JP2012144789A - Cu-Co-Si-Zr ALLOY MATERIAL - Google Patents

Cu-Co-Si-Zr ALLOY MATERIAL Download PDF

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JP2012144789A
JP2012144789A JP2011005088A JP2011005088A JP2012144789A JP 2012144789 A JP2012144789 A JP 2012144789A JP 2011005088 A JP2011005088 A JP 2011005088A JP 2011005088 A JP2011005088 A JP 2011005088A JP 2012144789 A JP2012144789 A JP 2012144789A
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phase particles
solution treatment
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alloy
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Yasuhiro Okafuji
康弘 岡藤
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Jx Nippon Mining & Metals Corp
Jx日鉱日石金属株式会社
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/06Alloys based on copper with nickel or cobalt as the next major constituent
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026Alloys based on copper

Abstract

A Cu—Co—Si—Zr copper alloy material suitable for materials for electronic and electrical equipment such as a movable connector, which has excellent bending workability and can be made highly conductive, and a method for producing the same.
It contains 1.0 to 2.5 wt% Co, 0.2 to 0.7 wt% Si, 0.001 to 0.5 wt% Zr, and the Co / Si element ratio is 3.5. -5.0, containing 3,000 to 500,000 particles / mm 2 of second phase particles with a diameter of 0.20 μm or more and less than 1.00 μm, good grain size 10 μm or less, conductivity 60% IACS or more Cu-Co-Si-Zr alloy material having excellent bending workability. The alloy material may contain 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 to 10.00 μm, and the 0.2% proof stress may be 600 MPa or more. The alloy material has a temperature of hot heating performed after casting and before solution treatment at a temperature 45 ° C. higher than the following solution treatment temperature, and a cooling rate from the temperature at the start of hot rolling to 600 ° C. The solution treatment temperature is selected in the range of (50 × Cowt% + 775) ° C. or more and (50 × Cowt% + 825) ° C. or less, and the aging treatment after the solution treatment is preferably 450 to It can be produced at 650 ° C. in 1 to 20 hours.
[Selection figure] None

Description

  The present invention relates to a material for electronic and electrical equipment that is excellent in bending workability and can be made highly conductive, and particularly relates to a Cu-Co-Si-Zr copper alloy material suitable for electronic and electrical equipment materials such as movable connectors.

Electronic and electrical equipment materials are required to have properties such as electrical conductivity, strength, and bending workability. In recent years, there is an increasing demand for higher currents in electrical and electronic parts, particularly movable connectors. In order not to increase the size of the movable connector, it is necessary to use a material that has good bendability even at a thickness of 0.2 mm or more and at the same time ensures high conductivity and strength.
Conventionally, as precipitation-strengthening-type copper alloys having characteristics capable of achieving high strength without deteriorating conductivity, Cu—Ni—Si based copper alloys, Cu—Co—Si based, Cu—Co—Si—Zr based and Cu -Ni-Co-Si based copper alloys are known. In order to produce these copper alloys, after the additive elements are dissolved in the solution treatment, Ni 2 Si, Co 2 Si, etc. are precipitated or crystallized as second phase particles in the matrix by cold rolling and aging heat treatment. I am letting. However, since the solid solution amount of Ni 2 Si is relatively large, it is difficult to achieve a conductivity of 60% IACS or more with a Cu—Ni—Si based copper alloy. Therefore, research has been made on Cu-Co-Si, Cu-Co-Si-Zr, and Cu-Ni-Co-Si alloys that have Co 2 Si as a main precipitate and have high conductivity. Has been. These copper alloys cannot achieve the target strength unless they are sufficiently dissolved and fine precipitates are deposited. However, various solutions have been studied because when the solution is formed at a high temperature, the crystal becomes coarse and the bending workability deteriorates.

  In Japanese Patent Application Laid-Open No. 2009-242814 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-266787 (Patent Document 2), in order to produce a precipitation-strengthened copper alloy for electrical and electronic component materials such as lead frames, Therefore, the crystal grain size is controlled by utilizing the effect of suppressing the crystal grain growth to improve the bending workability. In the above document, the second phase particles are precipitated in the cooling process of hot working or the temperature rising process of solution heat treatment, and are also precipitated by aging precipitation heat treatment after chamfering (Patent Document 1, “0025”, etc.). In addition, in International Publication No. 2010/016429 (Patent Document 3), Cu—Co—Si (—Zr) alloy having a specific composition allows two different sizes of precipitates to exist, It is described that suppression of crystal grain growth and increase in strength can be obtained.

JP 2009-242814 A JP 2008-266787 A International Publication No. 2010/016429

  In general, specific target values for preventing the movable connector from becoming large are a conductivity of 60% IACS or higher, a 0.2% proof stress YS of 600 MPa or higher, or a tensile strength TS of 630 MPa or higher. The ratio (MBR / t) between the bending radius R and the plate thickness t at which a crack that is an index does not occur is 0.5 or less (0.3 mm plate, Bad Way). The bending workability varies depending on the crystal grain size and the size and number of the second phase particles, but the crystal grain size for obtaining MBR / t of 0.5 or less with a 0.3 mm thick plate is Cu—Co—. In the case of Si-based and Cu-Ni-Co-Si-based alloys, it is generally considered to be 10 μm or less. The crystal grains grow by the solution treatment, and the crystal grain size is determined by the temperature and time of the solution treatment, the additive element, and the size and number of the second phase particles.

However, Patent Documents 1 and 2 are not essential for Co but target a wide range of second phase particles. In the method of controlling the crystal grain size by the second phase particle precipitate described in Patent Document 1, the crystal grain size is controlled. However, it is inferior in conductivity and cannot achieve high current. In Patent Document 2, attention is focused on the second phase particles having a diameter of 50 to 1000 μm because there is an effect of suppressing the growth of recrystallized grains in the solution treatment, but this size Co-based second phase particles are solidified by solution treatment. It may melt and disappear. Therefore, it is necessary to adjust the solution temperature and time so that the precipitate does not dissolve, and only a Cu—Co—Si—Zr alloy having poor conductivity or bendability can be obtained. Further, the second phase particle precipitate having this range size may be precipitated after solutionization, and does not directly show the effect of controlling the crystal grain size. In this document, the second phase particle density on the grain boundaries and the diameter and volume density of the second phase particles are evaluated by observation with a transmission electron microscope (TEM), but the crystal grain size can be controlled to 10 μm or less. If the second phase is precipitated until the particle is overlapped, there is a possibility that accurate numerical values cannot be grasped due to the overlap of particles.
Patent Document 3 also focuses on Co-based second phase particles as having an effect of controlling the growth of the crystal grain size, but the particle sizes are 0.005 to 0.05 μm and 0.05 to 0 in diameter. The Cu—Co—Si—Zr alloy was inferior in bendability.
As described above, since the recent precipitation-strengthened copper alloys have been intended for use in thin plates for electronic components such as lead frames, excellent bending workability with a thick plate of about 0.3 mm has not been studied.

As a result of intensive studies to solve the above problems, the present inventor has made the following invention.
(1) It contains 1.0 to 2.5 wt% Co, 0.2 to 0.7 wt% Si, 0.001 to 0.5 wt% Zr, and the Co / Si element ratio is 3.5 to A Cu—Co—Si—Zr alloy material having a diameter of 0.20 μm or more and less than 1.00 μm, containing 3,000 to 500,000 particles / mm 2, and having an electrical conductivity EC A copper alloy material having a good bending workability of 60% IACS or more and a crystal grain size of 10 μm or less.
(2) The copper alloy material according to (1), containing 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 μm to 10.00 μm.
(3) The copper alloy material according to (1) or (2), wherein the 0.2% proof stress YS is 600 MPa or more.
(4) The temperature of the hot heating performed after the casting and before the solution treatment is a temperature higher by 45 ° C. or more than the solution treatment temperature selected below, and cooling from the temperature at the start of hot rolling to 600 ° C. The rate is 100 ° C./min or less, and the solution treatment temperature is selected in the range of (50 × Cowt% + 775) ° C. or more and (50 × Cowt% + 825) ° C. or less, (1) to (3) The manufacturing method of the copper alloy material of description.
(5) The method for producing a copper alloy material according to (4), wherein the aging treatment after the solution treatment is performed at 450 to 650 ° C. for 1 to 20 hours.

  In the production of a Cu—Co—Si—Zr alloy material having a specific composition, the present invention adjusts the solution treatment temperature in order to avoid crystal coarsening, and the hot heating temperature before the solution treatment is also a solution treatment. It adjusts so that it may adapt to temperature, the cooling rate after hot heating is also adjusted, and the 2nd phase particle | grains which have a specific particle size precipitate a specific amount. By adjusting the second phase particles, a crystal grain size of 10 μm or less can be obtained, and practical strength can be achieved in addition to bending workability suitable for a movable connector and conductivity capable of increasing current.

It is a reference figure explaining the diameter of a 2nd phase particle.

(Cu-Co-Si-Zr alloy material)
The alloy material of the present invention contains 1.0 to 2.5 wt% (shown in% unless otherwise specified), preferably 1.5 to 2.2% Co, 0.2 to 0.7%, Preferably it contains 0.3 to 0.55% Si. Preferably, the balance other than the following Zr consists of Cu and unavoidable impurities, but various elements that are usually employed as components to be added to copper alloys by those skilled in the art within the range in which the structure of the present invention can achieve the intended effect, For example, it may further contain Cr, Mg, Mn, Ni, Sn, Zn, P, Ag and the like.
The stoichiometric ratio of Co / Si when the second phase particles are Co 2 Si is theoretically 4.2, but in the present invention, it is 3.5 to 5.0, preferably 3.8 to 4 In the range, second phase particles Co 2 Si and Co—Si—Zr compounds suitable for precipitation strengthening and crystal grain size adjustment are formed. If the amount of Co and / or Si is too small, the effect of precipitation strengthening is small. If the amount is too large, the solution is not dissolved and the conductivity is poor. When the second phase particles Co 2 Si are precipitated, a precipitation strengthening effect appears, and after the precipitation, the matrix purity becomes high, so that the conductivity is improved. Furthermore, when a specific amount of second phase particles having a specific size is present, the growth of crystal particles is inhibited and the crystal grain size can be reduced to 10 μm or less.

The alloy material of the present invention contains 0.001 to 0.5 wt%, preferably 0.01 to 0.4%, of Zr, and has improved strength and electrical conductivity. This effect is at a level higher than expected from a Cu-Co-Si-only system. If Zr is less than 0.001 wt%, the intended effect of increasing the strength and electrical conductivity cannot be obtained, and if it exceeds 0.5 wt%, coarse silicide is generated and the strength and bending workability are reduced.
The crystal grain size of the alloy material of the present invention is 10 μm or less. When the thickness is 10 μm or less, good bending workability can be achieved.
The copper alloy material of the present invention may have various shapes such as a plate material, a strip material, a wire material, a rod material, and a foil, and may be a movable connector plate material or a strip material, but is not particularly limited.

(Second phase particles)
The second phase particles of the present invention are particles that are generated when other elements are contained in copper and that form a phase different from the copper matrix (matrix). The number of second phase particles having a diameter of 50 nm or more can be arbitrarily set to a copper plate rolling parallel section (surface parallel to the rolling surface and parallel to the thickness direction) subjected to electrolytic polishing and pickling etching after mirror finishing by mechanical polishing. It is obtained by measuring the number of particles in the corresponding diameter range from a scanning electron micrograph of one visual field obtained by selecting five locations. Here, the diameter refers to an average value of L1 and L2 by measuring the short diameter (L1) and long diameter (L2) of the particles as shown in FIG.
Most of the second phase particles of the present invention are Co 2 Si or Co—Si—Zr compounds, but other intermetallic compounds such as Ni 2 Si may be in the range. The element which comprises 2nd phase particle can be confirmed using EDX attached to FE-SEM (Japan FEI Co., Ltd. model XL30SFEG), for example.

In the copper alloy material of the present invention, the second phase particles of 0.20 μm or more and less than 1.00 μm are 3,000 to 500,000 particles / mm 2 , preferably 10,000 to 200,000 particles / mm 2 , The content is preferably 13,000 to 100,000 pieces / mm 2 , mainly precipitated after hot rolling and before solution treatment, but may be precipitated by solution treatment. The second phase particles precipitated before the solution treatment suppress the growth of the crystal grain size in the solution treatment, but may be dissolved. Therefore, it is preferable to adjust the solution treatment conditions to suppress the variation in the number as much as possible.
The second phase particles having a diameter of 1.00 μm or more and 10.00 μm or less are preferably 10 to 2,000 particles / mm 2 , more preferably 20 to 1,000 particles / mm 2 , and most preferably 30 to 500 particles. / Mm 2 contained. The second phase particles in this diameter range are precipitated by slowing the cooling rate after hot heating, and the particle size can be adjusted by first aging treatment if necessary. The preferable range of the number of second phase particles having the above-mentioned diameter is also linked to the number of second phase particles of 0.20 μm or more and less than 1.00 μm. Within this range, high-temperature solution treatment is possible, and growth of crystal grain size in the solution treatment is suppressed, while sufficiently solid-solved Co, Si, and Zr are removed by the second (second) aging treatment. By being finely precipitated, high strength, high conductivity, and good bending workability can be achieved. However, if it exceeds 2,000 pieces / mm 2 , the bendability is lowered, which is not preferable.
The number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm and 1.00 μm or more and 10.00 μm or less does not change much before and after the solution treatment and after the second aging treatment. It can be evaluated with the test piece.

When the second phase particles having a diameter exceeding 10.00 μm are present, the precipitation of the fine second phase particles is hindered and the precipitation strengthening effect cannot be obtained. Therefore, the alloy material of the present invention preferably contains second phase particles having a diameter of more than 10.00 μm, preferably 1 piece / mm 2 or less, more preferably 0.01 pieces / mm 2 or less.
The second phase particles of 0.05 μm or more and less than 0.20 μm are precipitated during hot rolling, subsequent cooling, and first aging treatment, but are almost dissolved in the solution treatment, and the subsequent cooling and (second 2) Precipitates by aging treatment. The second phase particles of less than 0.05 μm are dissolved in the solution treatment and precipitated in large quantities by the (second) aging treatment. Therefore, these second phase particles do not have an effect of adjusting the crystal grain size, but contribute to strength improvement.

(Physical properties of alloy materials)
The electrical conductivity EC of the alloy material of the present invention is 60% IACS or more, preferably 65% IACS or more. Within this range, it is possible to manufacture components capable of increasing the current.
The favorable bending workability in the present invention means a 0.3 mm thick plate having a minimum bending radius MBR / t of 0.5 or less (Bad Way). When the 0.3 mm thick plate has an MBR / t of 0.5 or less, the characteristics required during the manufacture and use of electronic components, particularly movable connectors, are satisfied. In addition, when the alloy material of the present invention is made thinner than 0.3 mm, a better bending workability can be obtained.
The 0.2% yield strength YS of the alloy material of the present invention is preferably 600 MPa or more, more preferably 650 MPa or more, and the tensile strength TS is preferably 630 MPa or more, more preferably 660 MPa or more. Within the above range, it is particularly sufficient as a material for electronic parts such as a movable connector plate.

(Production method)
The manufacturing method process of the alloy material of the present invention is the same as that of a normal precipitation-strengthened copper alloy, and is melt casting → (homogenization heat treatment) → hot rolling → cooling → (first aging treatment) → face cutting → cold. Rolling → solution treatment → cooling → (cold rolling) → second aging treatment → final cold rolling → (tempered strain relief annealing). The steps in parentheses can be omitted, and the final cold rolling may be performed before aging heat treatment.
In the present invention, homogeneous heating treatment and hot rolling are performed after casting, but the homogeneous heating treatment may be heating in hot rolling (in the present specification, heating performed in homogeneous heating and hot rolling is performed. Collectively referred to as “hot heating”).
The temperature of the hot heating may be any temperature at which the additive element is substantially dissolved, and specifically, it is 40 ° C. or higher, preferably 45 ° C. or higher from the solution treatment temperature selected below. The upper temperature limit for hot heating is individually defined by the metal composition and equipment, but is usually 1,000 ° C. or lower. The heating time depends on the plate thickness, but is preferably 30 to 500 minutes, more preferably 60 to 240 minutes. It is preferable that almost all additive elements such as Co and Si dissolve during hot heating.
The cooling rate after hot heating is 100 ° C./min or less, preferably 5 to 50 ° C./min. At this cooling rate, the second phase particles finally having a diameter of 0.20 μm or more and less than 10.00 μm are deposited within the target range. However, conventionally, only the fine second-phase particles have been deposited because they have been rapidly cooled by a water-cooled shower or the like for the purpose of suppressing the coarsening of the second-phase particles.
Although the material is chamfered after cooling, it is preferable to further optionally perform the first aging treatment because the size and number of target second phase particles can be adjusted. The conditions for the first aging treatment are preferably 600 to 800 ° C. and 30 s to 30 h.

The temperature of the solution treatment performed after the arbitrary first aging treatment is selected in the range of (50 × Cowt% + 775) ° C. or more and (50 × Cowt% + 825) ° C. or less. A preferable treatment time is 30 to 500 s, more preferably 60 to 200 s. Within this range, the adjusted second phase particles remain and prevent the crystal grain size from increasing, while the finely precipitated Co, Si, and Zr are sufficiently dissolved in the second stage of the second stage. Precipitate as fine second phase particles by aging treatment.
A preferable cooling rate after the solution treatment is 10 ° C./s or more. If it falls below this cooling rate, second phase particles precipitate during cooling, and the amount of solid solution decreases. The upper limit of the cooling rate is not particularly limited, but it can be about 100 ° C./s, for example, when the equipment is generally adopted.
When the contents of Co, Si and Zr are lower than in the present invention, or when they are not gradually cooled after hot rolling and not subjected to the second aging treatment heating, there are few second phase particles precipitated before the solution treatment. When solution treatment is performed on an alloy with few precipitated second phase particles, the crystal grain size becomes coarse at a solution treatment time of more than 1 minute at a high temperature exceeding 850 ° C., so only a short heat treatment of about 30 seconds can be performed. In addition, since the amount that can actually be dissolved is small, a sufficient precipitation strengthening effect cannot be obtained.

The temperature of the second aging treatment after the solution treatment is preferably 450 ° C. to 650 ° C. for 1 to 20 hours. Within this range, the diameter of the second phase particles remaining in the solution treatment can be maintained within the range of the present invention, and the added additive elements that have been solid solution are precipitated as fine second phase particles to enhance the strength. Contribute to.
The final rolling degree is preferably 5 to 40%, more preferably 10 to 20%. If it is less than 5%, the strength increase due to work hardening is insufficient, while if it exceeds 40%, the bending workability deteriorates.
In addition, when the final cold rolling is performed before the second aging heat treatment, the second aging heat treatment may be performed at 450 ° C. to 600 ° C. for 1 to 20 hours.
The strain relief annealing temperature is preferably 250 to 600 ° C., and the annealing time is preferably 10 s to 1 hour. Within this range, there is no change in the size and number of the second phase particles, and the crystal grain size does not change.

(Manufacturing)
An ingot having a thickness of 30 mm was cast into a molten metal made of electrolytic copper, Si, Co, and Zr by changing the amount and type of additive elements. This ingot was heated at the temperature in the table for 3 hours (hot), and formed into a plate having a thickness of 10 mm by hot rolling. Next, the oxide scale on the surface is ground and removed, and an aging heat treatment is performed for 15 hours. Thereafter, a solution treatment is performed by appropriately changing the temperature and time, and the solution is cooled at the cooling temperature in the table. Time aging heat treatment was performed, and the final thickness was 0.3 mm by the final cold rolling. The strain relief annealing time is 1 minute.

(Evaluation)
The concentration of the additive element in the copper alloy matrix was analyzed by ICP-mass spectrometry using the sample after the chamfering process.
The diameter and number of the second phase particles were determined by mechanically polishing the sample rolling parallel cross section before final cold rolling to finish it into a mirror surface, followed by electrolytic polishing and pickling etching, and using a scanning electron microscope I went to 5 photos. The observation magnifications are (a) 5 × 10 4 times when 0.05 μm or more and less than 0.20 μm, (b) 1 × 10 4 times when 0.20 μm or more and less than 1.00 μm, (c) 1.00 μm or more and 10.00 μm. The following are 1 × 10 3 times (represented in the table as “50-200 nm”, “200-1000 nm” and “1000-10000 nm”, respectively).
As for the crystal grain size, the average crystal grain size was measured by a cutting method in accordance with JIS H0501.
For the electrical conductivity EC, the specific resistance was measured by a four-terminal method in a thermostatic chamber maintained at 20 ° C. (± 0.5 ° C.) (distance between terminals: 50 mm).

With respect to the bending workability MBR / t, a strip test piece (width 10 mm × length 30 mm × thickness 0.3 mm) of TD (Transverse Direction) sampled so that the bending axis is perpendicular to the rolling direction is 90. A W bending test (JIS H3130, Bad Way) was performed, and the minimum bending radius (mm) at which no cracks occurred was defined as MBR (Minimum Bend Radius), and the evaluation was performed based on the ratio MBR / t with the plate thickness t (mm).
0.2% proof stress YS and tensile strength TS were measured three times according to JIS Z 2241 for samples of JIS Z2201-13B cut in the rolling parallel direction, and average values were obtained.

Co and Si concentration, Co / Si element ratio, number of second phase particles with diameter of 0.20 μm or more and less than 1.00 μm, conductivity EC and crystal grain size are within the scope of the present invention, and the amount of Zr added is changed The results are shown in Tables 1A-C.
From Table 1A and B, compared with the comparative example 3 which does not add Zr at all, Example 1 or 2 which added 0.01% or 0.3% of Zr has an increase in strength and electrical conductivity or electrical conductivity. Moreover, it was confirmed that the conductivity increased in proportion to the amount of Zr added. However, in Comparative Example 4 in which 1.0% was added, the strength and bending workability were lowered (the explanation of Table 1C will be described later).

Based on the above results, the results of changing the component composition and the production conditions with the Zr content being 0.1% are shown in Tables 2A to 2C (the description of Table 2C will be described later).
In order to satisfy the requirements of the present invention, Examples 1 to 11 were excellent in electrical conductivity, strength, bending workability with a thick plate, and suitable for a movable connector capable of increasing current.
Reference Example 22 has the same conditions as in Example 6, but after the solution treatment, cool at the cooling temperature in the table, and finish the final thickness to 0.3 mm by final cold rolling before the aging treatment. The aging treatment was performed for 3 hours at the same temperature, and the tempered strain relief annealing was performed in the same manner. Although the strength was slightly inferior to the physical properties of Example 6, the bendability was improved.

In Comparative Example 12, since the solution temperature is too high, the second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm disappear during the solution heat treatment, and the effect of suppressing crystal growth cannot be exhibited. Becomes larger and the bendability is poor.
Comparative Example 13 has a low Co / Si ratio, Comparative Example 14 has a high Co / Si ratio, and none of them obtains precipitation strengthening action due to the fine second phase particles, resulting in low strength, and the solid solution concentration of Co or Si is low. Since it becomes high, conductivity is also inferior.
In Comparative Example 15, the cooling rate after hot working was too slow, so there were many second phase particles having a diameter of 1.00 μm or more and less than 10.00 μm, and the bendability was poor.
In Comparative Example 16, the cooling rate after hot working is fast, and there are few second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm, and the effect of suppressing crystal growth cannot be exhibited, and the bendability is poor. In Comparative Example 17, the first aging treatment was performed at a high temperature to compensate for the fact that the cooling rate after hot working was high and the number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm was small. Second phase particles having a size of less than 00 μm were precipitated, but the bendability was poor because the crystal grain size was increased by heating at that time.
Since Comparative Example 18 has higher hot heating temperature and solution treatment temperature than Example 8, the effect of suppressing crystal growth cannot be exhibited, the crystal grain size becomes large, the bendability is poor, and the conductivity is also Example. Low compared to 8.
In Comparative Example 19, the solution treatment temperature is lower than that in Example 11, and the amount of the added element dissolved in the solution treatment is reduced, and the strength is low.
In Comparative Example 20, the Co concentration is high, the solution treatment temperature is relatively high, and the time is long. Therefore, the number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm is large, and the bendability is poor.
In Comparative Example 21, the Co concentration is high and the solution treatment temperature is the same as the hot working temperature, which is a high temperature. Therefore, the effect of suppressing the growth of the crystal grain size cannot be exhibited, and the diameter is 0.20 μm or more and less than 1.00 μm. The number of second phase particles is small, the number of second phase particles having a diameter of 1.00 μm to 10.00 μm is large, and the bendability is poor.

Although the present invention is not limited by theory, it is considered that the relationship between the steps of the production method and the disappearance and precipitation of the second phase particles is as follows. During the hot heating, the additive element dissolves in the copper. In the cooling stage in which the speed during hot rolling and after hot rolling is adjusted, second phase particles of 0.05 μm or more are precipitated. In the first aging treatment after hot rolling, the second phase particles of 0.05 μm or more are not precipitated, and a large amount of second phase particles of less than 0.05 μm are precipitated. The second phase particles having a size of less than 0.20 μm disappear by solid solution treatment with the temperature adjusted. In the cooling stage in which the speed after the solution treatment is adjusted, a small amount of second phase particles of 0.05 μm or more and less than 0.2 μm mainly precipitate. In the second aging treatment after the solution treatment, a large amount of second phase particles of less than 0.05 μm are precipitated.
Table 1C and Table 2C show how the second phase particles having a diameter range of (a) 50 nm or more and less than 200 nm, (b) 200 nm or more and less than 1000 nm, and (c) 1.000 nm or more and 10.000 nm change in the manufacturing process. The measured results are shown. In all measurements, second phase particles having a diameter exceeding 10,000 nm (10.00 μm) could not be confirmed. Since the number decreases logarithmically as the diameter increases, the number of display digits is changed.
(A) is a solution treatment condition of the present invention, so that it is a solid solution and becomes a number of about 1/5 to 1/10, and the number does not vary much after the second aging treatment. In (b), the number hardly increases or decreases under the solution treatment conditions and the second aging treatment conditions of the present invention. (C) is the hot heating and cooling conditions of the present invention, the number does not change at all before the solution treatment and before the final cold rolling.
When the first aging treatment temperature is high, the number of (b) increases (Comparative Example 17), and when the solution treatment temperature is high or the treatment time is long, the number of (b) decreases, and the lower limit of the present invention. There is a tendency to be less than the value (Comparative Examples 18 and 21).

Claims (5)

  1. It contains 1.0 to 2.5 wt% Co, 0.2 to 0.7 wt% Si, 0.001 to 0.5 wt% Zr, and the Co / Si element ratio is 3.5 to 5.0. in which a Cu-Co-Si-Zr alloy, 3,000 to 500,000 pieces of second phase particles of less than a diameter of 0.20 [mu] m 1.00 .mu.m / mm 2 contains the conductivity EC is 60% IACS A copper alloy material having good bending workability and having a crystal grain size of 10 μm or less.
  2. The copper alloy material according to claim 1, comprising 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 µm to 10.00 µm.
  3.   The copper alloy material according to claim 1 or 2, wherein the 0.2% proof stress YS is 600 MPa or more.
  4.   The temperature of the hot heating performed after the casting and before the solution treatment is 45 ° C. or more higher than the solution treatment temperature selected below, and the cooling rate from the hot rolling start temperature to 600 ° C. is 100 The copper according to any one of claims 1 to 3, wherein the solution treatment temperature is selected in a range of (50 x Cowt% + 775) ° C or higher and (50 x Cowt% + 825) ° C or lower. Manufacturing method of alloy material.
  5.   The method for producing a copper alloy material according to claim 4, wherein the aging treatment after the solution treatment is performed at 450 to 650 ° C for 1 to 20 hours.
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