WO2011129281A1 - 電子材料用Cu-Si-Co系合金及びその製造方法 - Google Patents
電子材料用Cu-Si-Co系合金及びその製造方法 Download PDFInfo
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- WO2011129281A1 WO2011129281A1 PCT/JP2011/058921 JP2011058921W WO2011129281A1 WO 2011129281 A1 WO2011129281 A1 WO 2011129281A1 JP 2011058921 W JP2011058921 W JP 2011058921W WO 2011129281 A1 WO2011129281 A1 WO 2011129281A1
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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
- 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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- 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
Definitions
- the present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Si—Co based alloy suitable for use in various electronic components.
- 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. In recent years, 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 amount of precipitation hardening type copper alloys is increasing instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials.
- precipitation-hardened copper alloys by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.
- Cu-Ni-Si alloy commonly called Corson copper alloy
- Corson copper alloy is a representative copper alloy that has relatively high electrical conductivity, strength, and bending workability, and is currently active in the industry. It is one of the alloys being developed. In this copper alloy, the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.
- coarse second-phase particles can be obtained by an appropriate composition and manufacturing process. It is important to control the crystal grains to a uniform and appropriate grain size.
- Patent Document 1 Co forms a compound with Si in the same way as Ni, improves mechanical strength, and Cu—Co—Si based alloys are more mechanical than Cu—Ni—Si based alloys when subjected to aging treatment. It is described that a Cu—Co—Si based alloy may be selected if both strength and conductivity are improved and cost is allowed. And in order to implement
- the copper alloy described in Patent Document 1 is manufactured by performing a heat treatment for the purpose of recrystallization and solution after cold working, immediately quenching, and performing an aging treatment as necessary.
- the recrystallization treatment after cold working should be performed at 700 to 920 ° C.
- the cooling rate should be as fast as possible
- it should be cooled at a rate of 10 ° C./s or more
- the aging treatment temperature should be 420 to 550 ° C. Are listed.
- Patent Document 2 describes a Cu—Co—Si based alloy developed for the purpose of realizing high strength, high conductivity, and high bending workability, and the copper alloy contains Co and A Si compound and a Co and P compound are present, the average crystal grain size of the matrix is 20 ⁇ m or less, and the aspect ratio in the plate thickness direction to the rolling direction is 1 to 3.
- a method for producing a copper alloy described in Patent Document 2 after hot rolling, cold rolling of 85% or more is performed, after annealing at 450 to 480 ° C. for 5 to 30 minutes, cold rolling of 30% or less is performed, Further, a method is described in which an aging treatment is performed at 450 to 500 ° C. for 30 to 120 minutes.
- the present inventor has intensively studied to solve the above-mentioned problems.
- the Cu—Co—Si based alloy has a lower solid solubility limit than the Cu—Ni—Si based alloy, and therefore second phase particles are likely to precipitate.
- the second phase particles are likely to be generated as discontinuous precipitates (also referred to as grain boundary reaction precipitates), which adversely affects the alloy characteristics. This is probably because Cu and Co have a larger difference in atomic radius than Cu and Ni.
- the crystal grains were made relatively coarse by slowly passing through the recrystallization temperature region during cooling after hot rolling, and solution treatment. It is important to adopt production conditions such as making crystal grains coarse before treatment, performing cold rolling under low or high processing conditions, and performing aging treatment at relatively high temperatures. I found.
- the present invention completed on the basis of the above knowledge, in one aspect, contains 0.5 to 4.0% by mass of Co and 0.1 to 1.2% by mass of Si, with the balance being Cu and inevitable impurities.
- the mass ratio of Co and Si (Co / Si) is 3.5 ⁇ Co / Si ⁇ 5.5
- the area ratio of the discontinuous deposition (DP) cell is 5% or less
- the discontinuous deposition ( DP) A copper alloy for electronic materials having an average value of the maximum width of the cell of 2 ⁇ m or less.
- the number of continuous precipitates having a particle size of 1 ⁇ m or more is 25 or less per 1000 ⁇ m 2 in a cross section parallel to the rolling direction.
- the copper alloy for electronic materials according to the present invention has a 0.2% yield strength reduction rate of 10% or less after heating at a material temperature of 500 ° C. for 30 minutes.
- the copper alloy for electronic materials according to the present invention has a bending portion obtained when a 90-degree bending process is performed in a Badway W bending test under the condition that the ratio of the plate thickness to the bending radius is 1.
- the surface roughness Ra is 1 ⁇ m or less.
- the copper alloy for electronic materials according to the present invention has an average crystal grain size of 10 to 30 ⁇ m in a cross section parallel to the rolling direction.
- the copper alloy for electronic materials according to the present invention has a peak 0.2% yield strength (peak YS), an overaged 0.2% yield strength (overaged YS), and a peak YS and an overaged YS.
- Difference ( ⁇ YS) satisfies the relationship of ⁇ YS / peak YS ratio ⁇ 5.0%.
- the peak 0.2% proof stress (peak YS) is the highest 0.2% proof stress when the aging treatment time is 30 hours and the aging treatment temperature is changed by 25 ° C.
- the overaging 0.2% yield strength is the 0.2% yield strength when the aging treatment temperature is 25 ° C. higher than the aging treatment temperature at which the peak YS was obtained.
- the copper alloy for electronic materials according to the present invention is selected from the group consisting of Cr, Sn, P, Mg, Mn, Ag, As, Sb, Be, B, Ti, Zr, Al, and Fe. It further contains at least one selected alloy element, and the total amount of alloy elements is 2.0% by mass or less.
- -Step 1 of melt casting an ingot having a predetermined composition in which the material temperature is 950 ° C. to 1070 ° C. and heated for 1 hour or more, followed by hot rolling, but the average cooling rate when the material temperature is lowered from 850 ° C. to 600 ° C. is 0.4 ° C. / S or more and 15 ° C./s or less, and an average cooling rate of 600 ° C. or less is 15 ° C./s or more
- step 3 where cold rolling and annealing are optionally repeated, but when aging treatment is performed as annealing, the material temperature is set to 450 to 600 ° C.
- step 4 has a processing degree of 40% or less or 70% or more, -Next, in step 4 of solution treatment, where the maximum temperature of the material in the solution treatment is 900 ° C. to 1070 ° C., and the time during which the material temperature is maintained at the maximum temperature is 480 seconds or less.
- the average cooling rate when the temperature drops from the highest temperature to 400 ° C. is 15 ° C./s or more, -Next, in step 5 for performing an aging treatment, however, in the case of performing cold rolling immediately before the aging treatment, the working degree is set to 40% or less or 70% or more, It is a manufacturing method of the copper alloy for electronic materials which concerns on this invention.
- the manufacturing method according to the present invention includes performing any one of (1) to (4 ′) after step 4.
- Cold rolling ⁇ aging treatment step 5) ⁇ cold rolling (1 ′) cold rolling ⁇ aging treatment (step 5) ⁇ cold rolling ⁇ (low temperature aging treatment or strain relief annealing)
- Cold rolling ⁇ Aging treatment Process 5)
- Second ' Cold rolling ⁇ Aging treatment
- Aging treatment Step 5)
- Aging treatment Step 5) ⁇ Cold rolling (3 ′) Aging treatment (Step 5) ⁇ Cold rolling ⁇ (Low temperature aging treatment or strain relief annealing)
- Aging treatment Step 5) ⁇ Cold rolling (3 ′) Aging treatment (Step 5) ⁇ Cold rolling ⁇ (Low temperature aging treatment or strain relief annealing)
- Aging treatment Step 5) ⁇ Cold rolling ⁇ Aging treatment (4 ′) Aging treatment (Step 5) ⁇ Cold rolling ⁇ Aging treatment ⁇ (Low temperature aging treatment or strain relief annealing)
- 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 alloy having an improved balance between strength and conductivity, and preferably improved bending workability.
- a Cu—Co—Si alloy having improved heat resistance, suppressed overaging softening in aging treatment, and reduced strength variation due to temperature difference in the material coil in aging treatment is obtained.
- the copper alloy for electronic materials according to the present invention contains 0.5 to 4.0% by mass of Co and 0.1 to 1.2% by mass of Si, and the balance is made of Cu and inevitable impurities. And a mass% ratio (Co / Si) of Si is 3.5 ⁇ Co / Si ⁇ 5.5.
- the amount of Co added is too small, the strength required for an electronic component material such as a connector cannot be obtained. On the other hand, if it is too large, a crystallization phase is generated at the time of casting, which causes casting cracks. Moreover, it causes a decrease in hot workability and causes hot rolling cracks. Therefore, the content is set to 0.5 to 4.0% by mass. A preferable addition amount of Co is 1.0 to 3.5% by mass. If the addition amount of Si is too small, the strength required as an electronic component material such as a connector cannot be obtained. On the other hand, if the addition amount is too large, the decrease in conductivity is remarkable. Therefore, the content is set to 0.1 to 1.2% by mass. A preferable addition amount of Si is 0.2 to 1.0% 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 ⁇ 5.5, and preferably 4 ⁇ Co / Si ⁇ 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.
- a region where the second phase particles of cobalt silicide are deposited in a layered manner along the grain boundary by the grain boundary reaction is referred to as a discontinuous deposition (DP) cell.
- cobalt silicide refers to second phase particles containing 35 mass% or more of Co and 8 mass% or more of Si, and can be measured by EDS (energy dispersive X-ray analysis).
- EDS energy dispersive X-ray analysis
- Discontinuous deposition (DP) cells are desirable because they adversely affect the balance between strength and conductivity and heat resistance, and promote overaging softening. Therefore, in the present invention, the area ratio of the discontinuous deposition (DP) cell is suppressed to 5% or less, and the average value of the maximum width of the discontinuous deposition (DP) cell is suppressed to 2 ⁇ m or less.
- the area ratio of the discontinuous deposition (DP) cell is preferably 4% or less, and more preferably 3% or less.
- the crystal grains are likely to increase, so the area ratio of the discontinuous precipitation (DP) cell is 1% or more is preferable, and 2% or more is more preferable.
- the average maximum width of the discontinuous deposition (DP) cell is preferably 1.5 ⁇ m or less, and more preferably 1.0 ⁇ m or less.
- the crystal grains are still likely to increase, so that it is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more. .
- the average value of the area ratio and the maximum width of the discontinuous deposition (DP) cell is measured by the following method.
- a cross section parallel to the rolling direction of the material is mirror-finished by mechanical polishing using diamond abrasive grains having a diameter of 1 ⁇ m, and then electropolished in a 5% phosphoric acid aqueous solution at 20 ° C. at a voltage of 1.5 V for 30 seconds. .
- the base of Cu is dissolved, and the second phase particles remain undissolved and appear.
- This cross section is observed at an arbitrary 10 locations at a magnification of 3000 (observation field of view 30 ⁇ m ⁇ 40 ⁇ m) using an FE-SEM (field emission scanning electron microscope).
- the area ratio is divided into two colors, white and black, using the image software for the discontinuous deposition (DP) cell and the other portions, and the discontinuous deposition (DP) cell occupies the observation field.
- the area is calculated by image analysis software.
- the area ratio is a value obtained by dividing the average value at 10 locations of the value by the value of the area of the observation visual field (1200 ⁇ m 2 ).
- the average value of the maximum widths is the average value of the observed discontinuous precipitation (DP) cells having the longest length in the direction perpendicular to the grain boundary in each observation field. Is the average value of the maximum width.
- the continuous precipitate refers to second phase particles precipitated in the grains.
- continuous precipitates having a particle size of 1 ⁇ m or more do not contribute to the improvement of strength, but also lead to deterioration of bending workability. Therefore, the number of continuous precipitates having a particle size of 1 ⁇ m or more is preferably 25 or less per 1000 ⁇ m 2 in a cross section parallel to the rolling direction, more preferably 15 or less, and 10 or less. Is even more preferred.
- the particle size of the continuous precipitate refers to the diameter of the minimum circle surrounding each continuous precipitate.
- 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 fine second phase particles (continuous precipitates) precipitated in the crystal grains contribute to the strength improvement, but the second phase particles (discontinuous precipitates) precipitated at the crystal grain boundaries are almost all. Does not contribute to 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 the strength improvement becomes dominant.
- the average crystal grain size is preferably 10 to 30 ⁇ m. Furthermore, the average crystal grain size is more preferably controlled to 10 to 20 ⁇ m from the viewpoint of achieving both high strength and good bending workability.
- the Cu—Co—Si based alloy according to the present invention achieves strength, conductivity and bending workability at a high level.
- the 0.2% proof stress (YS) is 800 MPa or more, and the bending surface roughness is high.
- the average thickness may be 0.8 ⁇ m or less, and the conductivity may be 40% IACS or more, preferably 45% IACS or more, more preferably 50% IACS or more.
- 0.2% proof stress ( YS) can be 830 MPa or more, the average bending surface roughness is 0.8 ⁇ m or less, and the conductivity is 45% IACS or more, preferably 50% IACS or more.
- 0.2% Yield strength (YS) can be 860 MPa or more, bending surface roughness average 1.0 ⁇ m or less, and conductivity can be 45% IACS or more, preferably 50% IACS or more.
- the Cu—Co—Si based alloy according to the present invention has a feature that it is difficult to soften overaging by suppressing the formation of discontinuous precipitation (DP) cells. This feature can reduce variations in strength due to variations in temperature conditions during aging treatment. Further, in the case of batch aging treatment in which the material is processed in a coil shape, a temperature difference of about 10 to 25 ° C. occurs between the outer peripheral portion and the central portion of the coil.
- the Cu—Co—Si based alloy according to the present invention can reduce variations in strength caused by the temperature difference between the outer peripheral portion and the central portion of the coil. In other words, it can be said that the production stability in the aging treatment is excellent.
- the copper alloy according to the present invention has a feature that it is difficult to soften over time. This is considered due to the suppression of discontinuous precipitates.
- the difficulty of overaging softening can be evaluated by performing an aging treatment on a product after strain relief annealing or cold rolling.
- a product after (low temperature) aging treatment cannot be evaluated by aging treatment for the product, but can be evaluated together with the (low temperature) aging treatment.
- the value of ⁇ YS / peak YS is used as an evaluation index of the difficulty of overaging softening. YS represents 0.2% yield strength.
- the peak YS is the highest YS value when the aging treatment time is 30 hours and the aging treatment temperature is changed by 25 ° C. Further, the 0.2% proof stress when the aging treatment temperature is 25 ° C. higher than the aging treatment temperature at which the peak YS was obtained is defined as overaging YS.
- ⁇ YS is defined as follows.
- ⁇ YS (Peak YS)-(Overaging YS)
- ⁇ YS / peak YS ratio was defined as follows.
- ⁇ YS / peak YS ⁇ YS / peak YS ⁇ 100 (%) That is, when the value of ⁇ YS / peak YS is small, it means that overaging softening hardly occurs.
- the ⁇ YS / peak YS value is 5.0% or less, preferably 4.0% or less, more preferably 3.0% or less, and most preferably 2.5% or less. can do.
- the Cu—Co—Si alloy according to the present invention is also excellent in bending workability, and Badway's W bending test is performed at 90 ° under the condition that the ratio of the plate thickness to the bending radius is 1.
- the surface roughness Ra of the bent portion can be 1 ⁇ m or less as measured according to JIS B0601, and can also be 0.7 ⁇ m or less.
- the copper alloy for electronic materials according to the present invention is excellent in heat resistance because it can suppress softening caused by the growth of discontinuous precipitates, and after heating at a material temperature of 500 ° C. for 30 minutes.
- the 0.2% proof stress reduction rate can be 10% or less, preferably 8% or less, and more preferably 7% or less.
- the copper alloy for electronic materials according to the present invention can suppress softening caused by the growth of discontinuous precipitates, overaging softening in aging treatment is suppressed, and the temperature in the material coil during aging treatment is reduced.
- the intensity variation due to the difference can be reduced.
- the rate of decrease in 0.2% proof stress when aged for 30 hours at a temperature 25 ° C. higher than the peak aging treatment temperature can be 5% or less, preferably 4.0% or less, more preferably May be 3% or less, most preferably 2.5% or less.
- the basic process for producing the Cu—Co—Si based alloy according to the present invention includes melting and casting an ingot having a predetermined composition, hot rolling, cold rolling and annealing (aging treatment and recrystallization annealing). Including). Thereafter, solution treatment and aging treatment are performed under predetermined conditions. After the aging treatment, strain relief annealing may be further performed. Cold rolling can be appropriately sandwiched before and after the heat treatment. While discontinuous precipitation, each grain is coarser, the aging treatment is higher, and the degree of workability during cold rolling is suppressed as low workability or high workability. Process conditions should be set. The suitable conditions for the following steps will be described.
- 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.
- the material temperature is 850 ° C. for the purpose of slow cooling and coarse recrystallization to suppress discontinuous precipitation.
- the average cooling rate when the temperature is lowered to 600 ° C. is preferably 15 ° C./s or less, and more preferably 10 ° C./s or less.
- the cooling rate is too slow, coarsened second phase particles including continuous and discontinuous types are precipitated, so it is preferably 0.4 ° C./s or more, and preferably 1 ° C./s or more. More preferably, it is more preferably 3 ° C./s or more.
- the cooling rate in this temperature range can be controlled by blowing a cooling gas such as air and changing the temperature and flow rate of the cooling gas when cooling in the atmosphere. Further, when cooling in the furnace, it can be controlled by adjusting the furnace temperature or the gas flow rate / temperature in the furnace.
- the average cooling rate of 600 ° C. or less is preferably 15 ° C./s or more, and more preferably 50 ° C./s or more.
- the cooling here is generally performed by water cooling, and the cooling rate can be controlled by adjusting the amount of water and the water temperature.
- the degree of work is preferably 40% or less or 70% or more, and the degree of work is more preferably 30% or less or 80% or more. If the degree of work is too low, the number of annealing and cold rolling increases and the time required for production becomes long.If it is too high, it takes time for cold rolling due to work hardening, and the load applied to the rolling mill becomes high. Is typically 5 to 30% or 70 to 95%.
- annealing is preferably performed at a material temperature of 450 to 600 ° C. for 3 to 24 hours, more preferably at a material temperature of 475 ° C. to 550 ° C. for 6 to 20 hours.
- recrystallization annealing instead of an aging treatment, it is not necessary to pay particular attention to the cold rolling work degree in the next step. This is because recrystallization annealing is usually performed at a high temperature of 750 ° C. or higher, so that discontinuous precipitation is not a problem.
- the maximum temperature of the material in the solution treatment is set to 900 ° C. to 1070 ° C. If the maximum temperature reached is less than 900 ° C., sufficient solid solution is not achieved and coarse second-phase particles remain, so that desired strength and bending workability cannot be obtained. From the viewpoint of obtaining high strength, the highest ultimate temperature is preferably higher, specifically 1020 ° C. or higher, more preferably 1040 ° C. or higher. However, when the temperature exceeds 1070 ° C., the crystal grains become extremely coarse and the improvement in strength cannot be expected, and the temperature is close to the melting point of copper, which is a bottleneck in production.
- 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 20 seconds or more. More preferably.
- the cooling rate after the solution treatment is preferably as high as possible.
- the average cooling rate when the material temperature decreases from the highest temperature to 400 ° C. is preferably 15 ° C./s or more, and more preferably 50 ° C./s or more.
- the cooling is generally performed by cooling with cooling gas or water cooling. In cooling by blowing cooling gas, the cooling rate can be controlled by adjusting the furnace temperature, the temperature and flow rate of the cooling gas. In cooling by water cooling, the cooling rate can be controlled by adjusting the amount of water and the water temperature. The reason for paying attention to the average cooling rate from the highest temperature to 400 ° C.
- An aging treatment is performed after the solution treatment step.
- Cold rolling can be performed before, after, or before and after the aging treatment, and further aging treatment can be performed after the cold rolling.
- a condition for the aging treatment a known temperature and time which are known to cause continuous precipitates containing cobalt silicide to be finely and uniformly precipitated may be employed.
- An example of the aging treatment conditions is 1 to 30 hours in the temperature range of 350 ° C. to 600 ° C., more preferably 1 to 30 hours in the temperature range of 425 to 600 ° C.
- cold rolling and strain relief annealing or low temperature aging treatment is performed as necessary.
- cold rolling it is desirable to carry out under the conditions described above in order to suppress discontinuous precipitation.
- the heating conditions are sufficient for the conventional conditions, and in the case of the stress relief annealing for which the purpose is to remove the strain introduced by rolling, for example, 300
- the treatment can be performed for 10 s to 10 minutes in a temperature range of from 0 to 600 ° C.
- low temperature aging treatment for the purpose of improving the strength and conductivity by aging precipitation, for example, it can be performed in a temperature range of 300 ° C. to 500 ° C. for 1 to 30 hours.
- the following steps can be performed. (1) Cold rolling ⁇ aging treatment ⁇ cold rolling ⁇ (low temperature aging treatment or strain relief annealing as necessary) (2) Cold rolling ⁇ Aging treatment ⁇ (Low temperature aging treatment or strain relief annealing as necessary) (3) Aging treatment ⁇ cold rolling ⁇ (low temperature aging treatment or strain relief annealing as necessary) (4) Aging treatment ⁇ cold rolling ⁇ aging treatment ⁇ (low temperature aging treatment or strain relief annealing as necessary)
- 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.
- Table 1 shows the composition of the copper alloys used in the examples and comparative examples.
- Cu—Co—Si based copper alloys having the above component compositions were produced under the production conditions of A1 to A20 (invention examples) and B to J (comparative examples) shown in Table 2. All the copper alloys were manufactured according to the following basic manufacturing process. A copper alloy having a predetermined component composition was melted at 1300 ° C. 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. The cooling conditions after the hot rolling are as shown in Table 2. Cooling was performed in the furnace, and the average cooling rate up to 600 ° C.
- the first cold rolling was performed at the working degree shown in Table 2.
- the first temporary treatment was performed under the conditions of material temperature and heating time described in Table 2.
- the second cold rolling was performed at the working degree described in Table 2.
- solution treatment was carried out under the conditions of material temperature and heating time described in Table 2. Cooling was performed in the furnace, and the average cooling rate up to 400 ° C. was controlled by adjusting the furnace temperature, the cooling gas flow rate, and the cooling gas temperature.
- the third cold rolling was carried out at the working degree shown in Table 2.
- the second aging treatment was carried out under the conditions of material temperature and heating time described in Table 2.
- the fourth cold rolling was performed under the conditions described in Table 2.
- strain relief annealing or low temperature aging treatment was carried out under the conditions shown in Table 2 to obtain test pieces. In addition, chamfering, pickling, and degreasing were appropriately performed between each step.
- A1 is the optimum manufacturing condition.
- A2 is an example in which the degree of work in the fourth cold rolling is reduced with respect to A1.
- A3 is an example in which the degree of work in the third cold rolling is smaller than A1.
- A4 is an example in which the maximum temperature reached in the solution treatment is higher than that of A1.
- A5 is an example in which the maximum temperature reached in the solution treatment is lower than that of A1.
- A6 is an example in which the first temporary effect process is omitted from A1.
- A7 is an example in which the temperature of the first temporary effect treatment is increased with respect to A1.
- A8 is an example in which the first cold rolling is omitted from A1, and the degree of work of the second cold rolling is increased instead.
- A9 is an example in which the cooling rate after the end of hot rolling is increased with respect to A1.
- A10 is an example in which the cooling rate after completion of hot rolling is lower than that of A1.
- A11 is an example in which the degree of work in the first cold rolling is smaller than A1.
- A12 is an example in which the cooling rate in the solution treatment is slower than A1.
- A13 is an example in which the maximum temperature reached in the solution treatment is further increased with respect to A1.
- A14 is an example in which the final low-temperature aging treatment for A1 is a strain relief annealing.
- A15 is an example in which the third cold rolling is omitted from A1.
- A16 is an example in which the third cold rolling is omitted with respect to A1, and the final low-temperature aging treatment is strain relief annealing.
- A17 is an example in which the fourth cold rolling and the low temperature aging treatment are omitted from A1.
- A18 is an example in which the third cold rolling and the low temperature aging treatment are omitted from A1.
- A19 is an example in which the low temperature aging treatment is omitted from A1.
- A20 is an example in which the degree of work of the third cold rolling is increased with respect to A1.
- B is an example in which the degree of work in the fourth cold rolling is inappropriate.
- C is an example in which the degree of processing in the third cold rolling is inappropriate.
- D is an example in which the highest temperature reached during solution treatment in the solution treatment is inappropriate.
- E is an inappropriate example in which the first temporary treatment was performed at a higher temperature than necessary.
- F is an example in which the degree of processing in the first cold rolling is inappropriate.
- G is an inappropriate example because the cooling rate after hot rolling is too high.
- H is an inappropriate example because the cooling rate after hot rolling is too low.
- I is an example in which the degree of work in the fourth cold rolling is inappropriate.
- J is an example in which the degree of processing in the first cold rolling is inappropriate.
- GS Average crystal grain size
- the specimen is filled with resin so that the observation surface has a cross section in the thickness direction parallel to the rolling direction, and the observation surface is mirror-finished by mechanical polishing, followed by hydrochloric acid having a concentration of 36% with respect to 100 parts by volume of water.
- hydrochloric acid having a concentration of 36% with respect to 100 parts by volume of water.
- a solution mixed at a ratio of 10 parts by volume 5% by weight of ferric chloride was dissolved with respect to the weight of the solution.
- the sample was immersed in the resulting solution for 10 seconds to reveal the metal structure.
- this metal structure was magnified 100 times with an optical microscope, and a photograph was taken in the range of an observation visual field of 0.5 mm 2 .
- the aging treatment time is 30 hours
- the aging treatment temperature is 300 ° C, 325 ° C, 350 ° C, 375 ° C, 400 ° C, 425 ° C, 450 ° C, 475 ° C, 500 ° C, 525 ° C, 550 ° C
- Aging treatment was performed under 13 conditions of 575 ° C. and 600 ° C.
- 0.2% proof stress was measured for each test piece after aging treatment.
- the highest 0.2% proof stress was defined as peak YS
- the 0.2% proof stress of a test piece having an aging treatment temperature 25 ° C. higher than the aging treatment temperature at which peak YS was obtained was defined as overaging YS.
- the 0.2% proof stress was measured by conducting a tensile test in the rolling parallel direction according to JIS-Z2241.
- the test piece of the second aging treatment (the test piece obtained in step A17 of the example) and the test piece of the low temperature aging treatment (steps A1 to A13, A15, A20 of the example and the comparative example)
- the peak YS and the overaged YS were obtained by performing the above-described aging treatment instead of the second aging treatment or the low temperature aging treatment on the test pieces of the same lot.
- ⁇ YS / Peak YS ⁇ YS was defined as follows.
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Abstract
Description
特許文献1には、CoはNiと同様にSiと化合物を形成し、機械的強度を向上させ、Cu-Co-Si系合金は時効処理させた場合にCu-Ni-Si系合金より機械的強度、導電性共に良くなり、コスト的に許されるのであれば、Cu-Co-Si系合金を選択してもよいことが記載されている。そして、特性を好適に実現するためには、結晶粒度が1μmを越え25μm以下とすることが必要であることが記載されている。特許文献1に記載の銅合金は、冷間加工後に、再結晶と溶体化させる目的で熱処理を行い、直ちに焼き入れを行い、また必要に応じて時効処理を行うことで製造される。冷間加工後に再結晶処理を700~920℃で行うこと、冷却速度は出来るだけ素早く、10℃/s以上の速度で冷却することが望ましいこと、時効処理温度は420~550℃とすることが記載されている。
- 所定の組成を有するインゴットを溶解鋳造する工程1と、
- 次いで、材料温度を950℃~1070℃として1時間以上加熱した後に熱間圧延をする工程2と、ただし、材料温度が850℃から600℃まで低下する際の平均冷却速度を0.4℃/s以上15℃/s以下とし、600℃以下の平均冷却速度を15℃/s以上とし、
- 次いで、冷間圧延及び焼鈍を随意に繰り返す工程3と、ただし焼鈍として時効処理を行う場合は材料温度を450~600℃として3~24時間実施し、時効処理直前に冷間圧延を行う場合は加工度を40%以下又は70%以上とし、
- 次いで、溶体化処理をする工程4と、ただし、溶体化処理における材料の最高到達温度を900℃~1070℃とし、材料温度が最高到達温度に保持されている時間を480秒以下とし、材料温度が最高到達温度から400℃に低下するときの平均冷却速度を15℃/s以上とし、
- 次いで、時効処理を行う工程5と、ただし、時効処理直前に冷間圧延を行う場合は加工度を40%以下又は70%以上とし、
を含む本発明に係る電子材料用銅合金の製造方法である。
(1)冷間圧延→時効処理(工程5)→冷間圧延
(1’)冷間圧延→時効処理(工程5)→冷間圧延→(低温時効処理又は歪取焼鈍)
(2)冷間圧延→時効処理(工程5)
(2’)冷間圧延→時効処理(工程5)→(低温時効処理又は歪取焼鈍)
(3)時効処理(工程5)→冷間圧延
(3’)時効処理(工程5)→冷間圧延→(低温時効処理又は歪取焼鈍)
(4)時効処理(工程5)→冷間圧延→時効処理
(4’)時効処理(工程5)→冷間圧延→時効処理→(低温時効処理又は歪取焼鈍)
ただし、低温時効処理は300℃~500℃で1~30時間実施する。
また、本発明の好ましい形態によれば、耐熱性が改良され、時効処理における過時効軟化が抑制され、時効処理における材料コイル内温度差による強度のバラツキが低減されたCu-Co-Si系合金が得られる。
本発明に係る電子材料用銅合金は、Coを0.5~4.0質量%、及び、Siを0.1~1.2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≦5.5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0.1~1.2質量%とした。好ましいSiの添加量は0.2~1.0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。
本発明においては、粒界反応によって粒界に沿ってコバルトシリサイドの第二相粒子が層状に析出している領域を不連続析出(DP)セルという。本発明においては、コバルトシリサイドとはCoが35質量%以上、Siが8質量%以上含まれる第二相粒子のことを指し、EDS(エネルギー分散型X線分析)で計測可能である。
図1及び図2を参照すると、粒界に沿って層状の模様を有するセルを形成している領域一つ一つがそれぞれの不連続析出(DP)セル11である。一般には、不連続析出(DP)セル内ではコバルトシリサイド相とCu母相が層状になっている場合が多い。層間隔は様々であるが、おおよそ0.01μm~0.5μmである。
材料の圧延方向に平行な断面を、直径1μmのダイヤモンド砥粒を用いて機械研磨により鏡面に仕上げた後、20℃の5%リン酸水溶液中で1.5Vの電圧にて30秒間電解研磨する。この電解研磨によりCuの母地が溶解し、第2相粒子が溶け残って現出する。この断面をFE-SEM(電界放射型走査電子顕微鏡)を用いて倍率3000倍(観察視野30μm×40μm)で任意の10箇所を観察する。
面積率は、上記の定義に従って不連続析出(DP)セルと、そうでない部分とを画像ソフトを用いて白と黒の2色に塗り分け、観察視野のうち不連続析出(DP)セルが占める面積を画像解析ソフトにより算出する。その値の10箇所での平均値を観察視野の面積の値(1200μm2)で割った値を面積率とする。
最大幅の平均値は、観察される不連続析出(DP)セルのうち、粒界に直角な方向の長さの最も大きなものの長さを各観察視野で求め、それらの10箇所での平均値を最大幅の平均値とする。
連続型析出物とは粒内に析出した第二相粒子のことを指す。連続型析出物のうち、粒径が1μm以上の連続型析出物は、強度向上に寄与しないばかりでなく、曲げ加工性の劣化につながる。そこで、粒径が1μm以上である連続型析出物は、圧延方向に平行な断面において1000μm2あたり25個以下であるのが好ましく、15個以下であるのがより好ましく、10個以下であるのが更により好ましい。本発明において、連続型析出物の粒径とは個々の連続型析出物を取り囲む最小円の直径を指す。
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微細な第二相粒子(連続型析出物)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(不連続型析出物)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10μm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10~30μm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、10~20μmに制御することがより好ましい。
本発明に係るCu-Co-Si系合金は強度及び導電性及び曲げ加工性を高次元で達成するものであり、一実施形態において、0.2%耐力(YS)を800MPa以上、曲げ表面粗さ平均0.8μm以下、且つ、導電率を40%IACS以上、好ましくは45%IACS以上、より好ましくは50%IACS以上とすることができ、別の一実施形態において、0.2%耐力(YS)を830MPa以上、曲げ表面粗さ平均0.8μm以下、且つ、導電率を45%IACS以上、好ましくは50%IACS以上とすることができ、更に別の一実施形態において、0.2%耐力(YS)を860MPa以上、曲げ表面粗さ平均1.0μm以下、且つ、導電率を45%IACS以上、好ましくは50%IACS以上とすることができる。
本発明に係るCu-Co-Si系合金は、不連続析出(DP)セルの形成を抑制することにより、過時効軟化しにくい特長を有する。本特長により、時効処理の際の温度条件のバラつきによる強度のバラつきを低減することができる。また、材料をコイル状として処理を行うバッチ式での時効処理の場合には、コイルの外周部と中心部でその温度差が10~25℃程度生じる。本発明に係るCu-Co-Si系合金はコイルの外周部と中心部でその温度差によって生じる強度のバラつきも小さくすることができる。言い換えれば、時効処理における製造安定性に優れるともいえる。
本発明では過時効軟化のしにくさの評価指標としてΔYS/ピークYSの値を用いる。YSは0.2%耐力を表す。また、ピークYSは時効処理時間を30hとし、時効処理温度を25℃ずつ変化させて時効処理を行った際の最も高いYSの値である。また、ピークYSが得られた時効処理温度よりも25℃高い時効処理温度としたときの0.2%耐力を過時効YSとする。
ΔYSは以下の様に定義される。
ΔYS=(ピークYS)-(過時効YS)
また、ΔYS/ピークYS比を以下の様に定義した。
ΔYS/ピークYS=ΔYS/ピークYS×100(%)
すなわち、ΔYS/ピークYSの値が小さい場合、過時効軟化を起こしにくいことを意味する。一実施形態においてはΔYS/ピークYSの値は5.0%以下であり、好ましくは4.0%以下であり、更に好ましくは3.0%以下であり、最も好ましくは2.5%以下とすることができる。
本発明に係るCu-Co-Si系合金を製造するための基本工程は、所定の組成を有するインゴットを溶解鋳造し、熱間圧延した後、冷間圧延及び焼鈍(時効処理及び再結晶焼鈍を含む)を適宜繰り返す。その後、溶体化処理及び時効処理を所定の条件で行うことである。時効処理の後、歪取焼鈍を更に行っても良い。熱処理の前後には適宜冷間圧延を挟むこともできる。不連続型析出は、結晶粒が粗大である方が、時効処理は高温の方が、冷間圧延時の加工度は低加工度又は高加工度の方が抑制されることに留意しながら各工程の条件を設定すべきである。以下の各工程の好適な条件について説明する。
ここでの平均冷却速度は以下のように定義される。
平均冷却速度(℃/s)=(850-600(℃))/(850℃から600℃まで低下するのに要した時間(s))
ここでの平均冷却速度は以下のように定義される。
平均冷却速度(℃/s)=(600-100(℃))/(600℃から100℃まで低下するのに要した時間(s))
加工度(%)=(圧延前の板厚-圧延後の板厚)/圧延前の板厚×100
なお、時効処理ではなく再結晶焼鈍を行う場合は次工程の冷間圧延加工度について特に留意する必要はない。再結晶焼鈍は通常750℃以上の高温で行うので、不連続析出はさほど問題にならないからである。
ここでの平均冷却速度は以下のように定義される。
平均冷却速度(℃/s)=(最高到達温度-400(℃))/(材料取出し時(材料温度が最高到達温度から低下を開始した時)から400℃まで低下するのに要した時間(s))
(1)冷間圧延→時効処理→冷間圧延→(必要に応じて低温時効処理又は歪取焼鈍)
(2)冷間圧延→時効処理→(必要に応じて低温時効処理又は歪取焼鈍)
(3)時効処理→冷間圧延→(必要に応じて低温時効処理又は歪取焼鈍)
(4)時効処理→冷間圧延→時効処理→(必要に応じて低温時効処理又は歪取焼鈍)
所定の成分組成を有する銅合金を、高周波溶解炉を用いて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。熱間圧延終了後の冷却条件は表2に記載の通りである。冷却は炉内で行い、600℃までの平均冷却速度の制御は炉内温度や冷却ガス流量および冷却ガス温度の調節により行った。
次いで、第一冷間圧延を表2に記載の加工度で実施した。
次いで、第一時効処理を表2に記載の材料温度及び加熱時間の条件で実施した。
次いで、第二冷間圧延を表2に記載の加工度で実施した。
次いで、溶体化処理を表2に記載の材料温度及び加熱時間の条件で実施した。冷却は炉内で行い、400℃までの平均冷却速度の制御は炉内温度や冷却ガス流量および冷却ガス温度の調節により行った。
次いで、第三冷間圧延を表2に記載の加工度で実施した。
次いで、第二時効処理を表2に記載の材料温度及び加熱時間の条件で実施した。
次いで、第四冷間圧延を表2に記載の条件で実施した。
最後に、歪取焼鈍又は低温時効処理を表2に記載の条件で実施して、各試験片とした。
なお、各工程の合間には適宜面削、酸洗、脱脂を行った。
A1は最適な製造条件である。
A2はA1に対して第4冷間圧延における加工度を小さくした例である。
A3はA1に対して第3冷間圧延における加工度を小さくした例である。
A4はA1に対して溶体化処理における最高到達温度を高くした例である。
A5はA1に対して溶体化処理における最高到達温度を低くした例である。
A6はA1に対して第一時効処理を省略した例である。
A7はA1に対して第一時効処理の温度を高くした例である。
A8はA1に対して第1冷間圧延を省略し、代わりに第2冷間圧延の加工度を大きくした例である。
A9はA1に対して熱間圧延終了後の冷却速度を高くした例である。
A10はA1に対して熱間圧延終了後の冷却速度を低くした例である。
A11はA1に対して第1冷間圧延における加工度を小さくした例である。
A12はA1に対して溶体化処理における冷却速度を遅くした例である。
A13はA1に対して溶体化処理における最高到達温度を更に高くした例である。
A14はA1に対して最終の低温時効処理を歪取焼鈍にした例である。
A15はA1に対して第3冷間圧延を省略した例である。
A16はA1に対して第3冷間圧延を省略し、最終の低温時効処理を歪取焼鈍にした例である。
A17はA1に対して第4冷間圧延及び低温時効処理を省略した例である。
A18はA1に対して第3冷間圧延及び低温時効処理を省略した例である。
A19はA1に対して低温時効処理を省略した例である。
A20はA1に対して第3冷間圧延の加工度を大きくした例である。
Bは第4冷間圧延における加工度が不適切な例である。
Cは第3冷間圧延における加工度が不適切な例である。
Dは溶体化処理における溶体化での最高到達温度が不適切な例である。
Eは第一時効処理を必要以上に高温で実施した不適切な例である。
Fは第1冷間圧延における加工度が不適切な例である。
Gは熱間圧延終了後の冷却速度が高すぎたために不適切な例である。
Hは熱間圧延終了後の冷却速度が低すぎたために不適切な例である。
Iは第4冷間圧延における加工度が不適切な例である。
Jは第1冷間圧延における加工度が不適切な例である。
(1)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。
(2)不連続析出(DP)セルの面積率(DP面積率)及び不連続析出帯の最大幅の平均値(DP最大幅平均値)
FE-SEMとしてPHILIPS社製型式XL30SFEGを使用して、先述した方法で測定した。また、不連続析出(DP)セルを構成する第二相粒子がコバルトシリサイドであることをEDS(エネルギー分散型X線分析)を用いて確認した。
(3)0.2%耐力(YS)
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)を測定した。
(4)ピーク0.2%耐力(ピークYS)及び過時効0.2%耐力(過時効YS)
ピークYS及び過時効YSは、最終工程が低温時効処理ではなく冷間圧延又は歪取焼鈍として得られた試験片(実施例の工程A14、A16、A18、A19、及び比較例の工程Jで得られた試験片)については、得られた試験片に対して更に以下の時効処理を行うことで求めた。
同一ロットの試験片について、時効処理時間を30hr、時効処理温度を300℃、325℃、350℃、375℃、400℃、425℃、450℃、475℃、500℃、525℃、550℃、575℃、600℃の13条件でそれぞれ時効処理を行い、時効処理後のそれぞれの試験片について0.2%耐力を測定した。そのうち、最も高い0.2%耐力をピークYSとし、ピークYSが得られた時効処理温度よりも25℃高い時効処理温度とした試験片の0.2%耐力を過時効YSとした。0.2%耐力は、圧延平行方向の引張り試験をJIS-Z2241に従って行い、測定した。
一方、最終工程が第二時効処理の試験片(実施例の工程A17で得られた試験片)、並びに低温時効処理の試験片(実施例の工程A1~A13、A15、A20及び比較例の工程B~Iで得られた試験片)については、同一ロットの試験片について、第二時効処理又は低温時効処理に代えて今述べた時効処理を行うことでピークYS及び過時効YSを求めた。
(5)ΔYS/ピークYS
ΔYSを以下の様に定義した。
ΔYS=(ピークYS)-(過時効YS)
また、ΔYS/ピークYS比を以下の様に定義した。
ΔYS/ピークYS比=ΔYS/ピークYS×100(%)
(6)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。
(7)曲げ表面の平均粗さ
Badway(曲げ軸が圧延方向と同一方向)のW曲げ試験として、W字型の金型を用いて試料板厚と曲げ半径の比が1となる条件で90°曲げ加工を行った。続いて、共焦点顕微鏡を用いて曲げ加工部表面の表面粗さRa(μm)をJIS B 0601に従って求めた。
(8)材料温度500℃として30分加熱した後の0.2%耐力の低下率
加熱前後で、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)を測定した。加熱処理前の0.2%耐力をYS0、加熱処理後の0.2%耐力をYS1とすると、低下率(%)=(YS0-YS1)/YS0×100で表される。
(9)粒径が1μm以上の連続型析出物の個数密度
材料の圧延方向に平行な断面を、直径1μmのダイヤモンド砥粒を用いて機械研磨により鏡面に仕上げた後、20℃の5%リン酸水溶液中で1.5Vの電圧にて30秒間電解研磨した。この電解研磨によりCuの母地が溶解し、第2相粒子が溶け残って現出した。この断面をFE-SEM(電界放射型走査電子顕微鏡:PHILIPS社製)を用いて倍率3000倍(観察視野30μm×40μm)で任意の10箇所を観察し、粒径1μm以上の連続型析出物の個数を数え、1000μm2当たりの平均個数を算出した。連続型析出物がコバルトシリサイドを含有することをEDS(エネルギー分散型X線分析)を用いて確認した。
No.1-1~1-20、No.2-1~2-20、No.3-1~3-14、No.4-1~4-14、No.5-1~5-14、No.6-1~6-14、No.7-1~7-14、No.8-1~8-14、No.9-1~9-14、No.10-1~10-14、No.11-1~11-14、No.12-1~12-14、No.13-1~13-14、No.14-1~14-14、No.15-1~15-14、No.16-1~16-20、No.17-1~17-20は本発明の実施例である。中でも製造条件A1によって製造したNo.1-1、No.2-1、No.3-1、No.4-1、No.5-1、No.6-1、No.7-1、No.8-1、No.9-1、No.10-1、No.11-1、No.12-1、No.13-1、No.14-1、No.15-1、No.16-1及びNo.17-1は同一組成同士を比べたときに強度及び導電性のバランスが最も優れている。
一方、製造条件Bで製造したNo.1-23、No.2-23、No.3-17、No.4-17、No.5-17、No.16-23、No.17-23及び製造条件Iで製造したNo.1-28、No.2-28、No.16-28、及びNo.17-28は何れも第4冷間圧延における加工度が不適切であったために、低温時効処理工程で不連続析出物が成長した。そのため、DPセルの面積率、最大幅の平均値が高くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Cで製造したNo.1-22、No.2-22、No.3-16、No.4-16、No.5-16、No.16-22、及びNo.17-22は何れも第3冷間圧延における加工度が不適切であったために、その後の時効処理で不連続析出物が成長した。そのため、DPセルの面積率、最大幅の平均値が高くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Dで製造したNo.1-26、No.2-26、No.3-20、No.4-20、No.5-20、No.16-26、及びNo.17-26は何れも溶体化処理における最高到達温度が低かったために、未固溶の第2相粒子(以前の工程で生成した不連続析出物も含む)が多く残存した。そして、その後の時効処理で不連続析出物が成長した。そのため、DPセルの面積率、最大幅の平均値が高くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Eで製造したNo.1-27、No.2-27、No.3-21、No.4-21、No.5-21、No.16-27、及びNo.17-27は何れも第一時効処理を必要以上に高温で実施したために、連続析出物及び不連続析出物が粗大に成長した。そのため、溶体化後に連続析出物及び不連続析出物が多く残存し、最終的なDPセルの面積率、最大幅の平均値が高くなり、1μm以上の連続析出物の個数が多くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Fで製造したNo.1-21、No.2-21、No.3-15、No.4-15、No.5-15、No.16-21、No.17-21、並びに、製造条件Jで製造したNo.1-29、No.2-29、No.16-29、及びNo.17-29は何れも第1冷間圧延における加工度が不適切だったために、その後の時効処理で不連続析出物が成長した。そのため、溶体化後に不連続析出物が多く残存し、最終的なDPセルの面積率、最大幅の平均値が高くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Gで製造したNo.1-24、No.2-24、No.3-18、No.4-18、No.5-18、No.16-24、及びNo.17-24は何れも熱間圧延終了後の冷却速度が高すぎたために、再結晶粒の成長が不十分となってしまい、その後の時効処理で不連続析出物が成長した。そのため、溶体化後に不連続析出物が多く残存し、最終的なDPセルの面積率、最大幅の平均値が高くなり、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
製造条件Hで製造したNo.1-25、No.2-25、No.3-19、No.4-19、No.5-19、No.16-25、及びNo.17-25は何れも熱間圧延終了後の冷却速度が低すぎたために、再結晶粒のほか、不連続析出物及び連続析出物を含めた第2相粒子が粗大に成長した。そのため、溶体化後に不連続・連続析出物が多く残存し、最終的に粗大な不連続・連続析出物が多く存在し、各組成に対応する発明例に比べて強度及び導電性のバランスが低下し、曲げ性、耐熱性も悪化した。
また、No.18-1、No.20-1、No.21-1は、製造条件A1で製造したが、組成が本発明の範囲外であったため、強度及び導電性のバランスが低下した。
また、No.19-1は、製造条件A1で製造したが、Co濃度及びSi濃度が高く、本発明の範囲外であったため、熱間圧延時に割れが生じた。そのため、本組成での製品の製造を中止した。
12 連続型析出物
Claims (11)
- Coを0.5~4.0質量%、及び、Siを0.1~1.2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≦5.5で、不連続析出(DP)セルの面積率が5%以下であり、不連続析出(DP)セルの最大幅の平均値が2μm以下である電子材料用銅合金。
- 粒径が1μm以上である連続型析出物が、圧延方向に平行な断面において1000μm2あたり25個以下である請求項1記載の電子材料用銅合金。
- 材料温度500℃として30分加熱した後の0.2%耐力の低下率が10%以下である請求項1又は2記載の電子材料用銅合金。
- BadwayのW曲げ試験を板厚と曲げ半径の比が1となる条件で90°曲げ加工を行ったときの曲げ部の表面粗さRaが1μm以下である請求項1~3何れか一項記載の電子材料用銅合金。
- 圧延方向に対し平行な断面における平均結晶粒径が10~30μmである請求項1~4何れか一項記載の電子材料用銅合金。
- ピーク0.2%耐力(ピークYS)、過時効0.2%耐力(過時効YS)、及びピークYSと過時効YSの差(ΔYS)が、ΔYS/ピークYS比≦5.0%の関係を満たす請求項1~5何れか一項記載の電子材料用銅合金:
ここで、ピーク0.2%耐力(ピークYS)とは時効処理時間を30時間とし、時効処理温度を25℃ずつ変化させて時効処理を行った際の最も高い0.2%耐力であり、過時効0.2%耐力(過時効YS)とはピークYSが得られた時効処理温度よりも25℃高い時効処理温度としたときの0.2%耐力である。 - 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、合金元素の総量が2.0質量%以下である請求項1~6何れか一項記載の電子材料用銅合金。
- - 所定の組成を有するインゴットを溶解鋳造する工程1と、
- 次いで、材料温度を950℃~1070℃として1時間以上加熱した後に熱間圧延をする工程2と、ただし、材料温度が850℃から600℃まで低下する際の平均冷却速度を0.4℃/s以上15℃/s以下とし、600℃以下の平均冷却速度を15℃/s以上とし、
- 次いで、冷間圧延及び焼鈍を随意に繰り返す工程3と、ただし焼鈍として時効処理を行う場合は材料温度を450~600℃として3~24時間実施し、時効処理直前に冷間圧延を行う場合は加工度を40%以下又は70%以上とし、
- 次いで、溶体化処理をする工程4と、ただし、溶体化処理における材料の最高到達温度を900℃~1070℃とし、材料温度が最高到達温度に保持されている時間を480秒以下とし、材料温度が最高到達温度から400℃に低下するときの平均冷却速度を15℃/s以上とし、
- 次いで、時効処理を行う工程5と、ただし、時効処理直前に冷間圧延を行う場合は加工度を40%以下又は70%以上とし、
を含む請求項1~7何れか一項記載の電子材料用銅合金の製造方法。 - 工程4の後、(1)~(4’)の何れかを実施することを含む請求項8記載の電子材料用銅合金の製造方法:
(1)冷間圧延→時効処理(工程5)→冷間圧延
(1’)冷間圧延→時効処理(工程5)→冷間圧延→(低温時効処理又は歪取焼鈍)
(2)冷間圧延→時効処理(工程5)
(2’)冷間圧延→時効処理(工程5)→(低温時効処理又は歪取焼鈍)
(3)時効処理(工程5)→冷間圧延
(3’)時効処理(工程5)→冷間圧延→(低温時効処理又は歪取焼鈍)
(4)時効処理(工程5)→冷間圧延→時効処理
(4’)時効処理(工程5)→冷間圧延→時効処理→(低温時効処理又は歪取焼鈍)
ただし、低温時効処理は300℃~500℃で1~30時間実施する。 - 請求項1~7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1~7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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CN102844452A (zh) | 2012-12-26 |
EP2559777A4 (en) | 2014-04-09 |
JP4830035B2 (ja) | 2011-12-07 |
CN102844452B (zh) | 2015-02-11 |
US9499885B2 (en) | 2016-11-22 |
TW201142050A (en) | 2011-12-01 |
US20130098511A1 (en) | 2013-04-25 |
EP2559777A1 (en) | 2013-02-20 |
TWI438286B (zh) | 2014-05-21 |
JP2011219843A (ja) | 2011-11-04 |
KR20120137507A (ko) | 2012-12-21 |
KR101443481B1 (ko) | 2014-09-22 |
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