, for example.
  • At least one of Ag, Ni, Fe, Si, Sn, Mg, Zn, Cr, and P can be selectively introduced into a high strength copper alloy at a prescribed weight percent ranging from 0.01% to 2%, for example.
  • the material can be subjected to stress relaxation annealing in which it is heated to a temperature ranging from 200° C. to 700° C. for 0.5 hour to 15 hours, or it is heated to a temperature ranging from 300° C. to 950° C. for a prescribed time ranging from 10 seconds to 1000 seconds, for example.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286714A (zh) * 2011-08-15 2011-12-21 江西理工大学 一种铜镍锡合金的制备方法
US20160062074A1 (en) * 2014-08-29 2016-03-03 Jx Nippon Mining & Metals Corporation High-Strength Titanium Copper Foil and Method for Producing Same
CN105385879A (zh) * 2014-08-29 2016-03-09 Jx日矿日石金属株式会社 高强度钛铜箔及其制造方法
RU2587114C2 (ru) * 2014-09-22 2016-06-10 Дмитрий Андреевич Михайлов Медный сплав для коллекторов электрических машин
CN110042269A (zh) * 2012-07-19 2019-07-23 Jx日矿日石金属株式会社 高强度钛铜箔及其制备方法
US11174534B2 (en) 2017-03-30 2021-11-16 Jx Nippon Mining & Metals Corporation High strength titanium copper strip and foil having layered structure
US11180829B2 (en) 2017-03-30 2021-11-23 Jx Nippon Mining & Metals Corporation High strength titanium copper strip and foil having layered structure
US11739397B2 (en) 2018-11-09 2023-08-29 Jx Nippon Mining & Metals Corporation Titanium copper foil, extended copper article, electronic device component, and auto-focus camera module
US12000029B2 (en) 2018-11-09 2024-06-04 Jx Metals Corporation Titanium copper foil, extended copper article, electronic device component, and auto-focus camera module

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JP2005317463A (ja) * 2004-04-30 2005-11-10 Nikko Metal Manufacturing Co Ltd 高周波信号伝送用材料および端子
JP4761586B1 (ja) * 2010-03-25 2011-08-31 Ｊｘ日鉱日石金属株式会社 高強度チタン銅板及びその製造方法
JP6703878B2 (ja) 2016-03-31 2020-06-03 Ｊｘ金属株式会社 チタン銅箔および、その製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102286714A (zh) * 2011-08-15 2011-12-21 江西理工大学 一种铜镍锡合金的制备方法
CN110042269A (zh) * 2012-07-19 2019-07-23 Jx日矿日石金属株式会社 高强度钛铜箔及其制备方法
US20160062074A1 (en) * 2014-08-29 2016-03-03 Jx Nippon Mining & Metals Corporation High-Strength Titanium Copper Foil and Method for Producing Same
CN105385878A (zh) * 2014-08-29 2016-03-09 Jx日矿日石金属株式会社 高强度钛铜箔及其制造方法
CN105385879A (zh) * 2014-08-29 2016-03-09 Jx日矿日石金属株式会社 高强度钛铜箔及其制造方法
US9436065B2 (en) * 2014-08-29 2016-09-06 Jx Nippon Mining & Metals Corporation High-strength titanium copper foil and method for producing same
US10215950B2 (en) * 2014-08-29 2019-02-26 Jx Nippon Mining & Metals Corporation High-strength titanium copper foil and method for producing same
RU2587114C2 (ru) * 2014-09-22 2016-06-10 Дмитрий Андреевич Михайлов Медный сплав для коллекторов электрических машин
US11174534B2 (en) 2017-03-30 2021-11-16 Jx Nippon Mining & Metals Corporation High strength titanium copper strip and foil having layered structure
US11180829B2 (en) 2017-03-30 2021-11-23 Jx Nippon Mining & Metals Corporation High strength titanium copper strip and foil having layered structure
US11739397B2 (en) 2018-11-09 2023-08-29 Jx Nippon Mining & Metals Corporation Titanium copper foil, extended copper article, electronic device component, and auto-focus camera module
US12000029B2 (en) 2018-11-09 2024-06-04 Jx Metals Corporation Titanium copper foil, extended copper article, electronic device component, and auto-focus camera module

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JP2004091871A (ja) 2004-03-25

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