WO2017115963A1 - Copper alloy material for automobile and electrical and electronic components and method of producing the same - Google Patents

Copper alloy material for automobile and electrical and electronic components and method of producing the same Download PDF

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WO2017115963A1
WO2017115963A1 PCT/KR2016/008028 KR2016008028W WO2017115963A1 WO 2017115963 A1 WO2017115963 A1 WO 2017115963A1 KR 2016008028 W KR2016008028 W KR 2016008028W WO 2017115963 A1 WO2017115963 A1 WO 2017115963A1
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copper alloy
rolling
alloy material
heat treatment
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French (fr)
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Cheol Min Park
Hyo Moon Nam
Jun Hyung Kim
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Poongsan Corp
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Poongsan Corp
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Priority to JP2018553031A priority patent/JP6801163B2/ja
Priority to US16/066,642 priority patent/US11091827B2/en
Publication of WO2017115963A1 publication Critical patent/WO2017115963A1/en
Priority to PH12018501391A priority patent/PH12018501391A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent

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  • the present invention relates to a copper alloy material for automobile and electrical and electronic components and a method of producing the same, and more particularly, to a copper alloy material having superior tensile strength, spring limit, electrical conductivity and bendability as a small and precision connector, a spring material, a semiconductor leadframe, an automobile and electrical and electronic connector, and an information transfer or direct electrical material such as a relay material, and a method of producing the same.
  • a variety of copper alloy materials for automobile and electrical and electronic components which are suitable for different requirements for applications such as connectors, terminals, switches, relays and lead frames, are used.
  • the corresponding components need small size and low weight.
  • connectors for automobiles are classified into 0.025 inches, 0.050 inches, 0.070 inches, 0.090 inches and 0.250 inches connectors depending on width thereof, and are called "025, 050, 070, 090 and 250 connectors" depending on thickness of connectors.
  • the size of connectors is gradually decreasing.
  • the number of pins of connector terminals is increased to 100 or more, as compared to 50 to 70 in the prior art.
  • the width of copper alloy materials is gradually decreasing to 0.30 mm, 0.25 mm and 0.15 mm from 0.4 mm in the prior art.
  • the width reduction of copper alloy materials causes bending phenomenon of pin parts during terminal work to a thickness of 0.15 mm at typical levels of tensile strength and spring limit (about tensile strength of 610 MPa and spring limit of 450 MPa) of copper alloy materials.
  • copper alloy materials used for automobile and electrical and electronic components need to have improved strength, more specifically, a tensile strength of 620 MPa or higher, and a spring limit of 460 MPa or higher.
  • Copper alloy materials produced in a solid solution strengthened form based on addition of alloy elements, such as phosphor bronze or brass, are generally used as common automobile and electrical and electronic components, but solid solution strengthened copper alloy materials exhibit superior strength to general pure copper, but have a drawback of lower electrical conductivity as compared to pure copper.
  • phosphor bronze has good bendability in a direction vertical to rolling, whereas it cracks during bending work in a rolling direction.
  • brass and phosphor bronze may cause short, such as contact short due to material softening even application to heated parts, for example, terminals near automobile engines and use thereof is thus strictly restricted.
  • copper alloys commonly used for automobile and electrical and electronic components are corson based copper alloys (Cu-Ni-Si based copper alloys) and exhibits a difference between bending work in a rolling direction and a direction vertical to rolling due to worked textures formed during rolling in the production step by rolling after precipitation heat treatment in order to improve strength.
  • levels of required tensile strength and spring limit are increased in accordance with size reduction and density increase of copper alloy materials for automobile and electrical and electronic components, but tensile strength and spring limit of conventional corson based copper alloys (Cu-Ni-Si based copper alloys) do not satisfy these levels and thus disadvantageously cause a bending phenomenon.
  • copper alloy materials commonly used for automobile or electrical and electronic components need bendability in a rolling direction and a direction vertical to rolling as well as high tensile strength, high spring limit and high electrical conductivity, which are required in accordance with size reduction and density increase of components.
  • tensile strength and spring limit are in inversely proportional to bendability, there is a considerably high demand for development of copper alloy materials having all of the aforementioned properties.
  • research is actively underway on Cu-Ni-Si alloys which satisfy bendability in a rolling direction and in a direction vertical to rolling while retaining high tensile strength and high spring limit.
  • Japanese Patent Laid-open Publication No. 2006-283059 discloses improvement in bendability by controlling crystal orientation such that an area proportion of ⁇ 001 ⁇ 100> plane having a cubic crystal orientation reaches 50% or higher and Japanese Patent Laid-open Publication No. 2011-017072 discloses improvement in bendability by adjusting an area proportion of a brass crystal orientation ⁇ 110 ⁇ 112>, an area proportion of a copper crystal orientation ⁇ 121 ⁇ 111> and an area proportion of a cubic crystal orientation ⁇ 001 ⁇ 100> to 20% or less, 20% or less, and 5 to 60%, respectively.
  • An object of the present invention devised to solve the problem lies on a method of producing a copper alloy material for automobile and electrical and electronic components which has superior tensile strength, spring limit, electrical conductivity and bendability.
  • the object of the present invention can be achieved by providing a method of producing a copper alloy material for automobile and electrical and electronic components including (a) melting constituent components and casting an ingot from the constituent components, wherein the constituent components include 1.0 to 4.0 wt% of nickel (Ni), 0.1 to 1.0 wt% of silicon (Si), 0.1 to 1.0 wt% of tin (Sn), the balance of copper and an inevitable impurity, wherein the inevitable impurity includes one or more transition metals selected from the group consisting of Ti, Co, Fe, Mn, Cr, Nb, V, Zr and Hf and is present in a total amount of 1 wt% or less, (b) subjecting the resulting ingot to hot-rolling at a temperature of 750 to 1,000°C for 1 to 5 hours, (c) subjecting the resulting product to intermediate cold rolling at a rolling reduction of 50% or higher, (d) subjecting the resulting product to high-temperature high-speed solution heat treatment at 780 to 1,000°C for 1 to 300
  • the method may further include adjusting a plate shape, before or after (f) precipitation heat treatment.
  • the method may further include plating tin (Sn), silver (Ag), or nickel (Ni) after (g) stress relief.
  • the method may further include producing the copper alloy material obtained after (g) stress relief in the form of a plate, rod or tube.
  • 1.0 wt% or less of phosphorous (P) may be further added.
  • 1.0 wt% or less of zinc (Zn) may be further added.
  • 1.0 wt% or less of phosphorous (P) and 1.0 wt% or less of zinc (Zn) may be further added.
  • a copper alloy material for automobile and electrical and electronic components produced by the method as described above.
  • the present invention provides a method of producing a copper alloy material for automobile and electrical and electronic components which exhibits superior tensile strength, spring limit, electrical conductivity and bendability.
  • FIG. 1A illustrates a crystal plane fraction of a sample (Cu-1.8Ni-0.3Si-0.3Sn-0.01P) according to Example 1;
  • FIG. 1B illustrates a grain boundary fraction of a sample (Cu-1.8Ni-0.3Si-0.3Sn-0.01P) according to Example 1;
  • FIG. 2A illustrates a crystal plane fraction of a sample (Cu-2.2Ni-0.5Si-0.3Sn-0.01P-0.1Zn) according to Example 4.
  • FIG. 2B illustrates a grain boundary fraction of a sample (Cu-2.2Ni-0.5Si-0.3Sn-0.01P-0.1Zn) according to Example 4.
  • the copper alloy material according to the present invention includes 1.0 to 4.0 wt% of nickel (Ni), 0.1 to 1.0 wt% of silicon (Si), 0.1 to 1.0 wt% of tin (Sn), the balance of copper (Cu) and an inevitable impurity, wherein the inevitable impurity includes one or more transition metals selected from the group consisting of Ti, Co, Fe, Mn, Cr, Nb, V, Zr and Hf.
  • the copper alloy material may further include one or more of 1.0 wt% or less of phosphorous (P) and 1.0 wt% or less of zinc (Zn), if necessary.
  • the sum of the components is 2 wt% or less.
  • the content of Ni is 1.0 to 4.0 wt% and the content of Si is 0.1 to 1.0 wt%.
  • the weight of Ni is less than 1.0 wt% and the weight of Si is less than 0.1 wt%, sufficient strength cannot be obtained by precipitation heat treatment and the copper alloy material is unsuitable for application to automobile, electrical and electronic connectors, semiconductors and leadframes.
  • the content of Ni exceeds 4 wt% and the content of Si exceeds 1.0 wt%, Ni-Si crystals formed during casting are rapidly grown to coarse compounds during heating prior to hot rolling, thus causing side cracking during hot rolling.
  • Sn is an element which slowly diffuses in the Cu matrix, and inhibits growth of Ni-Si precipitates during precipitation heat treatment and finely distributes the Ni-Si precipitates to improve strength.
  • Sn is present in an amount of 0.1 wt% to 1.0 wt%.
  • Sn cannot exert an effect of distributing Ni-Si precipitates, thus deteriorating tensile strength and spring limit and, when Sn is present in an amount exceeding 1.0 wt%, Sn is present in the Cu matrix even after precipitation, thus rapidly deteriorating electrical conductivity.
  • the copper alloy material according to the present invention may further include 1.0 wt% or less of phosphorous (P).
  • Phosphorous (P) serves as a deoxidizer during molten metal dissolution in the production of the copper alloy material according to the present invention and creates various forms of precipitates such as Ni 3 P, Ni 5 P 2 , Fe 3 P, Mg 3 P 2 , and MgP 4 during precipitation heat treatment.
  • phosphorous (P) serves as a mediator for combining one or more of transition metals, such as Co, Fe, Mn, Cr, Nb, V, Zr and Hf, present in the copper alloy material, with Ni-Si precipitates. Accordingly, phosphorous (P) separates other impurities in the copper matrix structure to form a precipitate such as Cu-Ni-Si-P-X (wherein X includes one or more transition metals of Co, Fe, Mn, Cr, Nb, V, Zr, and Hf), thereby advantageously improving tensile strength and electrical conductivity.
  • the content of phosphorous in the copper alloy material according to the present invention is higher than 1.0 wt%, the electrical conductivity of the copper alloy material is excessively deteriorated.
  • the copper alloy material according to the present invention may further include 1.0 wt% or less of Zn.
  • the balance of Cu is decreased corresponding to the amount of added Zn.
  • Zn improves heat detachment resistance of Sn plating or solder during plating of copper alloy plates and inhibits heat detachment of the plating layer.
  • the content of Zn is 1.0 wt% or less.
  • electrical conductivity of the copper alloy material is greatly deteriorated.
  • Impurities Ti, Co, Fe, Mn, Cr, Nb, V, Zr, Hf
  • the impurities according to the present invention mean one or more transition metals selected from the group consisting of Ti, Co, Fe, Mn, Cr, Nb, V, Zr, and Hf.
  • the impurities form an intermetallic compound with NiSi using a P component as a mediator during precipitation heat treatment and the intermetallic compound is precipitated in the matrix, thus increasing strength.
  • the total amount of impurities exceeds 1 wt%, impurities still remain in the Cu matrix even after precipitation heat treatment, thus causing significant deterioration in electrical conductivity.
  • An ingot is cast from constituent components of the copper alloy material for automobile and electrical and electronic components according to the present invention.
  • the ingot includes 1.0 to 4.0 wt% of nickel(Ni), 0.1 to 1.0 wt% of silicon (Si), 0.1 to 1.0 wt% of tin (Sn), the balance of copper (Cu) and an inevitable impurity.
  • the ingot may include 1 wt% or less of one or more of phosphorous (P) and zinc (Zn).
  • P phosphorous
  • Zn zinc
  • one or more transition metals selected from the group consisting of Ti, Co, Fe, Mn, Cr, Nb, V, Zr and Hf may be present in the total amount of 1 wt% or less and the other impurity is inevitably contained via scraps, electrical copper and copper scraps.
  • the ingot product obtained in the previous step is preferably hot rolled at a temperature of 750C° to 1,000°C for 1 to 5 hours, more preferably, at 900°C to 1,000°C for 2 to 4 hours.
  • hot rolling is carried out at a temperature of 750°C or less for a time shorter than 1 hour, the ingot structure remains in the obtained product, thus causing deterioration in strength and bendability.
  • crystal grains in the obtained copper alloy become coarse, thus causing deterioration in bendability of components produced with a desired thickness.
  • the product obtained in the previous hot rolling step is subjected to intermediate cold rolling at room temperature.
  • Rolling reduction of intermediate cold rolling is preferably 50% or higher, more preferably, 80% or higher.
  • the rolling reduction of intermediate cold rolling is lower than 50%, sufficient dislocation is not generated in the Cu matrix, re-crystallization is delayed during the subsequent solution heat treatment, sufficient over-saturated state is not formed and sufficient tensile strength cannot be thus obtained.
  • Solution heat treatment is the most essential step to secure high tensile strength, high spring limit and superior bendability of the finally obtained copper alloy material.
  • Solution heat treatment is preferably carried out at a temperature of 780 to 1,000°C for 1 to 300 seconds, more preferably, at 950 to 1,000°C for 10 to 60 seconds.
  • the copper alloy material according to the present invention finally obtained after solution heat treatment has improved tensile strength and spring limit while maintaining bendability.
  • solution heat treatment temperature is lower than 780°C, or solution heat treatment time is shorter than 1 second, sufficient over-saturated state cannot be formed, sufficient NiSi precipitates are not obtained even after precipitation heat treatment, and tensile strength and spring limit are thus deteriorated, and when the solution heat treatment temperature is higher than 1,000°C, or solution heat treatment time is longer than 300 seconds, excessive NiSi precipitates are formed and bendability is thus deteriorated.
  • the hardness (Vickers hardness, 1 to 5 kgf) of the finally obtained copper alloy material ranges from 75 to 95 Hv, more preferably from 80 to 90 Hv
  • the mean particle size of crystal grains in the copper alloy material ranges from 3 to 20 ⁇ m, more preferably from 5 to 15 ⁇ m.
  • the product obtained after the solution heat treatment is subjected to final cold rolling.
  • the rolling reduction of the final cold rolling ranges from 10 to 60%, preferably, from 20 to 40%.
  • EBSD analysis result of the final cold rolled product shows that about 50 to 80% of low angle grain boundary is formed within the range defined above.
  • the rolling reduction of final cold rolling is less than 10%, ⁇ 110 ⁇ crystal plane and ⁇ 112 ⁇ crystal plane are not sufficiently formed and tensile strength is significantly deteriorated.
  • the final rolling reduction exceeds 60% ⁇ 110 ⁇ crystal plane and ⁇ 112 ⁇ crystal plane are rapidly formed, low angle grain boundary fraction is degraded and bendability is deteriorated.
  • the number of cold rolling (also, referred to as the number of "passes”) is preferably 7 (the number of passes) or less, more preferably, 4.
  • the number of rolling exceeds 10
  • initial dislocations are annihilated due to decreased work curing capability, and tensile strength and spring limit are deteriorated after final aging.
  • the product obtained by the previous step is preferably subjected to precipitation heat treatment at 400 to 600°C for 1 to 20 hours, more preferably, at 450 to 550°C for 5 to 15 hours.
  • Nuclei are formed and grown from fine Ni-Si precipitates present in the product obtained by the previous step during precipitation heat treatment and Ni-Si precipitates present on the grain boundary by final rolling work before precipitation heat treatment in the dislocation site in the Cu matrix.
  • low diffusion speed of Sn element inhibits growth of Ni-Si precipitates and uniformly distributes the Ni-Si precipitates in the Cu matrix and grain boundary. As a result, tensile strength, electrical conductivity, spring limit and bendability of the finally obtained copper alloy material are improved.
  • precipitation heat treatment temperature is lower than 400°C, or precipitation heat treatment time is shorter than one hour, the amount of heat required for precipitation heat treatment is insufficient, nuclei cannot be sufficiently formed and grown from Ni-Si precipitates to Ni-Si precipitated compounds in the Cu matrix, and tensile strength, electrical conductivity and spring limit are thus deteriorated.
  • dislocations formed during final rolling are further concentrated in a rolling direction, bendability in a bad way direction (direction parallel to rolling or rolling direction) during bending work is further deteriorated and anisotropy is formed during bending work.
  • precipitation heat treatment temperature exceeds 600°C or precipitation heat treatment time is 20 hours or longer, over-aging occurs and electrical conductivity of the obtained copper alloy material can be maximized, but tensile strength and spring limit of the final product are decreased.
  • the product obtained by the previous step is subjected to stress relief treatment at 300 to 700°C for 10 to 3,000 seconds, more preferably at 500 to 600°C for 15 to 300 seconds.
  • the stress relief treatment is a process of reducing, by heating, stress, which is formed by variation in plasticity of the obtained product and in particular, and is important to restore the spring limit after adjustment of plate-shape.
  • plate shape adjustment may be carried out according to the plate shape of the material.
  • tin (Sn), silver (Ag) or nickel (Ni) plating may be carried out according to applications.
  • the copper alloy material obtained after (g) stress relief may be produced into a plate, rod or tubular shape.
  • the plating may be a post-production step and may thus be applied as the final process.
  • crystal plane and low angle grain boundary fractions of the copper alloy material produced by the method of producing the copper alloy material according to the present invention have the following characteristics.
  • dislocations formed by deformation in the production step are formed according to share during bending work, thus causing deterioration in bendability.
  • the formation of dislocations is concentrated at a high angle grain boundary among the grain boundaries.
  • grain boundary fraction is analyzed in accordance with the following method and the fraction of low angle grain boundary is maximized to secure bendability.
  • the ⁇ 001 ⁇ crystal plane in the copper alloy material includes a cubic crystal orientation and a rotated-cubic crystal orientation
  • the ⁇ 110 ⁇ crystal plane includes a Brass crystal orientation and a Goss crystal orientation
  • the ⁇ 112 ⁇ crystal plane includes a Copper crystal orientation.
  • the cubic crystal orientation formed by the ⁇ 001 ⁇ crystal plane is related to bendability and is formed during thermal treatment of the production method according to the present invention
  • the Brass crystal orientation and Goss crystal orientation formed by the ⁇ 110 ⁇ crystal plane, and copper orientation formed by the ⁇ 112 ⁇ crystal plane greatly function to improve tensile strength and spring limit in the production method of the present invention and is formed during rolling.
  • Bendability is closely related to Cu matrix of fine textures, grain boundary and dislocation density.
  • stress during bending work is intensely generated in the relatively weak grain boundary site, dislocation density of the corresponding site is increased and cracks occur during continuous deformation.
  • Equation 1 The relation represented by the following Equation 1 satisfies between one grain orientation g1 and another grain orientation g2 adjacent thereto in an EBSD GB map.
  • Rotation matrix R is represented by one rotation axis [r1, r2, r3] and a rotation angle ⁇ , and the difference in orientation between the orientation g1 and the orientation g2 is represented by each g.
  • orientation difference g of the grain boundary is present.
  • a grain boundary having g of 15 degrees or more is referred to as a high angle grain boundary
  • a grain boundary having g of less than 15 degrees is referred to as a low angle grain boundary.
  • An area ratio between g of 15 degrees or more and g of less than 15 degrees is measured from measurement results of EBSD.
  • the copper alloy material according to the present invention has a ⁇ 001 ⁇ crystal plane fraction of 10% or less, more preferably 2 to 7%.
  • ⁇ 001 ⁇ crystal plane fraction is higher than 10%, ⁇ 001 ⁇ crystal plane is formed during thermal treatment such as solution heat treatment or precipitation heat treatment, bendability is increased, but ⁇ 110 ⁇ and ⁇ 112 ⁇ planes are relatively decreased, thus causing deterioration in tensile strength and spring limit.
  • the ⁇ 110 ⁇ crystal plane fraction is 30 to 60% and the ⁇ 112 ⁇ crystal plane fraction is 30 to 60%, and more preferably, the ⁇ 110 ⁇ crystal plane fraction is 35 to 50% and the ⁇ 112 ⁇ crystal plane fraction is 35 to 50%.
  • the fraction of low angle grain boundary is preferably 50 to 70%, more preferably, 60 to 70%.
  • the fraction of low angle grain boundary is 50% or less, dislocation density at the grain boundary is increased due to excessively high fraction of high angle grain boundary and bendability is rapidly deteriorated.
  • the fraction of low angle grain boundary fraction is 70% or higher, bendability is good, but tensile strength and spring limit cannot be sufficiently secured.
  • the fraction of the ⁇ 001 ⁇ crystal plane is adjusted to 10% or less, the fraction of the ⁇ 110 ⁇ crystal plane is adjusted to 30 to 60%, and the fraction of the ⁇ 112 ⁇ crystal plane is adjusted to 30 to 60%, thereby making the balance between ⁇ 001 ⁇ , ⁇ 110 ⁇ and ⁇ 112 ⁇ crystal planes, and the fraction of the low angle grain boundary is adjusted to 50 to 70% so that low angle grain boundary and high angle grain boundary can be kept in balance, and bendability, tensile strength and spring limit of the finally obtained copper alloy material are thus good.
  • Constituent elements were mixed based on the composition set forth in Table 2 and were subjected to dissolution using a high frequency induction furnace and ingot casting.
  • the ingot had a weight of 5 kg, a thickness of 30 mm, a width of 100 mm and a length of 150 mm.
  • the copper alloy ingot was hot rolled at 980°C to produce a plate and cooled in water and opposite surfaces thereof were face-cut to a thickness of 0.5 mm in order to remove oxide scale. Then, the ingot was subjected to cold work by cold rolling to a thickness of 0.4 mm and was sequentially subjected to solution heat treatment, cold rolling, precipitation heat treatment and stress relief treatment according to conditions set forth in Table 3.
  • the resulting samples are numbered as Example and Comparative Example, as set forth in Table 2.
  • Example and Comparative Example obtained in accordance with Tables 2 and 3 were produced into 0.25 mm copper alloy plate samples, and tensile strength, spring limit, bendability, electrical conductivity, crystal plane, and fraction of low angle grain boundary among grain boundaries of the samples were measured in accordance with the following method.
  • FIGS. 1 and 2 show measurement results of crystal plane and grain boundary fractions of copper alloy material samples produced in accordance with Examples 1 and 4 .
  • FIG. 1A shows a crystal plane fraction of a copper alloy material (Cu-1.8Ni-0.3Si-0.3Sn-0.01P) according to Example 1 and
  • FIG. 1B shows a grain boundary fraction of the copper alloy material.
  • FIG. 2A shows a crystal plane fraction of a copper alloy material (Cu-2.2Ni-0.5Si-0.3Sn-0.01P-0.1Zn) according to Example 4, and
  • FIG. 2B shows a grain boundary fraction of the copper alloy material.
  • FIGS. 1A shows a crystal plane fraction of a copper alloy material (Cu-1.8Ni-0.3Si-0.3Sn-0.01P) according to Example 1
  • FIG. 1B shows a grain boundary fraction of the copper alloy material.
  • FIG. 2A shows a crystal plane fraction of a copper alloy material (Cu-2.2Ni-0.5Si-0.3Sn-0.01P-
  • the copper alloy material according to Example 1 has a tensile strength of 654 MPa, electrical conductivity of 44% IACS, a spring limit of 502 MPa, and excellent bendability in a rolling direction and a direction vertical to rolling.
  • the fraction of ⁇ 001 ⁇ crystal plane is 3.5%
  • the fraction of ⁇ 110 ⁇ crystal plane is 40.4%
  • the fraction of ⁇ 112 ⁇ crystal plane is 41.2%
  • the fraction of low angle grain boundary is 64.3%
  • the fraction of high angle grain boundary is 35.7%.
  • the copper alloy material according to Example 4 has a tensile strength of 742 MPa, electrical conductivity of 41% IACS, spring limit of 547MPa, and superior bendability in both a rolling direction and a direction vertical to rolling.
  • Example 1 No. Crystal plane Grain boundary ⁇ 001 ⁇ ⁇ 110 ⁇ ⁇ 112 ⁇ Low angle grain boundary(2-15) High angle grain boundary(15-180)
  • Example 1 4.3 36.0 45.0 65.4 34.6
  • Example 2 4.4 37.8 44.9 64.9 35.1
  • Example 3 3.9 40.3 42.8 62.8 37.2
  • Example 4 3.5 40.4 41.2 64.3 35.7
  • Example 5 3.8 42.3 43.1 65.9 34.1
  • Example 6 3.9 39.8 42.1 62.8 37.2
  • Example 7 4.2 42.5 43.1 66.8 33.2
  • Example 8 3.6 35.4 44.3 68.3 31.7
  • Example 9 3.8 38.2 45.2 69.5 30.5
  • Example 10 3.2 39.4 44.2 67.8 32.2
  • Example 11 3.1 32.5 47.1 67.1 32.9
  • Example 12 3.5 33.5 48.1 69.0 31.0
  • Example 13 3.0 32.5 48.5 68.5 31.5
  • Comparative Example 1 6.5 42.5 43.2 67.5 32.5 Comparative Example 2
  • Tensile strength was measured in a rolling direction using a tensile strength tester in accordance with JIS Z 2241.
  • the unit of tensile strength is MPa.
  • Electric resistance was measured at 240Hz using a 4-probe method, and resistance and electrical conductivity were represented as percentage (%IACS) based on standard reference sample pure copper.
  • Spring limit was measured in accordance with JIS H3130. In accordance with a cantilever-type measurement method according to specification, permanent deformation was measured by fixing one end of a plate while stepwise increasing bending variation at the other end thereof. Spring limit was calculated using force at the measured permanent deformation.
  • the unit is MPa.
  • Bending test was conducted in a good way direction (bending in a direction vertical to a rolling direction) and in a bad way direction (bending in a direction parallel to a rolling direction) under the conditions of an inner bending radius R and a material thickness t.
  • the fraction of the ⁇ 001 ⁇ crystal plane is 10% or less
  • the fraction of the ⁇ 110 ⁇ crystal plane is 30 to 60%
  • the fraction of the ⁇ 112 ⁇ crystal plane is 30 to 60%
  • low angle grain boundary fraction of grain boundary is 50 to 70%
  • tensile strength is 620 to 1,000 MPa
  • spring limit is 460 to 750 MPa and cracks do not occur during bending work in a rolling direction (also referred to as direction parallel to rolling) and in a direction vertical to rolling.
  • Comparative Example 1 which includes Ni in an amount of less than 1 wt%, had good bendability due to insufficient amounts of Ni and Si precipitates, but had poor tensile strength and spring limit.
  • Comparative Example 2 which was subjected to solution heat treatment at a temperature of 700°C for 0.5 seconds, did not form an over-saturated solution due to supply of insufficient amount of heat. As a result, the sample of Comparative Example 2 did not secure sufficient tensile strength and spring limit even under the conditions of optimal precipitation heat treatment conditions.
  • Comparative Example 3 which was subjected to solution heat treatment at 1,050°C for 400 seconds, had poor bendability of the finally produced sample in the rolling direction due to rapid growth of grains in the copper alloy during solution heat treatment.
  • Comparative Example 4 which was subjected to final rolling of 80%, exhibited a rapid increase in fractions of ⁇ 110 ⁇ and ⁇ 112 ⁇ crystal planes of the obtained sample, a decrease in fraction of the low angle grain boundary, an increase in fraction of high angle grain boundary and deterioration in bendability both in a rolling direction and in a direction vertical to rolling.
  • Comparative Example 5 which was subjected to final cold rolling at a rolling ratio of 5%, could not secure sufficient tensile strength and spring limit due to excessively low fractions of ⁇ 110 ⁇ and ⁇ 112 ⁇ crystal planes of the obtained sample.
  • Comparative Example 6 which contains 4.5 wt% of Ni, suffered from side cracking during hot rolling in the production of the copper alloy material.
  • Comparative Example 7 which was subjected to precipitation heat treatment at 700°C for 25 hours, had good bendability of the sample obtained in the over-aging area, but had significantly reduced tensile strength and spring limit.
  • Comparative Example 8 which was subjected to precipitation heat treatment at 300°C for 1 hour, had poor electrical conductivity, tensile strength and spring limit due to incomplete growth of Ni-Si precipitates in the copper alloy sample.
  • Comparative Example 10 which was subjected to stress relief treatment at 200°C for 5 seconds, could not sufficiently reduce stress present in the finally produced copper alloy material, when the treatment temperature was lower than that of the production method of the present invention, and did not sufficiently recover spring limit.
  • the copper alloy material produced in accordance with the production method of the present invention has a ⁇ 001 ⁇ crystal plane fraction of 10% or less, ⁇ 110 ⁇ and ⁇ 112 ⁇ crystal plane fractions, respectively, of 30 to 60%, and a low angle grain boundary fraction of 50 to 70%, and has improved tensile strength, spring limit, bendability and electrical conductivity.
  • This material is very suitable for connectors and electric and electronic components which are advanced toward the trend of low weight, small size and high density.

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PCT/KR2016/008028 2015-12-28 2016-07-22 Copper alloy material for automobile and electrical and electronic components and method of producing the same Ceased WO2017115963A1 (en)

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