Source: http://www.freepatentsonline.com/9587299.html
Timestamp: 2019-01-23 23:57:35
Document Index: 731477725

Matched Legal Cases: ['Application No. 11780706', 'Application No. 2010', 'Application No. 201207897', 'Application No. 201180018491', 'Application No. 12847293', 'Application No. 201280047170', 'Application No. 12843355', 'Application No. 201280047171', 'Application No. 12849153', 'Application No. 2011', 'Application No. 101139714', 'Application No. 101141343', 'Application No. 201280049749', 'Application No. 12843355', 'Application No. 12849153', '§371', 'Application No. 2011']

Copper alloy for electronic equipment, method for producing copper alloy for electronic equipment, rolled copper alloy material for electronic equipment, and part for electronic equipment - MITSUBISHI MATERIALS CORPORATION
United States Patent 9587299
This copper alloy for electronic devices includes Mg at a content of 3.3 at % or more and 6.9 at % or less, with a remainder substantially being Cu and unavoidable impurities. When a concentration of Mg is given as X at %, an electrical conductivity σ (% IACS) is in a range of σ≦{1.7241/(−0.0347×X2+0.6569×X+1.7)}×100, and a stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less.
Maki, Kazunari (Saitama, JP)
Ito, Yuki (Okegawa, JP)
14/349937
C22C9/00; C22C9/02; C22F1/08; H01B1/02; C22C9/05
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Koshy, Jophy S.
1. A rolled copper alloy material for electronic devices, consisting of: a binary alloy of Cu and Mg, wherein the binary alloy is a Cu—Mg solid solution alloy supersaturated with Mg, the binary alloy consists of Mg at a content of 3.3 at % or more and 6.9 at % or less, and a remainder of Cu and unavoidable impurities, an amount of Zn as an unavoidable impurity is less than 0.01 mass %, a total amount of the unavoidable impurities is in a range of 0.3 mass % or less, the rolled copper alloy material is a sheet or a strip, the binary alloy has a measured value of electrical conductivity, σ, in a range of 31.2-44.1% IACS, wherein the measured value of electrical conductivity is less than or equal to an upper limit of electrical conductivity, in %, calculated by the formulaic expression, {1.7241/(−0.0347×X2+0.6569×X+1.7)}×100, wherein X is the content of the Mg in the binary alloy; a stress relaxation rate is in a range of 50% or less after heating at 150° C. for 1,000 hours, and a 0.2% proof stress σ0.2 in a direction parallel to a rolling direction is in a range of 400 MPa or more.
2. The rolled copper alloy material for electronic devices according to claim 1, wherein an average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less during observation by a scanning electron microscope.
9. A method for producing a rolled copper alloy material for electronic devices, the method comprising: a heating process of heating an ingot consisting of a binary alloy of Cu and Mg at a temperature of 400 to 900° C. to obtain a copper material; a first rapid cooling process of cooling the copper material; an intermediate heat treatment process of heating the copper material; a second rapid cooling process of cooling the copper material; a finishing working process of subjecting the copper material to rolling into a predetermined shape; a finishing heat treatment process of subjecting the copper material to a heat treatment after the finishing working process; and a third rapid cooling process of cooling the copper material, wherein in the first, second and third rapid cooling processes, the copper material is cooled to a temperature of 200° C. or lower at a cooling rate of 200° C./min or higher, wherein the produced rolled copper alloy material consists of the binary alloy of Cu and Mg, the rolled alloy material is a solution alloy supersaturated with Mg, the binary alloy consists of Mg at a content of 3.3 at % or more and 6.9 at % or less, and a remainder of Cu and unavoidable impurities, an amount of Zn as an unavoidable impurity is less than 0.01 mass %, a total amount of the unavoidable impurities is in a range of 0.3 mass % or less, the rolled copper alloy material is a sheet or a strip, the binary alloy has a measured value of electrical conductivity, σ, in a range of 31.2-44.1% IACS, wherein the measured value of electrical conductivity is less than or equal to an upper limit of electrical conductivity, in %, calculated by the formulaic expression, {1.7241/(−0.0347×X2+0.6569×X+1.7)}×100, wherein X is the content of the Mg in the binary alloy; a stress relaxation rate of the rolled copper alloy material is in a range of 50% or less after heating at 150° C. for 1,000 hours, and a 0.2% proof stress σ0.2 of the rolled copper alloy material in a direction parallel to a rolling direction is in a range of 400 MPa or more.
10. The method for producing a rolled copper alloy material for electronic devices according to claim 9, wherein, in the intermediate heat treatment process, the heat treatment is performed at a temperature of 400° C. or higher and 900° C. or lower, and in the finishing heat treatment process, the heat treatment is performed at a temperature of higher than 200° C. and 800° C. or lower.
11. A method for producing a rolled copper alloy material for electronic devices, the method comprising: a heating process of heating an ingot consisting of a binary alloy of Cu and Mg at a temperature of 400 to 900° C. to obtain a copper material; a first rapid cooling process of cooling the copper material; an intermediate heat treatment process of heating the copper material; a second rapid cooling process of cooling the copper material; a finishing working process of subjecting the copper material to rolling into a predetermined shape; a finishing heat treatment process of subjecting the copper material to a heat treatment after the finishing working process; and a third rapid cooling process of the cooling copper material, wherein in the first, second and third rapid cooling processes, the copper material is cooled to a temperature of 200° C. or lower at a cooling rate of 200° C./min or higher, wherein the produced rolled copper alloy material consists of the binary alloy of Cu and Mg, the rolled copper alloy material is a Cu—Mg solid solution alloy supersaturated with Mg, the binary alloy consists of Mg at a content of 3.3 at % or more and 6.9 at % or less, and a remainder of Cu and unavoidable impurities, an amount of Zn as an unavoidable impurity is less than 0.01 mass %, a total amount of the unavoidable impurities is in a range of 0.3 mass % or less, the rolled copper alloy material is a sheet or a strip, the binary alloy has a measured value of electrical conductivity, σ, in a range of 31.2-44.1% IACS, wherein the measured value of electrical conductivity is less than or equal to an upper limit of electrical conductivity, in %, calculated by the formulaic expression, {1.7241/(−0.0347×X2+0.6569×X+1.7)}×100, wherein X is the content of the Mg in the binary alloy; a stress relaxation rate of the rolled copper alloy material is in a range of 50% or less after heating at 150° C. for 1,000 hours, a 0.2% proof stress σ0.2 of the rolled copper alloy material in a direction parallel to a rolling direction is in a range of 400 MPa or more, and an average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater in the rolled copper alloy material is in a range of 1 piece/μm2 or less during observation by a scanning electron microscope.
12. The method for producing a rolled copper alloy material for electronic devices according to claim 11, wherein in the intermediate heat treatment process, the heat treatment is performed at a temperature of 400° C. or higher and 900° C. or lower, and in the finishing heat treatment process, the heat treatment is performed at a temperature of higher than 200° C. and 800° C. or lower.
This application is a U.S. National Phase Application under 35 U.S.C. §371 of International Patent Application No. PCT/JP2012/077736, filed Oct. 26, 2012, and claims the benefit of Japanese Patent Application No. 2011-237800, filed on Oct. 28, 2011, all of which are incorporated by reference in their entirety herein. The International Application was published in Japanese on May 2, 2013 as International Publication No. WO/2013/062091 under PCT Article 21(2).
In addition, for example, in Patent Document 2, a Cu—Ni—Si-based alloy (so-called Corson alloy) is provided. The Corson alloy is a precipitation hardening type alloy in which Ni2Si precipitates are dispersed, and has relatively high electrical conductivity, strength, and stress relaxation resistance. Therefore, the Corson alloy has been widely used in a terminal for a vehicle and a small terminal for signal, and has been actively developed in recent years.
In addition, as the other alloys, a Cu—Mg alloy described in Non-Patent Document 2, a Cu—Mg—Zn—B alloy described in Patent Document 3, and the like have been developed.
Patent Document 1: Japanese Unexamined Patent Application, First Publication No. H01-107943
Patent Document 2: Japanese Unexamined Patent Application, First Publication No. H11-036055
Patent Document 3: Japanese Unexamined Patent Application, First Publication No. H07-018354
Non-Patent Document 1: Koya Nomura, “Technical Trends in High Performance Copper Alloy Strip for Connector and Kobe Steel's Development Strategy”, Kobe Steel Engineering Reports Vol. 54, No. 1 (2004), p. 2 to 8
Non-Patent Document 2: Shigenori Hori and two co-researchers, “Intergranular (Grain Boundary) Precipitation in Cu—Mg Alloy”, Journal of the Japan Copper and Brass Research Association, Vol. 19 (1980), p. 115 to 124
Furthermore, in the Cu—Mg based alloy disclosed in Non-Patent Document 2 and Patent Document 3, an intermetallic compound precipitates as is the case with the Corson alloy, and the Young's modulus tends to be high. Therefore, as described above, the Cu—Mg based alloy is not preferable as the connector.
Moreover, in the Cu—Mg based alloy, many coarse intermetallic compounds are dispersed in a matrix phase, and thus cracking is likely to occur from the intermetallic compounds as the start points during bending. Therefore, there is a problem in that a part for electronic devices having a complex shape cannot be formed.
In order to solve the problems, the inventors had intensively researched, and as a result, they had learned that a work hardening type copper alloy of a Cu—Mg solid solution alloy supersaturated with Mg produced by solutionizing a Cu—Mg alloy and performing rapid cooling thereon exhibits low Young's modulus, high proof stress, high electrical conductivity, and excellent bending formability. In addition, it was found that the stress relaxation resistance can be enhanced by performing an appropriate heat treatment on the copper alloy made from the Cu—Mg solid solution alloy supersaturated with Mg after finishing working.
The present invention has been made based on the above-described knowledge, and a copper alloy for electronic devices according to the present invention consists of a binary alloy of Cu and Mg containing Mg at a content of 3.3 at % or more and 6.9 at % or less, with a remainder substantially being Cu and unavoidable impurities, wherein, when a concentration of Mg is given as X at %, an electrical conductivity σ (% IACS) is in a range of σ≦{1.7241/(−0.0347×X2+0.6569×X+1.7)}×100, and a stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less.
In addition, a copper alloy for electronic devices according to the present invention consists of a binary alloy of Cu and Mg containing Mg at a content of 3.3 at % or more and 6.9 at % or less, with a remainder substantially being Cu and unavoidable impurities, wherein an average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less during observation by a scanning electron microscope, and a stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less.
Moreover, a copper alloy for electronic devices according to the present invention consists of a binary alloy of Cu and Mg containing Mg at a content of 3.3 at % or more and 6.9 at % or less, with a remainder substantially being Cu and unavoidable impurities, wherein, when a concentration of Mg is given as X at %, an electrical conductivity σ (% IACS) is in a range of σ≦1.7241/(−0.0347×X2+0.6569×X+1.7)×100, an average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less during observation by a scanning electron microscope, and a stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less.
In the copper alloy for electronic devices having the above configuration, Mg is contained at a content of 3.3 at % or more and 6.9 at % or less so as to be equal to or more than a solid solubility limit, and the electrical conductivity σ is set to be in the range of the above expression when the Mg content is given as X at %. Therefore, the copper alloy is the Cu—Mg solid solution alloy supersaturated with Mg.
Otherwise, Mg is contained at a content of 3.3 at % or more and 6.9 at % or less so as to be equal to or more than a solid solubility limit, and the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less during observation by a scanning electron microscope. Therefore, the precipitation of the intermetallic compounds mainly containing Cu and Mg is suppressed, and the copper alloy is the Cu—Mg solid solution alloy supersaturated with Mg.
In addition, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is calculated by observing 10 visual fields at a 50,000-fold magnification in a visual field of about 4.8 μm2 using a field emission type scanning electron microscope.
The copper alloy made from the Cu—Mg solid solution alloy supersaturated with Mg has tendency to decrease the Young's modulus, and for example, even when the copper alloy is applied to a connector in which a male tab is inserted by pushing up a spring contact portion of a female or the like, a change in contact pressure during the insertion is suppressed, and due to a wide elastic limit, there is no concern for plastic deformation easily occurring. Therefore, the copper alloy is particularly appropriate for a part for electronic devices such as a terminal, a connector, a relay, and a lead frame.
In addition, in the copper alloy for electronic devices according to the present invention, since the stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less, even when the copper alloy is used under a high temperature environment, electrical conduction failure due to a reduction in contact pressure can be suppressed. Therefore, the copper alloy can be applied as the material of a part for electronic devices used under the high temperature environment such as an engine room.
Furthermore, in the copper alloy for electronic devices described above, it is preferable that a Young's modulus E be in a range of 125 GPa or less and a 0.2% proof stress σ0.2 be in a range of 400 MPa or more.
In the case where Young's modulus E is in a range of 125 GPa or less and the 0.2% proof stress σ0.2 is in a range of 400 MPa or more, the elastic energy coefficient (σ0.22/2E) is increased, and thus plastic deformation does not easily occur. Therefore, the copper alloy is particularly appropriate for a part for electronic devices such as a terminal, a connector, a relay, and a lead frame.
Here, in the finishing heat treatment process, it is preferable that the heat treatment be performed at a temperature of higher than 200° C. and 800° C. or lower. Moreover, it is preferable that the heated copper material be cooled to a temperature of 200° C. or lower at a cooling rate of 200° C./min or higher.
In this case, the stress relaxation resistance can be enhanced by the finishing heat treatment process, and the stress relaxation rate at 150° C. after 1,000 hours can be in a range of 50% or less.
A rolled copper alloy material for electronic devices according to the present invention consists of the copper alloy for electronic devices described above, a Young's modulus E in a direction parallel to a rolling direction is in a range of 125 GPa or less, and a 0.2% proof stress σ0.2 in the direction parallel to the rolling direction is in a range of 400 MPa or more.
According to the rolled copper alloy material for electronic devices having this configuration, the elastic energy coefficient (σ0.22/2E) is high, and plastic deformation does not easily occur.
FIG. 1 is a Cu—Mg system phase diagram.
In addition, when the Mg content is given as X at %, the electrical conductivity a (% IACS) is in a range of σ≦{1.7241/(−0.0347×X2+0.6569×X+1.7)}×100.
In addition, during observation by a scanning electron microscope, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less.
In addition, the stress relaxation rate of the copper alloy for electronic devices according to this embodiment at 150° C. after 1,000 hours is in a range of 50% or less. Here, the stress relaxation rate was measured by applying stress using a method based on a cantilevered screw type of JCBA-T309:2004 of The Japan Copper and Brass Association Technical Standards.
In addition, the copper alloy for electronic devices has a Young's modulus E of 125 GPa or less and a 0.2% proof stress σ0.2 of 400 MPa or more.
(Electrical Conductivity σ)
When the Mg content is given as X at %, in a case where the electrical conductivity σ is in a range of σ≦{1.7241/(−0.0347×X2+0.6569×X+1.7)}×100 in the binary alloy of Cu and Mg, the intermetallic compounds mainly containing Cu and Mg are rarely present.
That is, in a case where the electrical conductivity σ is higher than that of the above expression, a large amount of the intermetallic compounds mainly containing Cu and Mg are present and the size thereof is relatively large, and thus bending formability greatly deteriorates. In addition, since the intermetallic compounds mainly containing Cu and Mg are formed and the amount of solid-solubilized Mg is small, the Young's modulus is also increased. Therefore, production conditions are adjusted so that the electrical conductivity σ is in the range of the above expression.
In addition, in order to reliably achieve the operational effect, it is preferable that the electrical conductivity a (% IACS) be in a range of σ≦{1.7241/(−0.0300×X2+0.6763×X+1.7)}×100. In this case, a smaller amount of the intermetallic compounds mainly containing Cu and Mg is contained, and thus bending formability is further enhanced.
In order to further reliably achieve the operational effect, the electrical conductivity a (% IACS) is more preferably in a range of σ≦{1.7241/(−0.0292×X2+0.6797×X+1.7)}×100. In this case, since a further smaller amount of the intermetallic compounds mainly containing Cu and Mg is contained, bending formability is further enhanced.
In the copper alloy for electronic devices according to this embodiment, as described above, the stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less. In a case where the stress relaxation rate under this condition is low, even when the copper alloy is used under a high temperature environment, permanent deformation can be suppressed to be small, and a reduction in contact pressure can be suppressed. Therefore, the copper alloy for electronic devices according to this embodiment can be applied as a terminal used under a high temperature environment such as the vicinity of a vehicle engine room.
In addition, the stress relaxation rate at 150° C. after 1,000 hours is preferably in a range of 30% or less, and more preferably in a range of 20% or less.
In the copper alloy for electronic devices according to this embodiment, as a result of the observation by the scanning electron microscope, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less. That is, the intermetallic compounds mainly containing Cu and Mg rarely precipitate, and Mg is solid-solubilized in the matrix phase.
As a result of the observation of the structure, in a case where the intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less in the alloy, that is, in a case where the intermetallic compounds mainly containing Cu and Mg are absent or account for a small amount, good bending formability and low Young's modulus can be obtained.
Furthermore, in order to reliably achieve the operational effect described above, it is more preferable that the number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.05 μm or greater in the alloy be in a range of 1 piece/μm2 or less. In addition, the upper limit of the grain size of the intermetallic compound generated in the copper alloy of the present invention is preferably 5 μm, and is more preferably 1 μm.
In addition, the average number of intermetallic compounds mainly containing Cu and Mg is obtained by observing 10 visual fields at a 50,000-fold magnification and a visual field of about 4.8 μm2 using a field emission type scanning electron microscope and calculating the average value thereof.
Grain size is a factor which greatly affects stress relaxation resistance, and stress relaxation resistance deteriorates in a case where the grain size is smaller than a necessary value. In addition, in a case where the grain size is larger than a necessary value, bending formability is adversely affected. Therefore, it is preferable that the average grain size be in a range of 1 μm or greater and 100 μm or smaller. In addition, the average grain size is more preferably in a range of 2 μm or greater and 50 μm or smaller, and even more preferably in a range of 5 μm or greater and 30 μm or smaller.
First, the above-described elements are added to molten copper obtained by melting a copper raw material for component adjustment, thereby producing a molten copper alloy. Furthermore, for the addition of Mg, a single element of Mg, a Cu—Mg base alloy, or the like may be used. In addition, a raw material containing Mg may be melted together with the copper raw material. In addition, a recycled material and a scrap material of this alloy may be used.
Next, a heating treatment is performed for homogenization and solutionizing of the obtained ingot. Inside of the ingot, the intermetallic compounds mainly containing Cu and Mg and the like are present which are generated as Mg is condensed as segregation during solidification. Accordingly, in order to eliminate or reduce the segregation, the intermetallic compounds, and the like, a heating treatment of heating the ingot to a temperature of 400° C. or higher and 900° C. or lower is performed such that Mg is homogeneously diffused or Mg is solid-solubilized in the matrix phase inside of the ingot. In addition, the heating process S02 is preferably performed in a non-oxidizing or reducing atmosphere.
Here, when the heating temperature is in a range of less than 400° C., solutionizing is incomplete, and thus there is concern that a large amount of the intermetallic compounds mainly containing Cu and Mg may remain in the matrix phase. In contrast, when the heating temperature is in a range of higher than 900° C., a portion of the copper material becomes a liquid phase, and there is concern that the structure or the surface state thereof may become non-uniform. Therefore, the heating temperature is set to be in a range of 400° C. or higher and 900° C. or lower. The heating temperature is more preferably in a range of 500° C. or higher and 850° C. or lower, and even more preferably in a range of 520° C. or higher and 800° C. or lower.
In addition, the copper material heated to a temperature of 400° C. or higher and 900° C. or lower in the heating process S02 is cooled to a temperature of 200° C. or less at a cooling rate of 200° C./min or higher. By the rapid cooling process S03, Mg solid-solubilized in the matrix phase is suppressed from precipitating as the intermetallic compounds mainly containing Cu and Mg, and during observation by a scanning electron microscope, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater is preferably in a range of 1 piece/m2 or less. That is, the copper material can be a Cu—Mg solid solution alloy supersaturated with Mg. In the cooling process A03, the lower limit of the cooling temperature is preferably −100° C., and the upper limit of the cooling rate is preferably 10,000° C./min. When the cooling temperature is in a range of lower than −100° C., the effect cannot be enhanced, and the cost is increased. When the cooling rate is in a range of higher than 10,000° C./min, the effect cannot be enhanced, and the cost is also increased.
In addition, the temperature condition in this intermediate working process S04 is not particularly limited, and is preferably in a range of −200° C. to 200° C. for cold working or warm working. In addition, the working ratio is appropriately selected to approximate a final shape, and is preferably in a range of 20% or higher in order to reduce the number of intermediate heat treatment processes S05 to be performed until the final shape is obtained. In addition, the working ratio is more preferably in a range of 30% or higher. The upper limit of the working ratio is not particularly limited, and is preferably 99.9% from the viewpoint of preventing an edge crack. The working method is not particularly limited, and rolling is preferably employed in a case where a final form is a sheet or a strip. It is preferable that extruding or groove rolling be employed in a case where of a wire or a bar and forging or press be employed in a case of a bulk shape. Furthermore, for thorough solutionizing, S02 to S04 may be repeated.
Here, a heat treatment method is not particularly limited, and the heat treatment is preferably performed in a non-oxidizing atmosphere or a reducing atmosphere under the condition of 400° C. or higher and 900° C. or lower. The heat treatment is performed more preferably at a temperature of 500° C. or higher and 850° C. or lower and even more preferably at a temperature of 520° C. or higher and 800° C. or lower.
Here, in the intermediate heat treatment process S05, the copper material heated at a temperature of 400° C. or higher and 900° C. or lower is cooled to a temperature of 200° C. or lower at a cooling rate of 200° C./min or higher. The cooling temperature of the intermediate heat treatment process S05 is more preferably in a range of 150° C. or lower, and even more preferably in a range of 100° C. or lower. The cooling rate is more preferably in a range of 300° C./min or higher, and even more preferably in a range of 1000° C./min or higher. In contrast, in the intermediate heat treatment process S05, the lower limit of the cooling temperature is preferably −100° C., and the upper limit of the cooling rate is preferably 10,000° C./min. When the cooling temperature is lower than −100° C., the effect cannot be enhanced, and cost is increased. When the cooling rate is in a range of higher than 10,000° C./min, the effect cannot be enhanced, and the cost is also increased.
By the rapid cooling as such, Mg solid-solubilized in the matrix phase is suppressed from precipitating as the intermetallic compounds mainly containing Cu and Mg, and during observation by a scanning electron microscope, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater can be in a range of 1 piece/μm2 or less. That is, the copper material can be a Cu—Mg solid solution alloy supersaturated with Mg.
The heat treatment temperature is preferably in a range of higher than 200° and 800° C. or lower. In addition, in the finishing heat treatment process S07, heat treatment conditions (temperature, time, and cooling rate) need to be set so that the solutionized Mg does not precipitate. For example, it is preferable that the conditions be about 10 seconds to 24 hours at 250° C., about 5 seconds to 4 hours at 300° C., and about 0.1 seconds to 60 seconds at 500° C. The finishing heat treatment process S07 is preferably performed in a non-oxidizing atmosphere or a reducing atmosphere.
In addition, a cooling method of cooling the heated copper material to a temperature of 200° C. or lower at a cooling rate of 200° C./min or higher, such as water quenching, is preferable. The cooling temperature is more preferably in a range of 150° C. or lower, and even more preferably in a range of 100° C. or lower. The cooling rate is more preferably in a range of 300° C./min or higher, and even more preferably in a range of 1,000° C./min or higher. In contrast, the lower limit of the cooling temperature is preferably −100° C., and the upper limit of the cooling rate is preferably 10,000° C./min. When the cooling temperature is lower than −100° C., the effect cannot be enhanced, and the cost is increased. When the cooling rate is in a range of higher than 10,000° C./min, the effect cannot be enhanced, and the cost is also increased.
By the rapid cooling as such, Mg solid-solubilized in the matrix phase is suppressed from precipitating as the intermetallic compounds mainly containing Cu and Mg, and during observation by a scanning electron microscope, the average number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater can be in a range of 1 piece/μm2 or less. That is, the copper material can be a Cu—Mg solid solution alloy supersaturated with Mg. Furthermore, the finishing working process S06 and the finishing heat treatment process S07 described above may be repeatedly performed.
In this manner, the copper alloy for electronic devices according to this embodiment is produced. In addition, the copper alloy for electronic devices according to this embodiment has a Young's modulus E of 125 GPa or less and a 0.2% proof stress σ0.2 of 400 MPa or more. The Young's modulus E of the copper alloy for electronic devices according to this embodiment is more preferably in a range of 100 to 125 GPa, and the 0.2% proof stress σ0.2 thereof is more preferably in a range of 500 to 900 MPa.
In addition, when the Mg content is given as X at %, the electrical conductivity a (% IACS) is set to be in a range of σ≦1.7241/(−0.0347×X2+0.6569×X+1.7)×100.
Furthermore, by the finishing heat treatment process S07, the copper alloy for electronic devices according to this embodiment has a stress relaxation rate of 50% or less at 150° C. after 1,000 hours.
According to the copper alloy for electronic devices having the above-described configuration according to this embodiment, Mg is contained in the binary alloy of Cu and Mg at a content of 3.3 at % or more and 6.9 at % or less so as to be equal to or more than a solid solubility limit, and the electrical conductivity a (% IACS) is set to be in a range of σ≦1.7241/(−0.0347×X2+0.6569×X+1.7)×100 when the Mg content is given as X at %. Furthermore, during the observation by a scanning electron microscope, the average number of intermetallic compounds containing Cu and Mg and having grain sizes of 0.1 μm or greater is in a range of 1 piece/μm2 or less.
That is, the copper alloy for electronic devices according to this embodiment is the Cu—Mg solid solution alloy supersaturated with Mg.
In addition, in the copper alloy for electronic devices according to this embodiment, since the stress relaxation rate at 150° C. after 1,000 hours is in a range of 50% or less, even when the copper alloy is used under a high temperature environment, electrical conduction failure due to a reduction in contact pressure can be suppressed. Therefore, the copper alloy can be applied as the material of a part for electronic devices used under the high temperature environment such as an engine room.
In addition, since the copper alloy for electronic devices has a Young's modulus E of 125 GPa or less and a 0.2% proof stress σ0.2 of 400 MPa or more, the elastic energy coefficient (σ0.22/2E) is increased, and thus plastic deformation does not easily occur. Therefore, the copper alloy is particularly appropriate for a part for electronic devices such as a terminal, a connector, a relay, and a lead frame.
According to the method for producing the copper alloy for electronic devices according to this embodiment, by the heating process S02 of heating the ingot or the working material consisting of the binary alloy of Cu and Mg and having the above composition to a temperature of 400° C. or higher and 900° C. or lower, the solutionizing of Mg can be achieved.
In addition, since the rapid cooling process S03 of cooling the ingot or the working material heated to a temperature of 400° C. or higher and 900° C. or lower in the heating process S02 to a temperature of 200° C. or less at a cooling rate of 200° C./min or higher is included, the intermetallic compounds mainly containing Cu and Mg can be suppressed from precipitating in the cooling procedure, and thus the ingot or the working material after the rapid cooling can be the Cu—Mg solid solution alloy supersaturated with Mg.
Moreover, since the intermediate working process S04 of working the rapidly-cooled material (the Cu—Mg solid solution alloy supersaturated with Mg) is included, a shape close the final shape can be easily obtained.
In addition, in the intermediate heat treatment process S05, since the copper material heated to a temperature of 400° C. or higher and 900° C. or lower is cooled to a temperature of 200° C. or less at a cooling rate of 200° C./min or higher, the intermetallic compounds mainly containing Cu and Mg can be suppressed from precipitating in the cooling procedure, and thus the copper material after the rapid cooling can be the Cu—Mg solid solution alloy supersaturated with Mg.
In addition, in the method for producing the copper alloy for electronic devices according to this embodiment, after the finishing working process S06 for increasing strength through work hardening and working the material in a predetermined shape, the finishing heat treatment process S07 of performing the heat treatment is included in order to enhance stress relaxation resistance, to perform annealing and hardening at low temperature, or to remove residual strain. Therefore, the stress relaxation rate at 150° C. after 1,000 hours can be in a range of 50% or less. In addition, a further enhancement of mechanical properties can be achieved.
In addition, in this embodiment, the copper alloy for electronic devices which satisfies both the condition that “the number of intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater in the alloy is in a range of 1 piece/μm2 or less” and the condition of the “electrical conductivity σ” is described. However, a copper alloy for electronic devices which satisfies only one of the conditions may also be employed.
A copper raw material consisting of oxygen-free copper (ASTM B152 C10100) having a purity of 99.99 mass % or higher was prepared, the copper material was inserted into a high purity graphite crucible, and subjected to high frequency melting in an atmosphere furnace having an Ar gas atmosphere. Various additional elements were added to the obtained molten copper to prepare component compositions shown in Tables 1 and 2, and the resultant was poured into a carbon mold, thereby producing an ingot. In addition, the dimensions of the ingot were about 20 mm in thickness×about 20 mm in width×about 100 to 120 mm in length.
A heating process of heating the obtained ingot in the Ar gas atmosphere for 4 hours under the temperature conditions shown in Tables 1 and 2 was performed. Thereafter, water quenching was performed thereon (at a cooling temperature of 20° C. and a cooling rate of 1500° C./min).
Thereafter, at the room temperature, intermediate rolling was performed at a rolling ratio shown in Tables 1 and 2. In addition, an intermediate heat treatment was performed on the obtained strip material in a salt bath under the temperature conditions shown in Tables 1 and 2. Thereafter, water quenching was performed (at a cooling temperature of 20° C. and a cooling rate of 1500° C./min).
In addition, after the finish rolling, a finishing heat treatment was performed in a salt bath under the conditions shown in Tables. Thereafter, water quenching was performed on the resultant (at a cooling temperature of 20° C. and a cooling rate of 1500° C./min), thereby producing a strip material for property evaluation.
The grain size of the sample after being subjected to the intermediate heat treatment shown in Tables 1 and 2 was measured. Mirror polishing and etching were performed on each sample, the sample was photographed by an optical microscope so that the rolling direction thereof was the horizontal direction of the photograph, and the observation was performed in a visual field at 1,000-fold magnification (about 300 μm×200 μm). Subsequently, regarding the grain size, according to an intercept method of JIS H 0501, 5 segments having vertically and horizontally predetermined lengths were drawn in the photograph, the number of crystal grains which were completely cut was counted, and the average value of the cut lengths thereof was determined as the grain size.
A No. 13B specimen specified in JIS Z 2201 was collected from the strip material for property evaluation, and the 0.2% proof stress σ0.2 thereof was measured by an offset method in JIS Z 2241. In addition, the specimen was collected from the strip material for property evaluation in a direction parallel to the rolling direction.
A specimen having a size of 10 mm in width×60 mm in length was collected from the strip material for property evaluation, and the electrical resistance thereof was obtained by a four terminal method. In addition, the dimensions of the specimen were measured using a micrometer, and the volume of the specimen was calculated. In addition, the electrical conductivity thereof was calculated from the measured electrical resistance and the volume. In addition the specimen was collected so that the longitudinal direction thereof was parallel to the rolling direction of the strip material for property evaluation.
In a stress relaxation resistance test, stress was applied by the method based on a cantilevered screw type of JCBA-T309:2004 of The Japan Copper and Brass Association Technical Standards, and a residual stress ratio after being held at 150° C. for a predetermined time was measured.
The specimen (10 mm in width×60 mm in length) was collected from the strip material for property evaluation so that the longitudinal direction thereof was parallel to the rolling direction of the strip material for property evaluation.
At this time, an initial deflection displacement was set to be 2 mm so as to allow the surface maximum stress of the specimen to be 80% of the proof stress, thereby adjusting a span length. Span length is the distance from the fixed end of a specimen to the portion that comes into contact with the tip end of the bolt in the direction perpendicular to the load direction of the bolt for a deflection displacement load, when an initial deflection was imparted to the specimen. The surface maximum stress is determined by the following expression.
δ0: the initial deflection displacement (2 mm), and
Ls: the span length (mm).
The specimen of which the initial deflection displacement was set to be 2 mm was held in a thermostatic chamber at a temperature of 150° C. for 1,000 hours. Thereafter, the specimen with the test jig for a deflection displacement load in the cantilevered screw type was taken out to room temperature, and the bolt for a deflection displacement load was loosened to remove the load.
From the bending behavior of the specimen which was cooled to the room temperature and remained after being held at a temperature of 150° C. for 1,000 hours, the residual stress ratio (difference in permanent deflection displacement) was measured, and the stress relaxation rate was evaluated. In addition, the stress relaxation rate was calculated using the following expression.
Stress relaxation rate (%)=(δt/δ0)×100
δt: the permanent deflection displacement (mm) after being held at 150° C. for 1,000 hours−the permanent deflection displacement (mm) after being held at room temperature for 24 hours, and
δ0: the initial deflection displacement (mm).
Mirror polishing and ion etching were performed on the rolled surface of each sample. In order to check the precipitation state of the intermetallic compounds mainly containing Cu and Mg, observation was performed in a visual field at a 10,000-fold magnification (about 120 μm2/visual field) using an FE-SEM (field emission type scanning electron microscope).
Subsequently, in order to examine the density (piece/μm2) of the intermetallic compounds mainly containing Cu and Mg, a visual field at a 10,000-fold magnification (about 120 μm2/visual field) in which the precipitation state of the intermetallic compounds was not unusual was selected, and in the region, 10 continuous visual fields (about 4.8 μm2/visual field) were photographed at a 50,000-fold magnification. The grain size of the intermetallic compound was obtained from the average value of a major axis of the intermetallic compound (the length of the longest intragranular straight line which is drawn under a condition without intergranular contact on the way) and a minor axis (the length of the longest straight line which is drawn under a condition without intergranular contact on the way in a direction perpendicular to the major axis). In addition, the density (piece/μm2) of the intermetallic compounds mainly containing Cu and Mg and having grain sizes of 0.1 μm or greater was obtained.
A plurality of specimens having a size of 10 mm in width×30 mm in length were collected from the strip material for property evaluation so that the rolling direction and the longitudinal direction of the specimen were parallel to each other, a W bending test was performed using a W-shaped jig having a bending angle of 90 degrees and a bending radius of 0.25 mm.
Rolling ratio of
Temperature of intermediate Rolling ratio Finishing
Mg of heating intermediate heat of finish heat treatment
(at %) — process rolling treatment rolling Temperature Time
Invention 1 3.4 — 715° C. 70% 625° C. 60% 250° C. 60 min
Examples 2 4.1 — 715° C. 70% 625° C. 60% 280° C. 30 min
3 4.4 — 715° C. 70% 625° C. 60% 300° C. 1 min
4 5.0 — 715° C. 70% 625° C. 60% 330° C. 1 min
5 5.4 — 715° C. 70% 625° C. 60% 350° C. 30 sec
6 5.9 — 715° C. 70% 700° C. 60% 320° C. 1 min
7 6.4 — 715° C. 70% 700° C. 60% 280° C. 5 min
8 4.4 — 715° C. 70% 625° C. 70% 200° C. 24 h
9 4.3 — 715° C. 70% 625° C. 70% 350° C. 1 min
10 4.6 — 715° C. 70% 625° C. 70% 500° C. 1 sec
11 5.8 — 715° C. 70% 675° C. 60% 300° C. 5 min
12 5.8 — 715° C. 70% 650° C. 60% 300° C. 2 min
13 4.2 — 715° C. 70% 625° C. 60% 230° C. 1 sec
14 4.2 — 715° C. 70% 625° C. 60% 230° C. 60 sec
Rolling of Finishing
Temperature ratio of intermediate Rolling ratio heat
Mg of heating intermediate heat of finishing treatment
(at %) — process rolling treatment working Temperature Time
Comparative 1 0.9 — 715° C. 70% 600° C. 70% 300° C. 1 min
Examples 2 7.8 — 715° C. 70% — — — —
3 10.2  — 715° C. 70% — — — —
4 4.4 — 715° C. 70% 625° C. 70% — —
5 4.6 — 715° C. 70% 625° C. 70% 400° C. 1 h
P Temperature ratio of intermediate Rolling ratio heat
Sn (at of heating intermediate heat of finishing treatment
(at %) %) process rolling treatment working Temperature Time
Conventional 1 3.3 0.3 800° C. 70% 500° C. 70% 250° C. 1 min
Examples 2 4.4 0.3 800° C. 70% 500° C. 70% 250° C. 1 min
Grain size 0.2%
after intermediate Electrical Upper limit proof Stress Young's
heat treatment Edge conductivity of electrical Precipitates stress relaxation modulus Bending
(μm) crack % IACS conductivity (pieces/μm2) MPa rate GPa formability
Invention 1 15 A 44.1% 48.8% 0 530 19% 115 A
Examples 2 14 A 40.9% 45.3% 0 574 18% 112 A
3 16 A 38.0% 44.0% 0 605 20% 111 A
4 15 A 34.8% 41.9% 0 618 17% 110 A
5 15 A 32.8% 40.7% 0 640 18% 110 A
6 45 B 33.0% 39.5% 0 638 20% 108 A
7 51 B 31.2% 38.5% 0 661 20% 106 A
8 15 A 38.1% 44.0% 0 640 28% 111 A
9 14 A 39.1% 44.4% 0 615 15% 111 A
10 14 A 39.2% 43.2% 0 622 17% 112 A
11 33 B 37.2% 39.7% 0 642 22% 109 B
12 25 B 38.2% 39.7% 0 650 23% 108 B
13 15 A 40.3% 44.8% 0 595 47% 112 A
14 13 A 40.0% 44.8% 0 590 39% 111 A
Grain size after 0.2%
intermediate Electrical Upper limit proof Stress Young's
heat treatment Edge conductivity of electrical Precipitate stress relaxation modulus Bending
Comparative 1 10 A 72.8% 76.2% 0 430 21% 127 A
Examples 2 — E — — — — — — —
3 — E — — — — — — —
4 11 A 38.0% 44.0% 0 660 54% 111 A
5 14 A 47.9% 43.2% 10  380 19% 117 D
Conventional 1 10 B 14.0% — — 684 55% 110 A
Examples 2 8 B 12.9% — — 754 53% 109 A
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