WO2012026488A1 - 電子材料用Cu-Co-Si系合金 - Google Patents
電子材料用Cu-Co-Si系合金 Download PDFInfo
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- WO2012026488A1 WO2012026488A1 PCT/JP2011/069043 JP2011069043W WO2012026488A1 WO 2012026488 A1 WO2012026488 A1 WO 2012026488A1 JP 2011069043 W JP2011069043 W JP 2011069043W WO 2012026488 A1 WO2012026488 A1 WO 2012026488A1
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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
- 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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon 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
- 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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
Definitions
- the present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Co—Si alloy suitable for use in various electronic parts.
- Copper alloys for electronic materials used in various electronic parts such as connectors, switches, relays, pins, terminals, and lead frames are required to have both high strength and high conductivity (or thermal conductivity) as basic characteristics. Is done.
- high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.
- the copper alloy used for movable connectors and the like has been increased in current, and in order not to increase the size of the connector, it has good bendability even if it is thickened (0.3 mmt or more), A conductivity of 60% (65) IACS or higher and a 0.2% proof stress of about 650 MPa or higher are desired.
- a Cu—Ni—Si alloy generally called a Corson copper alloy is conventionally known.
- the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
- a Cu—Co—Si alloy has attracted attention.
- the Cu—Co—Si based alloy has an advantage that it can be made higher in conductivity than the Cu—Ni—Si based copper alloy because the amount of cobalt silicide (Co 2 Si) solid solution is small.
- Processes that greatly affect the properties of Cu-Co-Si-based copper alloys include solution treatment, aging treatment, and final rolling work degree. Among these, aging conditions depend on the distribution and size of cobalt silicide precipitates. This is one of the processes that greatly affects.
- Patent Document 1 Japanese Patent Laid-Open No. 9-20943 describes a Cu—Co—Si based alloy developed for the purpose of realizing high strength, high conductivity, and high bending workability.
- a method for producing a copper alloy 85% or more cold rolling is performed after hot rolling, annealing is performed at 450 to 480 ° C. for 5 to 30 minutes, cold rolling is performed at 30% or less, and further at 450 to 500 ° C. A method of performing an aging treatment for 30 to 120 minutes is described.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-55977 describes a Cu—Co—Si based alloy that focuses on the size and total amount of inclusions precipitated in the copper alloy as well as the composition of the copper alloy. It describes that after the solution treatment, an aging treatment is performed by heating at 400 ° C. to 600 ° C. for 2 hours to 8 hours.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2009-242814 discloses Cu—Co—Si as a precipitation-type copper alloy material that can stably realize a high conductivity of 50% IACS or more, which is difficult to achieve with a Cu—Ni—Si system.
- System alloys are exemplified.
- aging treatment is performed at 400 to 800 ° C. for 5 seconds to 20 hours, followed by cold rolling at 50 to 98%, solution treatment at 900 to 1050 ° C., and aging heat treatment at 400 to 650 ° C. The method of doing is described.
- Patent Document 4 (WO2009-096546) describes a Cu—Co—Si alloy characterized in that the size of a precipitate containing both Co and Si is 5 to 50 nm. It is described that the aging treatment after the solution recrystallization heat treatment is preferably performed at 450 to 600 ° C. for 1 to 4 hours.
- Patent Document 5 (WO 2009-116649) describes a Cu—Co—Si alloy having excellent strength, electrical conductivity, and bending workability.
- the aging treatment is performed at 525 ° C. ⁇ 120 minutes
- the rate of temperature rise from room temperature to the maximum temperature is in the range of 3 to 25 ° C./min
- the temperature drop is up to 300 ° C. Describes that cooling was performed in the furnace at a rate of 1 to 2 ° C./min.
- Patent Document 6 (WO2010-016428) describes that the strength, conductivity, and bending workability of a Cu—Co—Si alloy can be improved by adjusting the Co / Si ratio to 3.5 to 4.0. Is described.
- the aging heat treatment to be performed after the recrystallization heat treatment is performed under heating conditions of a temperature of 400 to 600 ° C. for 30 to 300 minutes (525 ° C. ⁇ 2 hours in the examples), a temperature rising rate of 3 to 25 K / min, It is described that the temperature lowering rate is 1 to 2 K / min.
- the result is ⁇ and GW is ⁇ , but BW also includes a result of ⁇ , and an accurate R / t cannot be evaluated.
- the evaluation thickness is as thin as 0.2 mmt, and it cannot cope with the increase in thickness such as 0.3 mmt.
- an object of the present invention is to provide a Cu—Co—Si alloy having an improved balance of conductivity, strength, and bending workability by improving the precipitation state of the second phase particles.
- the present invention completed on the basis of the above knowledge includes, in one aspect, 0.5 to 3.0 mass% of Co and 0.1 to 1.0 mass% of Si, with the balance being Cu and inevitable impurities.
- a second phase having a Co / Si mass% ratio (Co / Si) of 3.5 ⁇ Co / Si ⁇ 5.0 and a grain size in the range of 1 to 50 nm in a cross section parallel to the rolling direction.
- the copper alloy for electronic materials has an average particle diameter of 2 to 10 nm and an average distance between the second phase particles of 10 to 50 nm.
- the average crystal grain size in a cross section parallel to the rolling direction is 3 to 30 ⁇ m.
- the copper alloy for electronic materials according to the present invention is a group consisting of Ni, Cr, Sn, P, Mg, Mn, Ag, As, Sb, Be, B, Ti, Zr, Al, and Fe. At least one kind of alloy element selected from the above, and the total amount of the alloy elements is 2.0% by mass or less.
- a copper drawn product obtained by processing the copper alloy for electronic materials according to the present invention.
- the present invention in still another aspect is an electronic component comprising the copper alloy for electronic materials according to the present invention.
- a Cu—Co—Si based alloy having an improved balance of strength, conductivity, and bending workability can be obtained.
- FIG. 4 is a graph plotting the relationship between conductivity (EC) and 0.2% proof stress (YS) for 34-39.
- FIG. 4 is a graph plotting the relationship between conductivity (EC) and 0.2% proof stress (YS) for 40-41.
- FIG. 4 is a graph plotting the relationship between conductivity (EC) and 0.2% proof stress (YS) for 42-43.
- the boundary line of the favorable conditions for aging treatment was graphed with the x-axis being the material holding temperature (° C.) and the y-axis being the holding time (h) at the holding temperature.
- the copper alloy for electronic materials according to the present invention contains Co in an amount of 0.5 to 3.0% by mass and Si in an amount of 0.1 to 1.0% by mass with the balance being Cu and inevitable impurities. And a mass% ratio (Co / Si) of Si is 3.5 ⁇ Co / Si ⁇ 5.0.
- the amount of Co added is set to 0.5 to 3.0% by mass.
- a preferable amount of Co added is 0.7 to 2.0% by mass.
- the addition amount of Si is too small, the strength required as an electronic component material such as a connector cannot be obtained.
- the addition amount is too large, the decrease in conductivity is remarkable. Therefore, the content is set to 0.1 to 1.0% by mass.
- a preferable addition amount of Si is 0.15 to 0.6% by mass.
- the mass ratio of Co and Si As for the mass ratio of Co and Si (Co / Si), the composition of cobalt silicide, which is the second phase particle that leads to the improvement of strength, is Co 2 Si, and the mass ratio of 4.2 improves the characteristics most efficiently. obtain. If the mass ratio of Co and Si is too far from this value, any element will be present in excess, but the excess element is not appropriate because it does not lead to an increase in strength or a decrease in conductivity. . Therefore, in the present invention, the mass% ratio of Co and Si is 3.5 ⁇ Co / Si ⁇ 5.0, and preferably 3.8 ⁇ Co / Si ⁇ 4.5.
- the total amount of alloy elements is 2.0 mass% at the maximum, preferably 1.5 mass% at the maximum because a decrease in electrical conductivity and a deterioration in manufacturability become remarkable when it becomes excessive.
- the total amount of the alloy elements is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more.
- the alloy element content is preferably 0.5% by mass at the maximum for each alloy element. This is because if the amount of each alloy element exceeds 0.5% by mass, the above effect is not further promoted, and the decrease in conductivity and the deterioration in manufacturability become remarkable.
- second phase particle refers to all particles having a composition different from that of the parent phase.
- second phase particles composed of an intermetallic compound of Co and Si (cobalt silicide), Co and In addition to Si, second phase particles containing other additive elements and inevitable impurities are also included.
- the average particle diameter and the average distance between the particles are defined.
- the average particle diameter of the second phase particles having a particle diameter in the range of 1 to 50 nm in a cross section parallel to the rolling direction tends to be insufficient when it is too large, and conversely is too small. There is a tendency that sufficient conductivity cannot be obtained. Therefore, the average particle size is preferably controlled to 2 to 10 nm, more preferably 2 to 5 nm. It is also important to control not only the average particle diameter but also the average distance between the second phase particles. When the average distance between the second phase particles is reduced, high strength is obtained, and the average distance between the second phase particles is preferably 50 nm or less, and more preferably 30 nm or less. The lower limit is 10 nm from the amount of additive element that can be precipitated and the diameter of the precipitate.
- the average particle size of the second phase particles is measured by the following procedure. Photographed with a transmission electron microscope at a magnification of 1 million to contain 100 or more second phase particles of 1 to 50 nm, the major axis of each particle was measured, and the value obtained by dividing the total by the number of particles was the average particle size. To do.
- the major axis means the length of a line segment connecting two farthest points on the particle outline in each second phase particle in the observation field.
- the average distance between the second phase particles is measured by the following procedure. Photographed with a transmission electron microscope at 1 million magnification to contain 100 or more second phase particles of 1 to 50 nm, and the number of second phase particles in the observation field ⁇ (observation area ⁇ sample thickness) to the 1/3 power Is required.
- Crystal grain size The crystal grains affect the strength, and the Hall Petch rule that the strength is proportional to the ⁇ 1/2 power of the crystal grains generally holds, so that the crystal grains are preferably smaller.
- the precipitation strengthening type alloy it is necessary to pay attention to the precipitation state of the second phase particles.
- the second phase particles precipitated in the crystal grains contribute to the strength improvement, but the second phase particles precipitated in the crystal grain boundaries hardly contribute to the strength improvement. Therefore, the smaller the crystal grain, the higher the rate of grain boundary reaction in the precipitation reaction, so the grain boundary precipitation that does not contribute to strength improvement becomes dominant, and when the crystal grain size is less than 3 ⁇ m, the desired strength can be obtained. Can not.
- the average crystal grain size is preferably 3 to 30 ⁇ m. Furthermore, the average crystal grain size is more preferably controlled to 5 to 15 ⁇ m from the viewpoint of achieving both high strength and good bending workability.
- the Cu—Co—Si based alloy according to the present invention can have a 0.2% proof stress (YS) of 500 to 600 MPa and a conductivity of 65 to 75% IACS, preferably 0
- the 2% proof stress (YS) can be 600 to 650 MPa and the electrical conductivity can be 65 to 75% IACS, more preferably the 0.2% proof stress (YS) is 650 MPa or more and the electrical conductivity is It can have 65% IACS or higher.
- the Cu—Co—Si alloy according to the present invention is subjected to a W-bending test of Badway (bending axis is the same as the rolling direction) using a W-shaped mold at a thickness of 0.3 mm.
- the MBR / t which is a value obtained by dividing the minimum bending radius (MBR) at which a crack does not occur in the bent portion by the plate thickness (t), can be 1.0 or less, preferably 0.5 or less. More preferably 0.1 or less.
- the copper alloy according to the present invention can be manufactured by adopting the manufacturing process of the Corson alloy except that some processes are devised.
- This aging treatment increases strength and conductivity.
- Cold rolling is performed after aging, and then strain relief annealing is performed. Between the above steps, grinding, polishing, shot blast pickling and the like for removing oxide scale on the surface are appropriately performed.
- the order of cold rolling and aging treatment may be used.
- the hot rolling is preferably performed after heating at a material temperature of 950 ° C. to 1070 ° C. for 1 hour or longer, and preferably for 3 to 10 hours in order to form a more homogeneous solid solution.
- the temperature condition of 950 ° C. or higher is a higher temperature setting than other Corson alloys. If the holding temperature before hot rolling is less than 950 ° C, solid solution is insufficient, and if it exceeds 1070 ° C, the material may be dissolved.
- the temperature at the end of hot rolling is preferably 850 ° C. or higher. Therefore, the material temperature during hot rolling is preferably in the range of 600 ° C. to 1070 ° C., more preferably in the range of 850 to 1070 ° C. In the cooling process after completion of hot rolling, it is preferable to suppress the precipitation of the second phase particles by increasing the cooling rate as much as possible. There is water cooling as a method for speeding up the cooling.
- solution treatment is performed after repeating annealing (including aging treatment and recrystallization annealing) and cold rolling as appropriate.
- the solution treatment temperature is set to 850 ° C. to 1050 ° C., and the second phase particles are dissolved.
- the cooling after the solution treatment is also fast, and specifically, it is desirable to set it to 10 ° C./sec or more.
- the appropriate time during which the material temperature is maintained at the maximum temperature varies depending on the Co and Si concentrations and the maximum temperature, but it is typical in order to prevent grain coarsening due to recrystallization and subsequent crystal growth.
- the time during which the material temperature is maintained at the maximum temperature is controlled to 480 seconds or less, preferably 240 seconds or less, and more preferably 120 seconds or less.
- the number of coarse second-phase particles may not be reduced if the time during which the material temperature is maintained at the maximum temperature is too short, it is preferably 10 seconds or more, and 30 seconds or more. More preferably.
- An aging treatment is performed after the solution treatment step.
- the rate of temperature increase is given by (holding temperature ⁇ 350 ° C.) / (Time required for the material temperature to rise from 350 ° C. to the holding temperature).
- the holding temperature (° C.) of the material is x and the holding time (h) at the holding temperature is y, the following formula: 4.5 ⁇ 10 16 ⁇ exp ( ⁇ 0.075x) ⁇ y ⁇ 5.
- the holding temperature and holding time are set so as to satisfy 6 ⁇ 10 18 ⁇ exp ( ⁇ 0.075 ⁇ ).
- the aging treatment is preferably performed at a holding temperature and a holding time so as to satisfy the following formula: 4.5 ⁇ 10 16 ⁇ exp ( ⁇ 0.075x) ⁇ y ⁇ 7.1 ⁇ 10 17 ⁇ exp ( ⁇ 0.075x) Set.
- the average particle diameter of the second phase particles tends to fall within 2 to 5 nm.
- the above equation is represented in a graph with the x-axis being the material holding temperature (° C.) and the y-axis being the holding time (h) at the holding temperature.
- an improvement in conductivity can be expected by lowering the temperature lowering rate when the material temperature is lowered from the holding temperature to 350 ° C.
- it is set to 5 to 200 ° C./h, preferably 10 to 150 ° C./h, more preferably 20 to 100 ° C./h.
- the temperature lowering rate is given by (holding temperature ⁇ 350 ° C.) / (Time required for the temperature of the material to drop from the holding temperature to 350 ° C. after the start of temperature lowering).
- the temperature difference between the stages is 20 ° C. to 100 ° C.
- the holding time of each stage is 3 to 20 hours
- the multi-stage aging is performed toward the low temperature side. Is preferably performed.
- the temperature difference between the stages was set to 20 ° C. to 100 ° C. The reason is that if the temperature difference is less than 20 ° C., the second phase particles grow too much and the strength decreases, while if the temperature difference exceeds 100 ° C., precipitation occurs. This is because the speed is too slow and the effect is small.
- the temperature difference between the stages is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.
- the second-stage aging treatment can be performed at 380 to 460 ° C., which is a holding temperature lower by 20 to 100 ° C. The same applies to the third and subsequent stages.
- the distribution state of the second phase particles hardly changes even when the aging treatment is performed at a holding temperature of less than 350 ° C., it is not necessary to set the number of stages of aging treatment more than necessary.
- a suitable number of stages is two or three, and three is more preferable.
- the reason why the holding time of each stage is set to 3 to 20 h is that the effect cannot be obtained if the holding time is less than 3 h, while the aging time becomes too long and the manufacturing cost increases if the holding time exceeds 20 h.
- the holding time is preferably 4 to 15 hours, more preferably 5 to 10 hours.
- the temperature decreasing rate when the material temperature decreases from the holding temperature to 350 ° C. is described above, it is preferable to perform at the same temperature decreasing rate when the material temperature is 350 ° C. or higher even when performing multistage aging.
- the temperature drop rate for multi-stage aging is (holding temperature of the first stage-350 ° C) / (time required for the material temperature to drop from the holding temperature to 350 ° C after starting the cooling after the completion of the first stage-each Retention time in the stage). That is, the temperature drop rate is calculated by subtracting the holding time in each stage from the temperature drop time.
- the rolling degree is preferably 5 to 40%.
- strain relief annealing is performed as necessary.
- the annealing temperature is preferably 300 to 600 ° C. and 5 seconds to 10 hours.
- the Cu—Si—Co based alloy of the present invention can be processed into various copper products, such as plates, strips, tubes, rods and wires, and the Cu—Si—Co based copper alloy according to the present invention is a lead. It can be used for electronic parts such as frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries.
- Example 1 A Cu—Co—Si based copper alloy containing a component concentration of Co and Si having a mass concentration shown in Table 1 and having the balance consisting of Cu and inevitable impurities is obtained at 1300 ° C. in an Ar atmosphere using a high frequency melting furnace. And cast into an ingot having a thickness of 30 mm. Next, this ingot was heated to 1000 ° C. and held for 3 hours, and then hot-rolled to a plate thickness of 10 mm. The material temperature at the end of hot rolling was 850 ° C. Then, it cooled with water. Next, the first temporary treatment was performed under conditions of a material temperature of 600 ° C. and a heating time of 10 hours.
- the first cold rolling was performed at a workability of 95% or more.
- the material temperature is 850 ° C. and the heating time is 100 seconds
- the Co concentration is 1.2% by mass
- the material temperature is 900 ° C. and the heating time is 100%.
- the heating temperature is 950 ° C. and the heating time is 100 seconds
- the heating temperature is 1000 ° C. and the heating time is 100 seconds.
- the second aging treatment was performed under the conditions described in Table 1.
- the second cold rolling was carried out under the condition of a rolling reduction of 20%, and two types, one having a plate thickness of 0.3 mm and one having a plate thickness of 0.2 mm, were obtained.
- strain relief annealing was performed under the conditions of a material temperature of 400 ° C. and a heating time of 30 seconds to obtain test pieces.
- chamfering, pickling, and degreasing were appropriately performed between each step.
- test pieces were evaluated as follows. (1) 0.2% yield strength (YS) and tensile strength (TS) A tensile test in the rolling parallel direction was performed according to JIS-Z2241, and 0.2% yield strength (YS: MPa) and tensile strength (TS); MPa were measured. (2) Conductivity (EC) The volume resistivity was measured with a double bridge, and the conductivity (EC:% IACS) was determined. (3) Average crystal grain size (GS) The test piece was resin-filled so that the observation surface had a cross section in the thickness direction parallel to the rolling direction, the observation surface was mirror-finished by mechanical polishing, and subsequently a mass concentration of 36% with respect to 100 parts by volume of water.
- the average value of 10 fields of view was taken as the measured value.
- an electropolishing method generally used in the preparation of a transmission electron microscope sample is used, but measurement may be performed by forming a thin film by FIB (Focused Ion Beam).
- No. 40 is No. 40. This is an example in which a second stage aging treatment is added to 34, but the temperature during the first stage aging treatment is low and the time is short, so that the growth of the second phase particles is insufficient and the average particle size is 2 ⁇ m or less. It became. Therefore, the balance of characteristics was inferior compared to the inventive examples.
- No. No. 41 is No. 41.
- the second aging treatment was added to 35, but the temperature during the first aging treatment was high and the time was long, so the second phase particles grew too much and the average particle size was 10 ⁇ m or more. became. Therefore, the balance of characteristics was inferior compared to the inventive examples.
- the second stage and third stage aging treatments were added to 34, but the temperature during the first stage aging treatment was low and the time was short. Was 2 ⁇ m or less. Therefore, the balance of characteristics was inferior compared to the inventive examples.
- No. No. 43 is No. 43.
- the second and third aging treatments are added to 35, but the temperature during the first aging treatment is high and the time is long, so the second phase particles grow too much and the average particle size Became 10 ⁇ m or more. Therefore, the balance of characteristics was inferior compared to the inventive examples.
- Example 2 Regarding the Cu—Co—Si based copper alloy containing the component concentrations of Co, Si and other elements shown in Table 3 and having the remaining component composition consisting of Cu and inevitable impurities, No. A test piece was produced by the same production method as in No.27. About the obtained test piece, the characteristic evaluation was performed similarly to Example 1. The results are shown in Table 4. It can be seen that the effects of the present invention can be obtained even when various elements are added.
- Example 3> For the Cu—Co—Si based copper alloy containing the component concentrations of Co and Si shown in Table 5 and having the balance consisting of Cu and unavoidable impurities, No. 1 in Example 1 until the first temporary effect treatment.
- the first cold rolling was performed at a working degree of 95% or more.
- a solution treatment was performed under conditions of a material temperature of 900 ° C. and a heating time of 100 seconds, and then water cooling.
- the second cold rolling was performed at a predetermined degree of work described in Table 5, and then a second aging treatment was performed to produce a test piece having a plate thickness of 0.2 mm and a plate thickness of 0.3 mm.
- test piece was evaluated for characteristics in the same manner as in Example 1. The results are shown in Table 6. Even if the order of the aging treatment and the cold rolling is changed, it can be seen that the effect of the present invention can be obtained by performing the aging treatment with the aging temperature lowered by the degree of work ⁇ 2 ° C.
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Abstract
Description
本発明に係る電子材料用銅合金は、Coを0.5~3.0質量%、及び、Siを0.1~1.0質量%含有し、残部がCu及び不可避的不純物からなり、Co及びSiの質量%比(Co/Si)が3.5≦Co/Si≦5.0である組成を有する。
Siは添加量が少なすぎるとコネクタなどの電子部品材料として必要とされる強度が得られない一方で、多すぎると導電率の低下が著しい。そこで0.1~1.0質量%とした。好ましいSiの添加量は0.15~0.6質量%である。
また、上記合金元素の含有量は各合金元素につき最大0.5質量%とするのが好ましい。各合金元素の添加量が0.5質量%を超えると、上記効果がそれ以上推進されないだけでなく、導電率の低下や製造性の劣化が顕著になるためである。
本発明において、「第二相粒子」とは、母相とは異なる組成を有する粒子全般を指し、Co及びSiの金属間化合物(コバルトシリサイド)で構成される第二相粒子のほか、Co及びSi以外にも他の添加元素や不可避的不純物が含まれる第二相粒子も含まれる。
また、平均粒径のみならず、当該第二相粒子同士の平均距離を制御することも重要である。第二相粒子同士の平均距離を小さくすると高い強度が得られ、第二相粒子同士の平均距離を50nm以下とするのが好ましく、30nm以下とするのがより好ましい。下限は析出し得る添加元素の量と析出物の径から10nmである。
本発明においては、第二相粒子同士の平均距離は、以下の手順によって測定する。透過電子顕微鏡にて100万倍で1~50nmの第二相粒子が100個以上含まれるように撮影し、観察視野内の第2相粒子個数÷(観察面積×試料厚み)を1/3乗することで求められる。
結晶粒は、強度に影響を与え、強度が結晶粒の-1/2乗に比例するというホールペッチ則が一般的に成り立つため、結晶粒は小さい方が好ましい。しかしながら、析出強化型の合金においては、第二相粒子の析出状態に留意する必要がある。時効処理においては結晶粒内に析出した第二相粒子は、強度向上に寄与するが、結晶粒界に析出した第二相粒子はほとんど強度向上に寄与しない。したがって、結晶粒が小さいほど、析出反応における粒界反応の割合が高くなるため、強度向上に寄与しない粒界析出が支配的となり、結晶粒径が3μm未満の場合、所望の強度を得ることができない。一方、粗大な結晶粒は、曲げ加工性を低下させる。
そこで、所望の強度および曲げ加工性を得る観点から、平均結晶粒径が3~30μmとするのが好ましい。さらに、平均結晶粒径は、高強度および良好な曲げ加工性の両立という観点から、5~15μmに制御することがより好ましい。
本発明に係るCu-Co-Si系合金は一実施形態において、0.2%耐力(YS)が500~600MPaで、且つ、導電率が65~75%IACSを有することができ、好ましくは0.2%耐力(YS)が600~650MPaで、且つ、導電率が65~75%IACSを有することができ、より好ましくは0.2%耐力(YS)が650MPa以上で、且つ、導電率が65%IACS以上を有することができる。
次に本発明に係る銅合金の製造方法に関して説明する。
本発明に係る銅合金は一部の工程に工夫を加える他は、コルソン系合金の製造工程を採用することで製造可能である。
まず、材料温度が350℃から保持温度まで到達するときの昇温速度は、高すぎると析出サイトが少ないため、第二相粒子の数が少なくなり第二相粒子の粒子間距離が大きくなりやすい。一方で、低すぎると昇温中に第二相粒子が大きくなる。そこで、10~160℃/h、好ましくは10~100℃/h、より好ましくは10~50℃/hとする。昇温速度は、(保持温度-350℃)/(材料温度が350℃から保持温度まで上昇するのに要した時間)で与えられる。
次に、材料の保持温度(℃)をx、保持温度における保持時間(h)をyとした場合に、次式:4.5×1016×exp(-0.075x)≦y≦5.6×1018×exp(-0.075x)を満たすように保持温度及び保持時間を設定する。y>5.6×1018×exp(-0.075x)となると、第二相粒子が成長し過ぎて平均粒径が10nm超となる傾向にあり、4.5×1016×exp(-0.075x)>yとなると、第二相粒子の成長が不十分で平均粒径が2nm未満になる傾向にある。
時効処理は、好ましくは次式:4.5×1016×exp(-0.075x)≦y≦7.1×1017×exp(-0.075x)を満たすように保持温度及び保持時間を設定する。当該条件で時効処理を実施すると第二相粒子の平均粒径が2~5nmに入りやすい。
図4に、上記の式を、x軸を材料の保持温度(℃)とし、y軸を保持温度における保持時間(h)としてグラフに表した。
最後に、材料温度が保持温度から350℃まで低下するときの降温速度は、低くすることで導電率の向上が見込める。ただし、低すぎると強度が低下する。そこで、5~200℃/h、好ましくは10~150℃/h、より好ましくは20~100℃/hとする。降温速度は、(保持温度-350℃)/(降温を開始した後、材料温度が保持温度から350℃まで低下するのに要した時間)で与えられる。
なお、溶体化、冷間圧延、時効処理の順で実施する場合には、時効処理前に歪が加わっており、析出速度が速いため、時効温度を加工度(%)×2℃程度下げるとよい。
詳細な条件としては、1段目の時効処理を上記条件で行った後、段間の温度差を20℃~100℃、各段の保持時時間を3~20hとして低温側に向かって多段時効を行うのが好ましい。
表1に記載の質量濃度のCo及びSiを含有し、残部がCu及び不可避的不純物からなる成分組成を有するCu-Co-Si系銅合金を、高周波溶解炉を用いてAr雰囲気中で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。
次いで、このインゴットを1000℃に加熱して3時間保持後、板厚10mmまで熱間圧延した。熱間圧延終了時の材料温度は850℃であった。その後、水冷した。
次いで、第一時効処理を材料温度600℃、加熱時間10時間の条件で実施した。
次いで、第一冷間圧延を95%以上の加工度で実施した。
次いで、溶体化処理をCo濃度が0.5~1.0質量%のものは材料温度850℃、加熱時間100秒、Co濃度が1.2質量%のものは材料温度900℃、加熱時間100秒、Co濃度が1.5~1.9質量%のものは加熱温度950℃、加熱時間100秒、Co濃度が2.0質量%以上のものは加熱温度1000℃、加熱時間100秒の条件で実施し、その後は水冷した。
次いで、第二時効処理を表1に記載の条件で実施した。
次いで、第二冷間圧延を圧下率20%の条件で実施し、板厚0.3mmのものと板厚0.2mmのものの二種類を得た。
最後に、歪み取り焼鈍を材料温度400℃、加熱時間30秒の条件で実施して、各試験片とした。同一番号の試験片には板厚0.2mmと板厚0.3mmの二種類が存在する。
なお、各工程の合間には適宜面削、酸洗、脱脂を行った。
(1)0.2%耐力(YS)及び引張強さ(TS)
圧延平行方向の引張り試験をJIS-Z2241に従って行い、0.2%耐力(YS:MPa)及び引張強さ(TS);MPaを測定した。
(2)導電率(EC)
ダブルブリッジによる体積抵抗率測定を行って、導電率(EC:%IACS)を求めた。
(3)平均結晶粒径(GS)
試験片を観察面が圧延方向に対し平行な厚み方向の断面となるように樹脂埋めし、観察面を機械研磨にて鏡面仕上げを行い、続いて水100容量部に対して質量濃度36%の塩酸10容量部の割合で混合した溶液に、その溶液の重量に対して5%の重量の塩化第二鉄を溶解させた。こうして出来上がった溶液中に、試料を10秒間浸漬して金属組織を現出させた。次に、この金属組織を光学顕微鏡で100倍に拡大して観察視野0.5mm2の範囲の写真を撮った。続いて、当該写真に基づいて個々の結晶粒の圧延方向の最大径と厚み方向の最大径との平均を各結晶について求め、各観察視野に対して平均値を算出し、さらに観察視野15箇所の平均値を平均結晶粒径とした。
(4)曲げ加工性
<W曲げ>
0.2mmと0.3mmの厚みの試料を幅100mm、長さ200mmに切り出したものを曲げ用試験片として用いた。試験片をW字型の金型を用いてBadway(曲げ軸が圧延方向と同一方向)のW曲げ試験を行い、曲げ部分に亀裂が発生しない最小曲げ半径(MBR)を板厚(t)で除した値であるMBR/tを求めた。
<180°曲げ>
0.2mmの厚みの試料を幅100mm、長さ200mmに切り出したものを曲げ用試験片として用いた。所定の曲げ半径(R)で170°程度にBadwayに曲げた後、曲げ内側半径(R)の2倍の挟み物をし180°に押し曲げて180°曲げ試験を行い、曲げ部分に亀裂が発生しない最小曲げ半径(MBR)を板厚(t)で除した値であるMBR/tを求めた。
(5)粒径が1~50nmの範囲にある第二相粒子の平均粒径及び平均距離
各試験片の一部を用いて、ツインジェット式電解研磨装置によって、厚み10~100nmの観察用試料の作成を行い、透過型電子顕微鏡(HITACHI-H-9000)により先述した方法に従って測定した。10視野の平均値を測定値とした。
本実施例では、透過型電子顕微鏡の試料作成において一般に用いられる電解研磨法を使用したが、FIB(Focused Ion Beam:集束イオンビーム)による薄膜作成を行って測定しても良い。
No.1~33は発明例であり、溶体化処理後に行った第2時効処理条件が適切であったため、強度、導電率、及び曲げ加工性のバランスに優れていた。また、時効処理の段数を増やすことでこのバランスが更に向上したことが分かる。特に曲げ性については、0.2mm厚での評価結果はMBR/t=0であり、0.3mmと厚い板厚でも良好な結果が得られている。
一方、No.34は、時効処理時の温度が低く、時間も短かったために第二相粒子の成長が不十分で平均粒子径が2nm以下となった。そのため、発明例に比べて特性のバランスが劣った。
No.35は、時効処理時の温度が高く、時間も長かったために第二相粒子が成長し過ぎて平均粒子径が10nm以上となった。そのため、発明例に比べて特性のバランスが劣った。
No.36は、時効処理時の昇温速度が低すぎたために昇温中に第二相粒子が成長し過ぎて平均粒子径が10nm以上となった。そのため、発明例に比べて特性のバランスが劣った。
No.37は、時効処理時の昇温速度が高すぎたために析出サイトの数が少なくなり、粒子間距離が50nm以上となった。そのため、発明例に比べて特性のバランスが劣った。
No.38とNo.39は、時効処理時の昇温速度が高すぎたために析出サイトの数が少なくなり、粒子間距離が50nm以上となった。そのため、発明例に比べて曲げ性が劣った。
No.40は、No.34に対して二段目の時効処理を追加した例であるが、一段目の時効処理時の温度が低く、時間も短かったために第二相粒子の成長が不十分で平均粒子径が2μm以下となった。そのため、発明例に比べて特性のバランスが劣った。
No.41は、No.35に対して二段目の時効処理を追加した例であるが、一段目の時効処理時の温度が高く、時間も長かったために第二相粒子が成長し過ぎて平均粒子径が10μm以上となった。そのため、発明例に比べて特性のバランスが劣った。
No.42は、No.34に対して二段目及び三段目の時効処理を追加した例であるが、一段目の時効処理時の温度が低く、時間も短かったために第二相粒子の成長が不十分で粒子径が2μm以下となった。そのため、発明例に比べて特性のバランスが劣った。
No.43は、No.35に対して二段目及び三段目の時効処理を追加した例であるが、一段目の時効処理時の温度が高く、時間も長かったために第二相粒子が成長し過ぎて平均粒子径が10μm以上となった。そのため、発明例に比べて特性のバランスが劣った。
表3に記載の質量濃度のCo、Si及びその他の元素を含有し、残部がCu及び不可避的不純物からなる成分組成を有するCu-Co-Si系銅合金について、例1のNo.27と同様の製造方法によって試験片を製造した。得られた試験片について、例1と同様に特性評価を行った。結果を表4に示す。各種の元素を添加しても本発明の効果が得られることが分かる。
表5に記載の質量濃度のCo、Siを含有し、残部がCu及び不可避的不純物からなる成分組成を有するCu-Co-Si系銅合金について、第一時効処理までは例1のNo.5と同じ製造方法で、第一時効処理後に、第一冷間圧延を95%以上の加工度で実施した。
次いで、溶体化処理を材料温度900℃、加熱時間100秒の条件で実施し、その後は水冷した。
次いで、第二冷間圧延を表5に記載の所定の加工度で行い、その後に第二時効処理をおこなって板厚0.2mmのものと板厚0.3mmの試験片を製造した。なお、各工程の合間には適宜面削、酸洗、脱脂を行った。
得られた試験片について例1と同様に特性評価を行った。結果を表6に示す。時効処理と冷間圧延の順を変更しても、時効温度を加工度×2℃下げて時効処理することで本発明の効果が得られることがわかる。
Claims (5)
- Coを0.5~3.0質量%、及び、Siを0.1~1.0質量%含有し、残部がCu及び不可避的不純物からなり、Co及びSiの質量%比(Co/Si)が3.5≦Co/Si≦5.0であり、圧延方向に平行な断面において粒径が1~50nmの範囲にある第二相粒子の平均粒径が2~10nmであり、且つ、当該第二相粒子同士の平均距離が10~50nmである電子材料用銅合金。
- 圧延方向に対し平行な断面における平均結晶粒径が3~30μmである請求項1記載の電子材料用銅合金。
- Ni、Cr、Sn、P、Mg、Mn、Ag、As、Sb、Be、B、Ti、Zr、Al及びFeよりなる群から選ばれる少なくとも1種の合金元素を更に含有し、且つ、当該合金元素の総量が2.0質量%以下である請求項1又は2記載の電子材料用銅合金。
- 請求項1~3何れか一項記載の電子材料用銅合金を加工して得られた伸銅品。
- 請求項1~3何れか一項記載の電子材料用銅合金を備えた電子部品。
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US10056166B2 (en) | 2018-08-21 |
EP2607508A4 (en) | 2014-04-09 |
CN103052728B (zh) | 2015-07-08 |
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KR101917416B1 (ko) | 2018-11-09 |
CN103052728A (zh) | 2013-04-17 |
EP2607508B1 (en) | 2017-07-26 |
TWI429764B (zh) | 2014-03-11 |
JP4834781B1 (ja) | 2011-12-14 |
JP2012046774A (ja) | 2012-03-08 |
TW201209181A (en) | 2012-03-01 |
EP2607508A1 (en) | 2013-06-26 |
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US20130209825A1 (en) | 2013-08-15 |
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