WO2011122490A1 - Cu-Co-Si合金材 - Google Patents
Cu-Co-Si合金材 Download PDFInfo
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- WO2011122490A1 WO2011122490A1 PCT/JP2011/057442 JP2011057442W WO2011122490A1 WO 2011122490 A1 WO2011122490 A1 WO 2011122490A1 JP 2011057442 W JP2011057442 W JP 2011057442W WO 2011122490 A1 WO2011122490 A1 WO 2011122490A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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
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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
Definitions
- the present invention relates to a Cu—Co—Si copper alloy material that is excellent in bending workability and can be made highly conductive and is particularly suitable for materials for electronic and electrical devices such as movable connectors.
- 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.
- the solid solution amount of Ni 2 Si is relatively large, a conductivity of 60% IACS or more is difficult to achieve with a Cu—Ni—Si based copper alloy. Therefore, studies have been made on Cu—Co—Si and Cu—Ni—Co—Si alloys which have Co 2 Si as a main precipitate and have high conductivity. These copper alloys cannot achieve the target strength unless they are sufficiently dissolved and fine precipitates are deposited.
- various solutions have been studied because when the solution is formed at a high temperature, the crystal becomes coarse and the bending workability deteriorates.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2009-242814 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-266787 (Patent Document 2)
- the crystal grain size is controlled by utilizing the effect of suppressing the crystal grain growth to improve the bending workability.
- the second phase particles are precipitated in the cooling process of hot working or the temperature rising process of solution heat treatment, and also precipitated by aging precipitation heat treatment after chamfering (Patent Document 1, “0025”, etc.).
- Patent Document 1 International Publication No.
- Patent Document 3 is a Cu—Co—Si alloy having a specific composition, which controls the crystal grain size limitation and the fine size of precipitates. Describes a method of controlling the crystal grain size according to the solution temperature, the cooling rate after the solution treatment, and the aging heat treatment temperature.
- 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) of the bending radius R and the plate thickness t at which the crack, which is an index, does not occur is 0.5 or less (0.3 mm plate, Bad Way). This bendability varies depending on the crystal grain size and the size and number of the second phase grains.
- the crystal grain size for obtaining MBR / t of 0.5 or less with a 0.3 mm thick plate is Cu—Co—.
- the crystal grains grow by solution treatment, and the size of 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.
- Patent Documents 1 and 2 are not essential for Co but target a wide range of second phase particles.
- the crystal grain size is controlled.
- it is inferior in conductivity and cannot achieve high current.
- attention is focused on second-phase particles having a diameter of 50 to 1000 nm because they have an effect of suppressing the growth of recrystallized grains in the solution treatment.
- Co-based second-phase particles of this size 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 alloy having poor conductivity or bendability can be obtained.
- 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.
- 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 ⁇ m 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.
- the crystal grain size is controlled to 10 ⁇ m or less by the solution temperature, the cooling rate after the solution treatment, and the aging heat treatment temperature, but in this method, Co is dissolved to 1.5 mass% or more. The target strength cannot be obtained.
- the conventional precipitation-strengthened copper alloy has been intended for use in thin plates for electronic components such as lead frames, excellent bending workability in a thick plate of about 0.3 mm has not been studied.
- the copper alloy material according to (1) containing 10 to 1,000 particles / mm 2 of second phase particles having a diameter of 1.00 ⁇ m to 5.00 ⁇ m.
- 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 (1) to (3) The manufacturing method of the copper alloy material of description.
- the present invention adjusts the solution treatment temperature to avoid crystal coarsening, and the hot heating temperature before the solution treatment is also set to the solution treatment temperature. It adjusts so that it may adapt, the cooling rate after hot heating is also adjusted, and the 2nd phase particle
- the second phase particles By adjusting the second phase particles, a crystal grain size of 10 ⁇ m 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.
- FIG. 4 is a scanning electron microscope (SEM) photograph (5 ⁇ 10 4 times) taken in Example 3.
- SEM scanning electron microscope
- the alloy material of the present invention contains 1.5 to 2.5 wt% (hereinafter expressed as% unless otherwise specified), preferably 1.7 to 2.2% Co, 0.3 to 0.7%, Preferably, 0.4 to 0.55% Si is contained.
- the balance is made of Cu and unavoidable impurities, but various elements that are usually employed by those skilled in the art as components to be added to the copper alloy, such as Cr and Mg, within the range in which the structure of the present invention can achieve the intended effect. , Mn, Ni, Sn, Zn, P, Ag, and the like may be further included.
- the stoichiometric ratio of Co / Si contained is theoretically 4.2, but is actually 3.5 to 5.0, preferably 3.8 to 4.6. If so, second phase particles Co 2 Si 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 ⁇ m or less.
- the crystal grain size of the alloy material of the present invention is 10 ⁇ m or less. When the thickness is 10 ⁇ m 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.
- 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 (see FIG. 1) of one field of view obtained by selecting five locations.
- the diameter means the average value of L1 and L2 by measuring the short diameter (L1) and long diameter (L2) of the particles as shown in FIG.
- second phase particles of the present invention are Co 2 Si, but other intermetallic compounds such as Ni 2 Si may be in the range.
- the elements constituting the second phase particles can be confirmed using, for example, EDX attached to FE-SEM (Japan FEI Co., Ltd. Model XL30SFEG).
- the second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m are 3,000 to 150,000 particles / mm 2 , preferably 10,000 to 120,000 particles / mm 2 ,
- the content is preferably 13,000 to 100,000 / mm 2, and is precipitated mainly after hot heating and before solution treatment, but may be precipitated by solution treatment.
- the second phase particles precipitated before the solution treatment suppresses 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 reduce the variation in the number as much as possible.
- the second phase particles having a diameter of 1.00 ⁇ m or more and 5.00 ⁇ m or less are preferably 10 to 1,000 particles / mm 2 , more preferably 20 to 500 particles / mm 2 , and most preferably 30 to 400 particles / mm 2 . 2 is contained, precipitates by slowing the cooling rate after hot heating, and the particle size can be adjusted by first aging treatment if necessary.
- the preferable range is also linked to the number of second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m. Within this range, high-temperature solution treatment is possible, and growth of the crystal grain size is suppressed in the solution treatment, while sufficiently dissolved Co and Si are finely precipitated by the (second) aging treatment in the subsequent stage.
- the number of the second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m and 1.00 ⁇ m or more and 5.00 ⁇ m or less does not change much before and after the solution treatment and after the second aging treatment. Can be evaluated.
- second phase particles having a diameter exceeding 5.00 ⁇ m are present, precipitation of fine second phase particles is hindered and a precipitation strengthening effect cannot be obtained. Therefore, preferably 1 particle / mm 2 or less, more preferably 0.01 particles. / Mm 2 or less.
- the second phase particles of 0.05 ⁇ m or more and less than 0.20 ⁇ m 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 ⁇ m 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.
- 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.
- 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, homogenization heat treatment and hot rolling are performed after casting, but the homogenization heat treatment may be heating in hot rolling (in this specification, heating performed in homogenization heat treatment and hot rolling).
- 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 1000 ° C. or lower.
- the heating time depends on the plate thickness, it is preferably 30 to 500 minutes, and 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 5 to 100 ° C./min, more preferably 5 to 50 ° C./min.
- the second phase particles having a diameter of 0.20 ⁇ m to 5.00 ⁇ m finally precipitate in the target range.
- 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 10 h, but may be 15 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 preferred treatment time is 30 to 500 s, more preferably 60 to 200 s.
- the adjusted second phase particles remain and prevent the crystal grain size from increasing, while the finely precipitated Co and Si are sufficiently dissolved in the subsequent second 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.
- the Co and Si contents are lower than those of the present invention, or when the steel is 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.
- 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 900 ° C., so only a short heat treatment of about 30 seconds can be performed.
- 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 500 ° 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.
- 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.
- An ingot having a thickness of 30 mm was cast into a molten metal made of electrolytic copper, Si, and Co while changing the amount and type of the additive element. 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, followed by aging heat treatment for 15 hours, followed by solution treatment with appropriately changing temperature and time, cooling at the cooling temperature in the table, and 1 to 15 at the 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.
- 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.
- Observation magnifications are (a) 5 ⁇ 10 4 times for 0.05 ⁇ m or more and less than 0.20 ⁇ m, (b) 1 ⁇ 10 4 times for 0.20 ⁇ m or more and less than 1.00 ⁇ m, (c) 1.00 ⁇ m or more to 5.00 ⁇ m Less than is 1 ⁇ 10 3 times.
- the average crystal grain size was measured by a cutting method in accordance with JIS H0501.
- 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).
- 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 out in the rolling parallel direction, and average values were obtained.
- Tables 1 to 3 show the results.
- the particle size of Table 3 represents 50 nm or more and less than 200 nm, 200 nm or more and less than 1000 nm, and 1000 nm or more and 5000 nm or less. Second phase particles exceeding 5000 nm (5.00 ⁇ m) could not be confirmed. Since the number decreases logarithmically as the diameter increases, the number of display digits is changed.
- Examples 1 to 6 were excellent in electrical conductivity, strength, bending workability with a thick plate, and suitable for a movable connector capable of increasing current.
- Reference Invention Example 1 has the same conditions as in Example 2, but after the solution treatment, it was cooled at the cooling temperature in the table, and finished to a final thickness of 0.3 mm by final cold rolling, at the temperature in the table. The aging treatment was performed and the tempered strain relief annealing was performed. Although the strength was slightly inferior to that of Example 2, the bendability was slightly improved.
- Comparative Example 8 has a low Co concentration and a high cooling rate after hot working, and the number of second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m is also the number of second phase particles of 1.00 to 5.00 ⁇ m.
- the crystal grain size is the upper limit.
- the solution treatment time is relatively short and the amount of solid solution is small, the strength is relatively low. In order to compensate for this, the degree of processing was increased to ensure the strength, but the bending workability was inferior.
- the Co concentration is low and the strength is low.
- Comparative Example 10 since the solution temperature is too high, the second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m have disappeared during the solution heat treatment, and thus the effect of suppressing crystal growth cannot be exhibited. Poor bendability.
- Comparative Example 11 the Co / Si ratio is low, and in Comparative Example 12, the Co / Si ratio is high. In either case, the precipitation strengthening action by the fine second phase particles cannot be obtained, and the solid solution concentration of Co or Si becomes high. Also inferior.
- Comparative Example 13 since the cooling rate after hot working was too slow, the number of second phase particles having a diameter of 1.00 to 5.00 ⁇ m increased, and the bendability was poor.
- Comparative Example 14 the cooling rate after hot working is high, the number of second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m is small, and the number of second phase particles having a diameter of 1.00 to 5.00 ⁇ m is small. The effect of suppressing the resistance cannot be exhibited and the bendability is poor.
- Comparative Example 15 the cooling rate after hot working was increased, but the first aging treatment was performed at a high temperature to precipitate second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m. Since the number of second phase particles of 0.000 to 5.00 ⁇ m is small and the crystal grain size is increased by heating in the first aging treatment, the bendability is poor.
- Comparative Example 16 Since Comparative Example 16 has a higher hot heating temperature and solution treatment temperature than Example 4, the effect of suppressing crystal growth cannot be exhibited, the bendability is poor, and the conductivity is also lower than Example 4. Since Comparative Example 17 has a lower solution treatment temperature and a faster cooling temperature after solution treatment as compared to Example 7, the second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m and diameters of 1.00 to 5. The number of second phase particles of 00 ⁇ m is large, the bendability is poor, and the strength is low compared to Example 7. In Comparative Example 18, the Co concentration was high, the solution treatment temperature was high, and it was necessary to lengthen the time.
- the number of second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m was large, and the bendability was poor.
- Comparative Example 19 since the Co concentration was high and the solution treatment temperature and the hot working temperature were the same, the effect of suppressing the growth of the crystal grain size could not be exhibited, and the second phase having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m.
- the number of particles is small, the number of second phase particles having a diameter of 1.00 to 5.00 ⁇ m is large, and bendability is poor.
- the relationship between the steps of the production method and the disappearance and precipitation of the second phase particles is as follows.
- the additive element dissolves in the copper.
- second phase particles of 0.05 ⁇ m or more are precipitated.
- the second phase particles of 0.05 ⁇ m or more are not precipitated, and a large amount of second phase particles of less than 0.05 ⁇ m are precipitated.
- the second phase particles having a size of less than 0.20 ⁇ m disappear by solid solution treatment with the temperature adjusted.
- (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.
- 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.
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Abstract
Description
従来、導電性を劣化させずに高い強度が達成できる特性を有する析出強化型銅合金として、Cu-Ni-Si系銅合金、Cu-Co-Si系やCu-Ni-Co-Si系銅合金が知られている。これら銅合金を製造するには、溶体化処理で添加元素を固溶させた後、冷間圧延、時効熱処理によりマトリックス中に第2相粒子としてNi2SiやCo2Si等を析出又は晶析させている。しかし、Ni2Siの固溶量は比較的大きいため、60%IACS以上の導電率はCu-Ni-Si系銅合金では達成することが難しい。そのため、固溶量が低いCo2Siを主要析出物として有し、高い導電性を示すCu-Co-Si系やCu-Ni-Co-Si系合金が研究されている。これら銅合金は、充分に固溶させてから微細析出物を析出させないと、目標とする強度を達成できない。しかし、高温で溶体化すると結晶が粗大化し、曲げ加工性が悪くなる等の問題が生じるため、種々の対策が検討されてきた。
特許文献3では、溶体化温度、溶体化処理後の冷却速度、時効熱処理温度によって結晶粒径を10μm以下に制御しているが、この手法では1.5質量%以上にCoを固溶させることが出来ず目的とする強度が得られない。
このように、従来の析出強化型銅合金はリードフレーム等の電子部品への薄板利用を目的としてきたため、0.3mm程度の厚板における優れた曲げ加工性は検討されていなかった。
(1)1.5~2.5wt%のCo、0.3~0.7wt%のSi並びに残部はCu及び不可避的不純物よりなり、Co/Siの元素比は3.5~5.0であるCu-Co-Si合金材であり、直径0.20μm以上1.00μm未満の第2相粒子を3,000~150,000個/mm2含有し、導電率ECが60%IACS以上であり、結晶粒径が10μm以下である、良好な曲げ加工性を有する銅合金材。
(2)直径1.00μm以上5.00μm以下の第2相粒子を10~1,000個/mm2含有する(1)の銅合金材。
(3)0.2%耐力YSが600MPa以上である(1)又は(2)の銅合金材。
(4)鋳造後、溶体化処理前に行われる熱間加熱の温度が、下記で選択された溶体化処理温度から45℃以上高い温度であり、熱間圧延開始時温度から600℃までの冷却速度が100℃/分以下であり、溶体化処理温度は、(50×Cowt%+775)℃以上(50×Cowt%+825)℃以下の範囲で選択される、(1)~(3)いずれか記載の銅合金材の製造方法。
(5)溶体化処理後の時効処理は、450~650℃で1~20時間である(4)記載の銅合金材の製造方法。
本発明の合金材は、1.5~2.5wt%(以下特記しない限り%で示す)、好ましくは1.7~2.2%のCoを含有し、0.3~0.7%、好ましくは0.4~0.55%のSiを含有する。好ましくは残部はCu及び不可避的不純物よりなるが、本発明の構成が目的とする効果を達成できる範囲内において、当業者が通常銅合金へ添加する成分として採用する種々の元素、例えばCr、Mg、Mn、Ni、Sn、Zn、P、Agなどを更に含んでも良い。
含有されるCo/Siの化学量論比は、理論的には4.2であるが、実際には3.5~5.0、好ましくは3.8~4.6であり、その範囲内であると析出強化及び結晶粒径調整に適した第2相粒子Co2Siが形成される。Co及び/又はSiが少なすぎると析出強化効果が少なく、多すぎると固溶されず導電性にも劣る。第2相粒子Co2Siが析出すると、析出強化効果が表れ、析出後はマトリックス純度が高くなるため導電性が向上する。更に、特定サイズの第2相粒子が特定量存在すると、結晶粒子の成長が阻まれ結晶粒径を10μm以下にすることができる。
本発明の合金材の結晶粒径は10μm以下である。10μm以下であると良好な曲げ加工性が達成できる。
本発明の銅合金材は、例えば板材、条材、線材、棒材、箔などの種々の形状を有してもよく、可動コネクタ用板材又は条材でもよいが特に限定されるものではない。
本発明の第2相粒子とは、銅に他の元素が含まれる場合に生成し、銅母相(マトリックス)とは異なる相を形成する粒子をいう。直径50nm以上の第2相粒子の数は、機械研磨にて鏡面仕上げした後、電解研磨や酸洗エッチングをした銅板圧延平行断面(圧延面に平行、かつ厚み方向に平行な面)を任意に5箇所選択して得られた1視野の走査電子顕微鏡写真(図1参照)から該当する直径範囲の粒子数を測定して得られる。ここで、直径とは、図2のように粒子の短径(L1)と長径(L2)を測定し、L1とL2の平均値をいう。
本発明の第2相粒子の大部分はCo2Siであるが、Ni2Si等の他の金属間化合物も直径が範囲内であればよい。第2相粒子を構成する元素は、例えば、FE-SEM(日本FEI株式会社型式XL30SFEG)に付属のEDXを使用して確認できる。
又、直径1.00μm以上5.00μm以下の第2相粒子は、好ましくは10~1,000個/mm2、更に好ましくは20~500個/mm2、最も好ましくは30~400個/mm2含有され、熱間加熱した後の冷却速度を遅くして析出し、必要であれば第1時効処理することで粒径が調整できる。上記好ましい範囲は0.20μm以上1.00μm未満の第2相粒子の数にも連動する。この範囲であると高温溶体化が可能であり、溶体化処理での結晶粒径の成長が抑制される一方、充分に固溶されたCo及びSiが後段の(第2)時効処理により微細析出されて、高強度、高導電性、良好な曲げ加工性を達成することができる。しかし、1,000個/mm2を超えると曲げ性が低下するため好ましくない。
上記直径0.20μm以上1.00μm未満及び1.00μm以上5.00μm以下の第2相粒子の数は、溶体化処理前後及び第2時効処理後も余り変動しないので最終圧延前の試験片で評価できる。
0.05μm以上0.20μm未満の第2相粒子は、熱間圧延、その後の冷却、第1時効処理中に析出するが、溶体化処理でほとんど固溶してしまい、その後の冷却及び(第2)時効処理により析出する。0.05μm未満の第2相粒子は、溶体化処理で固溶し、(第2)時効処理により大量に析出する。従って、これらの第2相粒子は、結晶粒径の調整効果は無いが強度向上に寄与する。
本発明の合金材の導電率ECは、60%IACS以上、好ましくは65%IACS以上である。この範囲であると高電流化可能な部品が製造できる。
本発明で良好な曲げ加工性とは、0.3mm厚板で最小曲げ半径MBR/tが0.5以下(Bad Way)をいう。0.3mm厚板でMBR/tが0.5以下であると、電子部品、特に可動コネクタの製造、使用時に求められる特性を満たす。なお、本発明の合金材を0.3mm厚よりも薄くした場合にはさらに良好な曲げ加工性が得られる。
本発明の合金材の0.2%耐力YSは、好ましくは600MPa以上であり、更に好ましくは650MPa以上であり、引張り強さTSは好ましくは630MPa以上、更に好ましくは660MPa以上である。上記範囲内であると、特に可動コネクタ用板材等の電子部品用材料として充分である。
本発明の合金材の製造方法工程は、通常の析出強化型銅合金と同様であり、溶解鋳造→(均質化熱処理)→熱間圧延→冷却→(第1時効処理)→面削→冷間圧延→溶体化処理→冷却→(冷間圧延)→第2時効処理→最終冷間圧延→(調質歪取焼鈍)である。なお、括弧内の工程は省略可能であり、最終冷間圧延は時効熱処理前に行っても良い。
本発明では、鋳造後に均質化熱処理及び熱間圧延が行われるが、均質化熱処理は熱間圧延における加熱でもよい(なお、本件明細書では、均質化熱処理及び熱間圧延の際に行われる加熱を「熱間加熱」と総称する)。
熱間加熱の温度は、添加元素がほぼ固溶する温度であれば良く、具体的には下記で選択された溶体化処理温度から40℃以上、好ましくは45℃以上高温であると良い。熱間加熱の温度上限は、金属組成及び設備により個々に規定されるが通常は1000℃以下である。加熱時間は板厚みにもよるが、好ましくは30~500分、更に好ましくは60~240分である。熱間加熱時にはCoやSi等の添加元素はほとんど溶解することが好ましい。
熱間加熱後の冷却速度は、5~100℃/min、更に好ましくは5~50℃/minである。この冷却速度であると最終的に直径0.20μm~5.00μmとなる第2相粒子が目的の範囲で析出する。しかし、従来は第2相粒子の粗大化抑制を目的として水冷シャワー等で急冷されていたため微細な第2相粒子しか析出していなかった。
冷却後、材料は面削されるが、更に任意で第1時効処理を行うと目的の第2相粒子のサイズ、数を調整できるので好ましい。この第1時効処理の条件は、好ましくは600~800℃で30s~10hであるが15hでもよい。
溶体化処理後の好ましい冷却速度は、10℃/s以上である。この冷却速度を下回ると冷却中に第2相粒子が析出し、固溶量が低下する。冷却速度の好ましい上限は特にないが、一般に採用されている設備であると、例えば、100℃/s程度でも可能である。
本発明よりCo及びSi含有量が低かったり、熱間圧延後に徐冷されず、第2時効処理加熱もされない場合、溶体化処理前に析出している第2相粒子は少ない。析出第2相粒子が少ない合金を溶体化処理する場合、900℃を超える高温で1分を超える溶体化処理時間では結晶粒径が粗大化してしまうため、30秒程度の短時間の熱処理しかできず、実際に固溶可能な量が少ないため、充分な析出強化効果を得ることができない。
最終圧延加工度は、好ましくは5~40%、更に好ましくは10~20%である。5%未満であると、加工硬化による強度の上昇が不足し、一方、40%を超えると曲げ加工性が低下する。
また、最終冷間圧延を第2時効熱処理前に行う場合には、第2時効熱処理を450℃~600℃で1~20時間行えばよい。
歪取焼鈍温度は、好ましくは250~600℃であり、焼鈍時間は好ましくは10s~1時間である。この範囲であると第2相粒子のサイズ、数に変化はなく、結晶粒径も変わらない。
電気銅、Si、Coを原料とした溶湯に、添加元素の量、種類を変更して添加し、厚みが30mmのインゴットを鋳造した。このインゴットを表中の温度で3時間(熱間)加熱し、熱間圧延により厚み10mmの板にした。次に、表面の酸化スケールを研削除去し、15時間時効熱処理し、その後、温度、時間を適宜変更した溶体化処理を行い、表中の冷却温度で冷却し、表中の温度で1~15時間時効熱処理を行い、最終の冷間圧延で最終厚みを0.3mmに仕上げた。歪取焼鈍時間は1分である。
銅合金母地中の添加元素の濃度を、面削工程後のサンプルを使用してICP-質量分析法で分析した。
第2相粒子の直径及び個数は、最終冷間圧延前のサンプル圧延平行断面を機械研磨して鏡面に仕上げた後、電解研磨や酸洗エッチングをし、走査電子顕微鏡を用いて各倍率の顕微鏡写真5枚に対して行った。観察倍率は、(a)0.05μm以上0.20μm未満は5×104倍、(b)0.20μm以上1.00μm未満は1×104倍、(c)1.00μm以上5.00μm未満は1×103倍である。
結晶粒径は、JIS H0501に従い切断法にて平均結晶粒径を測定した。
導電率ECは、20℃(±0.5℃)に保たれた恒温槽中で四端子法により比抵抗を計測した(端子間距離50mm)。
0.2%耐力YS及び引張強さTSは、圧延平行方向に切り出したJIS Z2201-13B号のサンプルをJIS Z 2241に準じて3回測定して平均値を求めた。
実施例1~6は本発明の要件を満たすため、優れた導電性、強度、厚板での曲げ加工性を備え、高電流化可能な可動コネクタに適する材料であった。参考発明例1は、実施例2と同様の条件であるが、溶体化処理後、表中の冷却温度で冷却し、最終冷間圧延で最終厚みを0.3mmに仕上げ、表中の温度で時効処理を行い、調質歪取焼鈍したものであり、実施例2と比較して若干強度が劣るものの若干曲げ性が向上している。
比較例10は、溶体化温度が高すぎるので直径0.20μm以上1.00μm未満の第2相粒子が溶体化熱処理中に消滅してしまったため、結晶の成長を抑制する効果が発揮できず、曲げ性が悪い。
比較例11はCo/Si比が低く、比較例12はCo/Si比が高く、いずれも微細第2相粒子による析出強化作用を得られず、Co又はSiの固溶濃度が高くなるため導電性も劣る。
比較例13は熱間加工後の冷却速度が遅すぎたため、直径1.00~5.00μmの第2相粒子が多くなり、曲げ性が悪い。
比較例14は、熱間加工後の冷却速度が速く、0.20μm以上1.00μm未満の第2相粒子個数も直径1.00~5.00μmの第2相粒子個数も少なく、結晶の成長を抑制する効果が発揮できず、曲げ性が悪い。比較例15でも同様に、熱間加工後の冷却速度を速くしたが、第1時効処理を高温で行い、直径0.20μm以上1.00μm未満の第2相粒子を析出させたが、直径1.00~5.00μmの第2相粒子個数が少なく、かつ第1時効処理の加熱で結晶粒径が大きくなったため、曲げ性が悪い。
比較例16は実施例4に比べ、熱間加熱温度及び溶体化処理温度が高いため、結晶の成長を抑制する効果が発揮できず、曲げ性が悪く導電性も実施例4に比べ低い。
比較例17は実施例7に比べ、溶体化処理温度が低く、溶体化処理後の冷却温度が早いため、直径0.20μm以上1.00μm未満の第2相粒子及び直径1.00~5.00μmの第2相粒子個数が多く、曲げ性が悪く強度も実施例7に比べ低い。
比較例18はCo濃度が高く、溶体化処理温度が高く時間も長くする必要があったため直径0.20μm以上1.00μm未満の第2相粒子個数が多く、曲げ性が悪い。
比較例19はCo濃度が高く、溶体化処理温度と熱間加工温度が同じだったため、結晶粒径の成長を抑制する効果が発揮できず、直径0.20μm以上1.00μm未満の第2相粒子個数が少なく直径1.00~5.00μmの第2相粒子個数が多く、曲げ性が悪い。
表3に、(a)0.05μm以上0.20μm未満、(b)0.20μm以上1.00μm未満、(c)1.00μm以上5.00μm未満の第2相粒子が製造工程においてどのように変化するか測定した結果を示す。表3より(a)~(c)について下記が認められる。
(a)は本発明の溶体化処理条件であると固溶して5分の1から10分の1程度の数になり、第2時効処理後では数にあまり変動はない。(b)は本発明の溶体化処理条件及び第2時効処理条件であると数がほとんど増減しない。(c)は本発明の熱間加熱、冷却条件であると、溶体化処理前も最終冷間圧延前も数が全く変化しない。
Claims (5)
- 1.5~2.5wt%のCo、0.3~0.7wt%のSi並びに残部はCu及び不可避的不純物よりなり、Co/Siの元素比は3.5~5.0であるCu-Co-Si合金材であり、直径0.20μm以上1.00μm未満の第2相粒子を3,000~150,000個/mm2含有し、導電率ECが60%IACS以上であり、結晶粒径が10μm以下である、良好な曲げ加工性を有する銅合金材。
- 直径1.00μm以上5.00μm以下の第2相粒子を10~1,000個/mm2含有する請求項1の銅合金材。
- 0.2%耐力YSが600MPa以上である請求項1記載の銅合金材。
- 鋳造後、溶体化処理前に行われる熱間加熱の温度が、下記で選択された溶体化処理温度から45℃以上高い温度であり、熱間圧延開始時温度から600℃までの冷却速度が100℃/分以下であり、溶体化処理温度は、(50×Cowt%+775)℃以上(50×Cowt%+825)℃以下の範囲で選択される、請求項1~3いずれか1項記載の銅合金材の製造方法。
- 溶体化処理後の時効処理は、450~650℃で1~20時間である請求項4記載の銅合金材の製造方法。
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Also Published As
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US20130019997A1 (en) | 2013-01-24 |
JP2011208232A (ja) | 2011-10-20 |
TWI432586B (zh) | 2014-04-01 |
US9076569B2 (en) | 2015-07-07 |
TW201139704A (en) | 2011-11-16 |
CN102812139B (zh) | 2014-10-29 |
EP2554692A1 (en) | 2013-02-06 |
EP2554692B1 (en) | 2016-11-16 |
EP2554692A4 (en) | 2014-04-09 |
JP4620173B1 (ja) | 2011-01-26 |
CN102812139A (zh) | 2012-12-05 |
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