WO2012060359A1 - 銅合金熱間鍛造品及び銅合金熱間鍛造品の製造方法 - Google Patents
銅合金熱間鍛造品及び銅合金熱間鍛造品の製造方法 Download PDFInfo
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- WO2012060359A1 WO2012060359A1 PCT/JP2011/075149 JP2011075149W WO2012060359A1 WO 2012060359 A1 WO2012060359 A1 WO 2012060359A1 JP 2011075149 W JP2011075149 W JP 2011075149W WO 2012060359 A1 WO2012060359 A1 WO 2012060359A1
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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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- 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
- C22C9/04—Alloys based on copper with zinc 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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 copper alloy hot forged product and a method for producing a copper alloy hot forged product.
- the present invention relates to a copper alloy hot forged product excellent in strength, proof stress, thermal conductivity, electrical conductivity, and creep characteristics and a method for producing the copper alloy hot forged product.
- Copper is used in various industrial fields such as heat sinks, heat spreaders, end rings, terminals, base plates, connectors, electrodes, sensor components, molds, pressure vessels, etc., taking advantage of high thermal conductivity and electrical conductivity.
- so-called pure copper having a copper concentration of 99.9% or more including tough pitch copper, oxygen-free copper, and phosphorus deoxidized copper, has low strength. Therefore, in order to ensure strength, the amount of copper used per unit area is low. The cost increases and the volume and weight increase.
- heat sinks need excellent heat dissipation, but it is necessary that strength and hardness are not lowered by the temperature at the time of assembling process or mounting, soldering or brazing. And even if there is a temperature rise during use, a high creep characteristic that can withstand it is necessary.
- the end ring used in the motor is joined to the rotor bar by hard brazing, and requires high strength, high thermal conductivity, and electrical conductivity after brazing. And since there exists a temperature rise exceeding 100 degreeC in use, it is calculated
- heat sinks heat sinks with protrusions on the surface to increase the surface area, large terminals and connectors, electrodes, sensor-parts and other complicated shapes, and motor end rings
- heat sinks In order to process a donut-shaped shape like this, it can be processed by hot forging, cutting, pressing, or cold forging.
- cutting can process materials in various shapes, but a copper alloy with a high copper concentration has poor machinability, so it takes a lot of man-hours to process and the yield is poor. Economically problematic.
- copper hardens when trying to form by press or cold forging, copper hardens, so a large degree of processing cannot be added and complex shapes cannot be processed.
- Reheating at a high temperature of 950 ° C. increases the cost, and oxidation loss occurs when heated in the atmosphere.
- the forged product is easily deformed due to high-temperature reheating, and stickiness occurs between the materials. Therefore, heat treatment is performed at 950 ° C. in an inert gas or in vacuum, but the oxidation loss can be prevented, but the cost is increased, and there is a problem of deformation and stickiness.
- Patent Document 1 a copper alloy for hot forging in which the composition of Al, Si, Ni or the like is limited has been proposed (see Patent Document 1).
- the copper alloy described in Patent Document 1 has a problem that special solution treatment is required and electric / thermal conductivity is poor.
- the present invention has been made to solve such problems of the prior art, and manufacture of a copper alloy hot forged product and a copper alloy hot forged product excellent in strength, yield strength, thermal conductivity, and electrical conductivity. It is an object to provide a method.
- the present inventor examined the composition and metal structure of a copper alloy.
- a copper alloy having a predetermined composition hot forging is performed under predetermined conditions, and the ratio of the recrystallized grain group whose average crystal grain size is within the predetermined range and the ratio of the non-recrystallized grain are predetermined. It was found that a copper alloy hot forged product excellent in strength, proof stress, thermal conductivity, electrical conductivity, and the like can be obtained by making it within the above range.
- the present invention has been completed based on the knowledge of the present inventors. That is, in order to solve the above problems, the present invention provides 0.21 to 0.44 mass% Co, 0.06 to 0.13 mass% P, 0.003 to 0.08 mass% Sn, 0 0.0003-0.0030 mass% O and the balance is an alloy composition consisting of Cu and unavoidable impurities, between the Co content [Co] mass% and the P content [P] mass% 3.1 ⁇ ([Co] ⁇ 0.005) / ([P] ⁇ 0.006) ⁇ 4.9, and the average crystal grain size of the recrystallized grains in the cross-sectional metal structure is 0.8.
- a copper alloy hot forged product characterized in that the total of the proportion of the recrystallized grain group of 050 to 0.50 mm and the proportion of the non-recrystallized grain is 80% or more.
- the non-recrystallized grains referred to in this specification will be described.
- the recrystallized grains before hot forging are strained by hot forging, but those that remain without being recrystallized are called unrecrystallized grains. Whether or not strain remains in the crystal grains is clear from the metallographic structure, and recrystallized grains and unrecrystallized grains can be identified by observing the residual strain. Identify as follows.
- the recrystallized grain has a shape close to a regular hexagon.
- FIG. 1 shows an example of the diameter of a circumscribed circle circumscribing a crystal grain and the diameter of an inscribed circle inscribed in the crystal grain.
- the average crystal grain size of the recrystallized grains is measured according to JIS H 0501. And when the metal structure of the observed visual field is a recrystallized grain, the collection of all the recrystallized grains in the visual field is called the recrystallized grain group in the visual field.
- the recrystallized grains in the field of view are the recrystallized grain group in which the average crystal grain size of the recrystallized grains is amm. . In this way, the average crystal grain size of the recrystallized grain group is measured for each visual field to be observed.
- cross-sectional metal structure referred to in this specification is a metal structure in a portion excluding a portion having a depth of 1 mm from the surface of the forged product in at least one cross section for cutting the forged product.
- the copper alloy hot forged product further contains at least one of 0.005 to 0.15 mass% Ni and 0.003 to 0.10 mass% Fe, and the Co content [Co] mass. %, Ni content [Ni] mass%, Fe content [Fe] mass%, and P content [P] mass%, 3.1 ⁇ ([Co] +0.9 ⁇ [Ni] + 0.8 ⁇ [Fe] ⁇ 0.005) / ([P] ⁇ 0.006) ⁇ 4.9 and 0.010 ⁇ 2 ⁇ [Ni] + 3 ⁇ [Fe] ⁇ 0.75 ⁇ [Co] relationship may be included.
- this copper alloy hot forged product even if it has either Ni or Fe, it is excellent in strength, proof stress, thermal conductivity, electrical conductivity and the like.
- the yield strength is 230 N / mm 2 or more
- the thermal conductivity at 20 ° C. is 300 W / m ⁇ K or more
- the conductivity at 20 ° C. is 75% IACS or more
- the yield strength is L (N / mm 2 )
- the thermal conductivity is M (W / m ⁇ K) and the conductivity is N (% IACS)
- the value of (L ⁇ M) is 77000 or more, or the value of (L ⁇ N)
- a hot pure forged product of general pure copper (C1020, C1100, C1220) has a thermal conductivity of 320 to 395 W / m ⁇ K at 20 ° C., an electrical conductivity of 83 to 102% IACS, and a proof stress of 40 to 80 N. / Mm 2 , taking into account that the product of proof stress and thermal conductivity is 17000-25000 and the product of proof stress and electrical conductivity is about 4500 to 6000, the above-described desirable values naturally have a great effect. Demonstrate.
- the industrial pure aluminum hot forging has a yield strength of about 30 N / mm 2 , a thermal conductivity at 20 ° C. of about 220 W / m ⁇ K, and a conductivity of about 60% IACS. Much better. More preferably, the yield strength is 250 N / mm 2 or more, the thermal conductivity at 20 ° C. is 310 W / m ⁇ K or more, or the conductivity is 77% IACS or more, and the product of the yield strength and the thermal conductivity is 82000 or more. Or the product of yield strength and electrical conductivity is 20000 or more.
- the total amount of creep deformation excluding the initial deformation is 0.05% or less.
- the average particle size of the precipitates in the recrystallized grains is 1.3 to 3.9 nm, or 90% or more of the precipitates is 0.7 to 7 nm.
- the average particle size of the precipitate is 1.3 to 3.9 nm, or 90% or more of the precipitate is 0.7 to 7 nm, so that the high yield strength and the high thermal conductivity are achieved.
- high electrical conductivity and can have high creep characteristics at 100 to 200 ° C., which is the use environment.
- the proportion of the recrystallized grain group in which the average crystal grain size of the recrystallized grain is 0.050 to 0.50 mm is 60% or more, or the ratio of the non-recrystallized grain is 60% or more. It is desirable.
- Such a preferable copper alloy hot forged product can have high creep characteristics at 100 to 200 ° C., which is the use environment.
- the yield strength after cooling is 125 N / mm 2 or more
- the thermal conductivity at 20 ° C. after the cooling is 280 W / m ⁇ K or more, or 20 ° C. after the cooling
- the electrical conductivity at 70 ° IACS or more is L (N / mm 2 ) after the cooling
- the thermal conductivity at 20 ° C. after the cooling is M (W / m ⁇ K), and 20 after the cooling.
- the conductivity at ° C is N (% IACS)
- the value of (L ⁇ M) is desirably 38000 or more
- the value of (L ⁇ N) is desirably 9600 or more.
- the end ring made of the hot forged product of the present invention is excellent in strength, thermal conductivity, and electrical conductivity for joining to the rotor bar.
- BAg-5 45 Ag- described in JIS Z 3261 30Cu-25Zn alloy brazing
- BAg-6 50Ag-34Cu-16Zn alloy brazing
- BAg-7 56Ag-22Cu-17Zn-5Sn alloy brazing are used, and their brazing temperatures are 745 to 845 ° C., 775 ⁇
- High temperatures of 870 ° C. and 650 ° C. to 750 ° C. are recommended.
- the end ring is required to have a heat resistance of about 800 ° C. which is a brazing temperature for a short time.
- the end ring used in the motor has a high centrifugal force due to its high speed, so it must be strong enough to withstand it. That is, the forged product is immersed in a salt bath of 825 ° C. corresponding to Ag brazing conditions for 300 seconds and heated, and the proof stress is 125 N / mm 2 or more, preferably 130 N / mm 2 or more, and heat at 20 ° C.
- the conductivity is 280 W / m ⁇ K or more, or the conductivity is 70% IACS or more, the product of the proof stress and the thermal conductivity is 38000 or more, or the product of the proof stress and the conductivity is 9600 or more.
- a hot forged product having a smooth surface such as an end ring is subjected to a cold work of 5 to 20% after a hot forging and before a precipitation heat treatment for 300 seconds in a salt bath at 825 ° C.
- the yield strength is 150 N / mm 2 or more
- the thermal conductivity at 20 ° C. is 280 W / m ⁇ K or more
- the conductivity is 70% IACS or more
- the product of the yield strength and the thermal conductivity is 48000.
- the product of the proof stress and the conductivity is 12000 or more.
- a stress of 50 N / mm 2 is applied at 200 ° C.
- the brazing equivalent product is coarse with an average crystal grain size of 0.05 mm, further 0.08 mm or more, so even if it is kept at a high temperature of 825 ° C. for a time equivalent to brazing, the grain growth of the precipitate is delayed, Although it is somewhat larger, the yield strength is high because there are still many fine precipitates that contribute to the yield strength.
- heat treatment to restore thermal conductivity and electrical conductivity that is, cooling after brazing for 5 to 50 minutes in the temperature range from 650 ° C to 550 ° C in the cooling process after brazing, or after hard brazing Once air-cooled, and held at a temperature of 550 ° C. to 650 ° C.
- the yield strength is increased.
- the average crystal grain size of the hot forged product is 0.05 mm, 0.08 mm or more, so that even when heated to 825 ° C., the working strain introduced by cold working remains, and the strength corresponding to the strain Is added. That is, even if the hot forged product is heated to 800 ° C. or higher by brazing, the average crystal grain size is larger than 0.05 mm or 0.08 mm, so that the growth of the precipitated particles is delayed and there are many precipitated particles that contribute to the proof stress.
- a higher proof stress of 150 N / mm 2 or more is obtained.
- the hot forged product has a large diffusion rate and a low diffusion rate, and has heat resistance. Therefore, even when a high stress is applied, the amount of deformation is small.
- the material to which cold working is added has a higher proof stress, so that the amount of creep deformation is small.
- Examples of the method for producing the copper alloy hot forged product described above include the following first to third production methods.
- the heating temperature of the forging material subjected to hot forging before hot forging is 925 to 1025 ° C., and the average crystal grain size at the end of the heating of the forging material is 0.10 to It is 5.0 mm.
- the forging material as used in this specification means both the material before forging, and the material after forging.
- At least one hot forging of a forging material subjected to hot forging is performed at 700 ° C. or more, and after the hot forging, the forging material is cooled at a cooling rate of 12 ° C./second or more.
- the holding time is t hours. It is characterized by performing. Preferably, after the heat treatment, cooling is performed at a cooling rate of 0.1 ° C./min to 3 ° C./min until reaching 400 ° C.
- implementing hot forging at 700 degreeC or more means making temperature just before forging 700 degreeC or more.
- the copper alloy hot forged product manufactured by the second manufacturing method has X and P content [P] mass%, where X (% IACS) is the electrical conductivity after the hot forging and before the heat treatment.
- At least one hot forging of a forging material subjected to hot forging is performed at 700 ° C. or more, and the forging material is subjected to the temperature range from 650 ° C. to 550 ° C. after the hot forging. Is cooled at a cooling rate of 12 ° C./second or more, and is maintained for 10 to 200 minutes in the temperature range of 400 to 540 ° C. after the cooling.
- implementing hot forging at 700 degreeC or more means making temperature just before forging 700 degreeC or more.
- the copper alloy hot forged product is excellent in strength, proof stress, thermal conductivity, and electrical conductivity.
- FIG. 1 is a diagram illustrating an example of a diameter of a circumscribed circle circumscribing a crystal grain and a diameter of an inscribed circle inscribed in the crystal grain.
- FIG. 2 is a diagram showing the composition of the alloy that produced the hot forged product.
- FIG. 3 is a diagram illustrating manufacturing conditions for each step of Test 1.
- FIG. 4 is a view showing the shape of a flat plate hot forged in Test 1.
- FIG. FIG. 5 is a diagram showing manufacturing conditions for each step of Test 2.
- FIG. FIG. 6 is a diagram showing the results of Test 1.
- FIG. 7 is a diagram showing the results of Test 1.
- FIG. 8 is a diagram showing the results of Test 1.
- FIG. 9 is a diagram showing the results of Test 1.
- FIG. 9 is a diagram showing the results of Test 1.
- FIG. 10 is a diagram showing the results of Test 1.
- FIG. 11 is a diagram showing the results of Test 1.
- FIG. 12 is a diagram showing the results of Test 1.
- FIG. 13 is a diagram showing the results of Test 1.
- FIG. 14 is a diagram showing the results of Test 2.
- FIG. 15 is a diagram showing the results of Test 2.
- FIG. 16 is a photograph showing the metal structure in each test.
- the copper alloy hot forged product according to the embodiment of the present invention will be described.
- the first invention alloy to the third invention alloy are proposed.
- the element symbol in parentheses [] such as [Cu] indicates the content value (mass%) of the element.
- a plurality of calculation formulas are presented in this specification using this content value display method. In each calculation formula, the calculation is performed as 0 when the element is not contained.
- the first to third invention alloys are collectively referred to as invention alloys.
- the first invention alloy comprises 0.21 to 0.44 mass% Co, 0.06 to 0.13 mass% P, 0.003 to 0.08 mass% Sn, and 0.00003 to 0.0030 mass%. And the balance is Cu and inevitable impurities, and the content of Co is 3.1 ⁇ ([between the Co content [Co] mass% and the P content [P] mass%. Co] ⁇ 0.005) / ([P] ⁇ 0.006) ⁇ 4.9.
- the second invention alloy has the same composition range of Co, P, Sn, and O as the first invention alloy, and further 0.001 to 0.3 mass% Zn, 0.002 to 0.2 mass% Mg, An alloy composition containing one or more of 0.001 to 0.3 mass% Ag, the balance being Cu and inevitable impurities, Co content [Co] mass% and P content [P]
- the mass% has a relationship of 3.1 ⁇ ([Co] ⁇ 0.005) / ([P] ⁇ 0.006) ⁇ 4.9.
- the composition range of Co, P, Sn, O, Zn, Mg, Ag is the same as that of the first invention alloy or the second invention alloy, and 0.005 to 0.15 mass% of Ni
- the alloy composition further includes any one or more of 0.003 to 0.10 mass% Fe, the balance being Cu and inevitable impurities, Co content [Co] mass%, and Ni content [ Ni] mass%, Fe content [Fe] mass%, and P content [P] mass%, 3.1 ⁇ ([Co] + 0.9 ⁇ [Ni] + 0.8 ⁇ [Fe] ⁇ 0.005) / ([P] ⁇ 0.006) ⁇ 4.9, and 0.010 ⁇ 2 ⁇ [ Ni] + 3 ⁇ [Fe] ⁇ 0.75 ⁇ [Co].
- the manufacturing method includes a heating process for heating the forging material before hot forging, a hot forging process for forging the heated forging material, a cooling process for cooling the forging material after hot forging, and a forging after cooling. And a precipitation heat treatment step for heating the material.
- the heating temperature in the heating step is 925 to 1025 ° C.
- Hot forging is performed at least once, and at least the temperature immediately before forging is set to 700 ° C. or higher.
- the cooling step after the hot forging, the temperature is cooled to 400 ° C. or less at a cooling rate of 12 ° C./second or the temperature region from 650 ° C. to 550 ° C.
- the conditions of the precipitation heat treatment are as follows: heat treatment temperature is 450 to 600 ° C., holding time is 0.2 to 10 hours, heat treatment temperature is T ° C., and holding time is t hours, and 520 ⁇ T + 20 ⁇ t 1/2 ⁇ 615. Satisfy the relationship.
- cooling is preferably performed at a cooling rate of 0.1 ° C./min to 3 ° C./min until reaching 400 ° C. Cold work may be performed between the cooling step and the precipitation heat treatment step.
- the above manufacturing method is referred to as a first manufacturing method.
- what kind of manufacturing history of the forging material provided to the manufacturing method of the copper alloy hot forging product of this embodiment may be used. For example, it may be after casting, after extrusion, after hot forging, or after cold working.
- the hot forging step in the first manufacturing method the following may be performed.
- the temperature range from 650 ° C. to 550 ° C. is cooled at a cooling rate of 12 ° C./second or more, and then held in the temperature range of 400 to 540 ° C. for 10 to 200 minutes.
- the holding for 10 to 200 minutes in the temperature range of 400 to 540 ° C. serves as a precipitation heat treatment step in the first manufacturing method.
- the above manufacturing method is referred to as a second manufacturing method.
- the lower limit of the composition range of Co is 0.21 mass%, preferably 0.24 mass%, more preferably 0.27 mass%, and 0.35 mass% when particularly high proof stress is required. It is.
- the upper limit of the Co composition range is 0.44 mass%, particularly 0.43 mass%, when high proof stress is required, and is preferably 0.40 mass% or less in view of balance between proof stress and cost.
- the upper limit of the composition range of P is 0.13 mass%, preferably 0.12 mass% in relation to Co, in order to obtain high yield strength.
- the lower limit of the composition range of P is 0.060 mass%, preferably 0.070 mass%, and 0.090 mass% in order to obtain high yield strength.
- Both Co and P elements are indispensable elements for achieving the object of the present invention, and the appropriate blending ratio of Co, P, etc. does not impair the thermal conductivity and electrical conductivity, and the proof stress, heat resistance, and high temperature. Improve strength, strength after brazing, and high temperature creep strength. Co and P exhibit a great effect within the composition range of the alloy according to the invention, and as the upper limit of the composition range is approached, there is a balance with cost, but these characteristics are further improved. Co and P combine to precipitate ultrafine precipitates that contribute to strength. Co-addition of Co and P suppresses dynamic recrystallization during hot forging and delays the formation of static recrystallization immediately after hot forging. However, when the effect exceeds the upper limit of the composition range of the alloy according to the present invention, almost no improvement in properties is recognized, and the above-described defects start to occur.
- the ratio of Co and P is very important. If conditions such as composition, heating temperature, and cooling rate are aligned, Co and P form fine precipitates with a Co: P mass concentration ratio of about 4: 1 to about 3.5: 1. To do.
- the precipitate is, for example, Co 2 P or Co 2. It is represented by a compound formula such as a P, Co x P y, etc., and if it is approximately spherical or approximately elliptical and has a particle size of about 2 to 3 nm, it greatly contributes to strength.
- the average particle size of precipitates represented by a plane which is a cross section of the forged product
- 1.5 to 3.9 nm preferably 1.7 to 3.5 nm, optimally 1.
- 90%, preferably 95% or more of the precipitate is 0.7 to 7 nm, and most preferably 95% or more is 0.00.
- the thickness is 7 to 5 nm, and high strength can be obtained by uniformly depositing precipitates.
- Precipitates are uniformly and finely distributed, the sizes are uniform, and the finer the particle size, the more the particle size, strength and high temperature strength of the recrystallized part are affected.
- the 0.7 nm particle size is generally limited to the ultra high-pressure transmission electron microscope (Transmission-Electron-Microscope, hereinafter referred to as TEM), observed at 750,000 times, and using special software to identify and measure dimensions. Is the size of Therefore, even if a precipitate of less than 0.7 nm is present, it is excluded from the calculation of the average particle diameter, and the range of “0.7 to 7 nm” has the same meaning as “7 nm or less”. . Of course, the precipitate does not include a crystallized product generated in the casting stage.
- the distance between the adjacent precipitation particles of 90% or more of the precipitation particles is 100 nm or less, preferably 75 nm or less, or within 25 times the average particle diameter, or in any 200 nm ⁇ 200 nm region at the microscope observation position described later , It is defined that there are at least 25 or more, preferably 50 or more precipitation particles, that is, there is no large non-precipitation zone that affects characteristics in a standard microscopic region, that is, there is no non-uniform precipitation zone. it can.
- the average particle size of the precipitate exceeds 3.9 nm, the contribution to the strength decreases, and when the average particle size is 1.3 nm or 1.5 nm, the precipitate also has a high strength. Saturated and poor in thermal and electrical conductivity. When the size of the precipitate is smaller than 1.5 nm, the thermal conductivity and the electrical conductivity are inferior because it is difficult to deposit all of the precipitate when it is too fine. Furthermore, the average particle size of the precipitate is preferably 3.5 nm or less. In particular, when the metal structure after hot forging is composed of recrystallized grains, the alloy is strengthened by the precipitate. The particle size is preferably 3.5 nm or less, and optimally 3.1 nm or less.
- the lower limit side is preferably 1.7 nm or more from the viewpoint of thermal conductivity and electrical conductivity. Even if the average particle size is small, if the proportion of coarse precipitates is large, it does not contribute to the strength. That is, since large precipitated particles exceeding 7 nm do not contribute to the strength so much, the ratio of the precipitated particle size of 7 nm or less needs to be 90% or more, preferably 95% or more. Furthermore, if the precipitate is not uniformly dispersed, that is, if there is a non-precipitation zone, the strength is low. With respect to the precipitate, it is most preferable that the three conditions of the small average particle size, the absence of coarse precipitate, and the uniform precipitation are satisfied.
- the precipitate when the value of the precipitation heat treatment conditional expression described above and below is lower than the lower limit value, the precipitate is fine, but since the amount of precipitation is small, the contribution to strength is small and the thermal conductivity is also deteriorated.
- the value of the precipitation heat treatment condition is higher than the upper limit value, the thermal conductivity is improved, but the precipitate becomes larger, coarse particles exceeding 7 nm increase, the number of precipitate particles decreases, and the strength due to precipitation is increased. The contribution is reduced.
- Sn is a small amount of 0.003 mass% or more, and in the heating that is the first step of hot forging, at a temperature of 925 ° C. or more, the solid solution of Co and P is promoted by heating in a short time. On the other hand, the formation of dynamic recrystallization and static recrystallization during hot forging is suppressed. Sn is added even if the material temperature at the time of hot forging is locally lowered, the degree of work is locally different, or even if it takes time for hot forging, Has the effect of maintaining a molten state.
- Sn is added at the heating stage, which is the first stage of the hot forging process, to make the metal structure coarser and Co and P to be in a solid solution state faster.
- solution of Co, P, etc. Lowering the sensitivity, that is, maintaining the solution state, and depositing a large amount of precipitates mainly composed of Co and P at the time of final deposition, and depositing these precipitates finely and uniformly dispersed
- it promotes the coarsening of crystal grains at a high temperature of 925 ° C. or higher, which is heated before forging, and suppresses recrystallization nucleation during hot forging.
- thermal conductivity and electrical conductivity are generally proportional, but the combination of the hot forging process and Sn, which has the effect of precipitating Co, P, etc. to an ideal state, is proportional. Thermal conductivity is better than the relationship.
- thermal conductivity is better than the relationship.
- by improving the heat resistance of the matrix of the hot forged product by solid solution of Sn it has the effect of maintaining the proof strength after the hard brazing and improving the creep characteristics.
- the content of Sn is required to be 0.003 mass% or more, but in order to exert the effect more, 0.005 mass% or more is preferable and optimal. Is preferably 0.007 mass% or more.
- Zn, Mg, and Ag improve the strength of the alloy by solid solution strengthening, and at the same time maintain the solid solution state of Co and P in a series of hot forging processes like Sn. Has the function of delaying crystals. Zn further improves solder wettability and brazing. Zn or the like has an action of promoting uniform precipitation of Co and P. Ag and Mg improve the proof stress and the creep characteristics after hard brazing. When the contents of Zn, Mg, and Ag are less than the lower limit of the composition range, the above effects cannot be exhibited.
- the upper limit of the Zn composition range is preferably 0.2 mass% or less, and more preferably 0.1 mass% or less.
- the Mg content is preferably 0.003 mass% or more, and is preferably 0.005 mass% or more.
- the upper limit of the Mg composition range is preferably 0.1 mass% or less, and more preferably 0.05 mass% or less. 0.003 mass% or more is preferable and, as for content of Ag, 0.005 mass% or more is good.
- the upper limit of the composition range of Ag is preferably 0.2 mass% or less, and more preferably 0.1 mass% or less.
- Fe and Ni will be described. Fe and Ni partially replace the function of Co, and at the same time, function to make Co and P bond more effectively. Accordingly, when Ni and Fe are further added from the basic relational expressions of Co and P, the following two relational expressions are established.
- the precipitates are reduced, and the finer and uniform dispersion of the precipitates is impaired.
- Ni, P, or the like is excessively dissolved in the matrix, resulting in poor thermal conductivity and electrical conductivity, and at the same time, the desired high yield strength cannot be obtained.
- the precipitation heat treatment is performed under the conditions of the combination of Co, Ni, Fe and P and the precipitation heat treatment that can be industrially carried out in the present invention, the value is approximately 0. of ([Co] + 0.9 ⁇ [Ni] + 0.8 ⁇ [Fe]).
- P is generally 0.006 mass%, which does not correspond to the formation of precipitates and exists in a solid solution state in the matrix. Therefore, by subtracting 0.005 mass% and 0.006 mass% from the mass concentration of ([Co] + 0.9 ⁇ [Ni] + 0.8 ⁇ [Fe]) and P, respectively, the mass ratio of Co and the like to P is calculated. It is necessary to decide.
- the precipitates of Co and the like and P generally have a Co: P mass concentration ratio of 4.3: 1 to 3.5: 1.
- Co 2 P, Co 2.a P, or Co 1 mainly .b P it is necessary to part of Co is Ni, Co x replaced by Fe Ni y Fe Z P a, Co x Ni y P z, etc. Co x Fe y P z are formed. If fine precipitates based on Co 2 P or Co 2.x P y are not formed, the high yield strength, high thermal conductivity and electrical conductivity, which are the subject matter of the present invention, Creep characteristics cannot be obtained.
- Ni has a function of substituting Co under the co-addition with Co and P, and the amount of decrease in thermal conductivity and electrical conductivity due to Ni is small.
- the value of the formula ([Co] + 0.9 ⁇ [Ni] + 0.8 ⁇ [Fe] ⁇ 0.005) / ([P] ⁇ 0.006) is 3.1 to 4.9. Even if it deviates from the center value, it has a function of minimizing the decrease in conductivity.
- a hot forged product generally has a complicated shape and is hot-worked at various working rates depending on each part.
- the metal structure obtained by hot forging depends on the heating conditions of the forging material to be hot forged, the number of hot forgings, the hot forging temperature, etc. Is different.
- the proportion of recrystallized grains having an average crystal grain size of 0.050 mm to 0.50 mm and non-recrystallized 80% or more in total is required.
- the alloy of the present invention has the property of suppressing the formation of recrystallization nuclei during hot forging.
- the microstructure of the hot forged product is recrystallized. To do.
- the proportion of the recrystallized grains in which the average crystal grain size of the recrystallized grains is 0.050 mm or less is 20% or more, the average grain size of the Co and P precipitates generated during the next precipitation heat treatment is It becomes large, precipitation is slightly insufficient, and high yield strength cannot be obtained as a whole.
- the electrical and thermal conductivity also deteriorates.
- the average crystal grain size of the recrystallized grains is 0.050 mm or more, the average grain size of the Co and P precipitates generated during the precipitation heat treatment is reduced, and high yield strength is obtained as a whole.
- the average crystal grain size is 0.050 mm or more
- the diffusion of constituent elements such as Co, P and Sn is delayed, so that the heat resistance of the matrix is improved, Yield strength and creep characteristics can be improved in the operating environment of 100 to 200 ° C.
- the average crystal grain size is 0.050 mm or more
- the re-dissolution of Co and P can be delayed, and fine precipitates of Co and P can remain. Even after hard brazing, higher yield strength can be obtained.
- higher yield strength can be obtained.
- higher proof stress can be obtained.
- the average crystal grain size is 0.050 mm to 0.50 mm, and the average crystal grain size is preferably 0.070 mm or more, and most preferably 0.080 mm or more.
- the average crystal grain size exceeds 0.50 mm, a problem occurs in ductility. More preferably, it is 0.30 mm or less, and optimally 0.20 mm or less.
- strain can be accumulated in the crystal grains having an average crystal grain size of 0.1 mm or more generated during heating before hot forging. Combined with the presence of fine precipitated particles after the precipitation heat treatment, higher proof stress can be obtained. Further, the proof stress and creep characteristics at the use environment of 100 to 200 ° C. can be enhanced. Since the precipitated particles that precipitate in the unrecrystallized grains are slightly larger than the precipitates of the recrystallized grains having an average crystal grain size of 0.050 mm or more, the contribution of the precipitates to the proof stress is reduced. Since the strain at the time of hot forging increases, the contribution to the proof stress by the strain increases.
- the proof stress of the invention alloy having unrecrystallized grains is slightly higher, but the average grain size is 0.050 mm or more in total.
- the average grain size is 0.050 mm or more in total.
- the proportion of these accounts for 80% or more in total, high yield strength, high thermal conductivity It becomes a hot forged product having high electrical conductivity.
- it can have high yield strength and creep characteristics in the use environment of 100 to 200 ° C.
- the non-recrystallized structure produced by hot forging is similar in shape to that produced by cold forging and cold working, but has a lower dislocation density and is more ductile than that produced by cold working. It is out.
- the ratio of recrystallized grains having an average crystal grain size of 0.050 mm to 0.50 mm in the hot forged product becomes 60% or more, and high yield strength and high thermal conductivity A hot forged product having high electrical conductivity is obtained.
- the processing rate is generally low.
- the crystal grains of the forging material before hot forging are coarsened 3. Since the hot forged product is large, static recrystallization is likely to occur and crystal growth is likely to occur.
- the proportion of the recrystallized grain group having an average crystal grain size of 0.080 mm to 0.30 mm is 60% or more, or
- the proportion of the recrystallized grain group having an average crystal grain size of 0.050 mm to 0.50 mm is 80% or more, and optimally, the recrystallized grain group having an average crystal grain size of 0.080 mm to 0.20 mm Is 80% or more.
- the average crystal grain size is more preferably 0.30 mm or less, and optimally 0.20 mm or less.
- a hot forged product in which the proportion of recrystallized grains having an average grain size of 0.050 mm to 0.50 mm before precipitation heat treatment is 60% or more is precipitated after hot forging.
- the proof stress is 60 to 130 N / mm 2
- the Vickers hardness is 50 to 85
- the conductivity is 33 to 49% IACS. Since the strength before the precipitation heat treatment is low, it is easy to correct or form the target shape.
- 1-20% light cold working may be performed after the hot forging and before the precipitation heat treatment.
- the yield strength of the hot forged product after heat treatment is significantly improved. Specifically, a yield strength of 280 to 390 N / mm 2 is obtained by cold working of 5 to 15%, and a more suitable heat sink or hot forged product for end rings is obtained. Furthermore, the proof stress and creep characteristics at 100 to 200 ° C., which is the usage environment, can be improved. Specifically, when a stress of 100 N / mm 2 was applied at 200 ° C. and a 1000 hour creep test was performed, the total creep deformation amount excluding initial deformation was excellent in creep deformation resistance of 0.15% or less. Become a hot forged product.
- the metal structure of the hot forged product is in an unrecrystallized state in the following cases. 1. 1. When hot forging rate is large 2. When the temperature is drastically reduced, including during hot forging, in places where thin forging is performed, and there is no time for dynamic and static recrystallization to occur. When the hot forging temperature is low Even if the hot forging temperature is low and the metal structure of the hot forged product is in an unrecrystallized state, the forged material is heated at least once to 925 ° C.
- the precipitates are fine, the alloy is strengthened, and at the same time, accumulated strain corresponding to the unrecrystallized state during hot forging remains after heat treatment, which is added, so high proof stress and high thermal conductivity High electrical conductivity can be obtained. Furthermore, since the original crystal grains are in an unrecrystallized state, the disappearance of the precipitates is delayed even when hard brazing is performed, and the proof stress and creep characteristics at 100 to 200 ° C., which is the use environment, can be improved. When the proportion of non-recrystallized grains is 60% or more, a hot forged product having high yield strength, high thermal conductivity, and high electrical conductivity can be obtained. As a more preferable condition, the proportion of non-recrystallized grains is 80% or more.
- the heating temperature before forging needs to heat the forged material to 925 ° C. or higher (preferably 940 ° C. or higher).
- 925 ° C. or higher there is an effect of inclusion of Sn, so that Co and P are dissolved in the matrix and the effect of suppressing the growth of crystal grains due to the precipitate of Co and P is lost, so the average crystal grain size is 0.10 mm or more It becomes a coarse metal structure.
- the solid solution state of Co and P is maintained.
- the forging material is forged 10 times or more, and it takes 5 to 15 minutes from the start to the end of hot forging. If the final hot forging temperature is at least 700 ° C or more, Most of Co, P is in a solution state.
- the average crystal grain size to be generated is 0.050 mm or more, further 0.080 mm or more, or The crystal grains having an average crystal grain size of 0.1 mm or more formed during hot forging heating are distorted, that is, in an unrecrystallized state.
- the crystal grains of the hot forged product are large, the re-solution of Co and P precipitated by the precipitation heat treatment is delayed at the time of brazing at about 800 ° C.
- the heating temperature is lower than 925 ° C. and the average crystal grain size is less than 0.10 mm, the solid solution state of Co, P, etc. is not maintained as the temperature decreases during hot forging and the hot forging time elapses.
- Precipitation of coarse precipitates that do not contribute much to the strength begins, and even if precipitation heat treatment is performed after forging, the remaining yield is reduced, so that high yield strength cannot be obtained.
- the particles precipitated by this precipitation heat treatment are larger than when the average crystal grain size is once coarsened to 0.1 mm or more, high yield strength cannot be obtained, and high creep characteristics cannot be obtained. Also, electrical and thermal conductivity is poor.
- the forging material is heated to 925 ° C. or more and forged at a temperature of 850 ° C. or less, the cooling rate is high in the thin wall portion, the crystal grains of the forging material are coarsened by heating, Co, P, etc.
- the metal structure becomes an unrecrystallized state.
- the maximum temperature reached is 925 ° C. or higher, then lowered to a predetermined temperature between 700 ° C. and 850 ° C., and the temperature is intentionally controlled in the furnace, By subjecting to forging, a desired non-recrystallized structure can be stably obtained.
- the alloy is strengthened by the effects of both the accumulated strain due to the unrecrystallized state and the precipitation of fine precipitates after the precipitation heat treatment. If the average cooling rate from 925 ° C. to the predetermined temperature is 3 ° C./min or more, preferably 5 ° C./min or more, the solid solution state of Co and P in the alloy is almost maintained. Moreover, since the temperature during hot forging is around 800 ° C., the crystal grains of the forged material are coarsened, Co, P, etc. are in a solid solution state, and Sn is contained. Even in the thick part having a low rate, the metal structure is partially unrecrystallized.
- the hot deformation resistance increases, so in view of the relationship between the power of the forging machine and the formability.
- the forging temperature may be determined. Even if the forging temperature is lowered, as described above, Co and P are in a solid solution state even if a time elapses until the predetermined low temperature is reached from the maximum attained temperature. Compared to copper alloys, the hot deformation resistance is much lower and the deformability is superior.
- the crystal grains of the forged material before forging are grown to change the average crystal grain size from 0.10 mm to 5.0 mm.
- the crystal grain size By setting the crystal grain size to 0.10 mm or more, most of Co, P, etc. can be in a solid solution state.
- the crystal grains of the material are coarsened at a high temperature, even if the forging temperature is intentionally lowered (the temperature immediately before forging is 700 ° C. or higher), the temperature decreases and the time is reduced by hot forging a plurality of times. Even if it is applied, Co, P, etc. can be kept in a solid solution state.
- the metal structure When the coarsened crystal grains are hot forged at a temperature of 850 ° C. or less, the metal structure can be brought into an unrecrystallized state, and when it is in an unrecrystallized state, strain can be accumulated in the hot forged product. .
- precipitates of Co and P are finely precipitated, and strain accumulated during hot forging is further added, so that the proof stress after precipitation heat treatment can be increased. Further, the proof stress and creep characteristics at 100 to 200 ° C., which is the use environment, can be enhanced.
- the forging temperature for making non-recrystallized grains is more preferably 830 ° C. or lower, and the lower limit is preferably 720 ° C.
- the electrical conductivity after hot forging and before heat treatment:% IACS is (45-25 [P] -20 [Co] -10 [Fe] -5 [Sn] -3 [Mg] -2 [Ni]) or more, and (55-25 [P] -20 [Co] -10 [Fe] -5 [Sn] -3 [Mg]- 2 [Ni]) or less is preferable.
- the lower limit is an ideal numerical value in which Co, P, etc. are in a solid solution state for industrial hot forging
- the upper limit is a numerical value of the limit where the precipitation margin remains in the forged product to achieve the present application. .
- the upper limit side is preferably (52-25 [P] -20 [Co] -10 [Fe] -5 [Sn] -3 [Mg] -2 [Ni]).
- the electrical conductivity after forging is 33 to 49% IACS, and the electrical conductivity after heat treatment is 75% IACS or more. Therefore, the larger the difference, the larger the precipitation amount. It is shown that. From the viewpoint of the amount of precipitation, the difference in conductivity before and after the precipitation heat treatment needs to be 32% IACS, preferably 36% IACS or more, and most preferably 40% IACS or more.
- the heating does not reach a predetermined temperature, for example, heating at 900 ° C., since the solid solution of Co, P, etc. is almost finished, hot forging immediately after heating, and immediately water cooling, when performing precipitation heat treatment, It is possible to reach the target near proof strength.
- a predetermined temperature for example, heating at 900 ° C., since the solid solution of Co, P, etc. is almost finished, hot forging immediately after heating, and immediately water cooling, when performing precipitation heat treatment, It is possible to reach the target near proof strength.
- a predetermined temperature for example, heating at 900 ° C., since the solid solution of Co, P, etc. is almost finished, hot forging immediately after heating, and immediately water cooling, when performing precipitation heat treatment, It is possible to reach the target near proof strength.
- the heating temperature is lower than 925 ° C., Co and P do not maintain a solid solution state, and large precipitated particles are precipitated.
- the precipitated particles that precipitate are larger when the forged material is heated to 925 ° C. or higher before hot forging.
- the average precipitated particle size becomes large, and precipitates with a size of more than 4 nm or 0.7 to 7 nm are less than 90% and do not reach the required yield strength.
- the heating of the forging material is lower than 925 ° C. in terms of metal structure, the crystal grains do not become large, and the metal structure after hot forging is a ratio of an average crystal grain size of 0.05 mm or less even if it is recrystallized grains There are many.
- the crystal grain of the original forging material is small.
- the grain size of the precipitated particles is increased, the yield strength is lowered, the creep characteristics at 100 to 200 ° C. are also degraded, and the yield strength is lowered and the creep characteristics are degraded even after brazing.
- the final forging should be performed at least at a forging temperature of 700 ° C. or higher, and preferably at 730 ° C. or higher in view of formability and cooling during forging. There is.
- cooling after hot forging After hot forging at a temperature of 700 ° C. or higher, rapidly cool to 400 ° C. or lower at a cooling rate of 12 ° C./second or more, preferably 20 ° C./second or higher, or after hot forging, a temperature range of 650 ° C. to 550 ° C. It is an absolute condition at the time of cooling that it passes through at a cooling rate of 12 ° C./second or more, preferably 20 ° C./second or more. In general, water cooling is preferable, but it is necessary to quickly pass through a region of 650 ° C. to 550 ° C. of the temperature at which precipitation starts.
- the precipitation heat treatment After cooling after hot forging, a precipitation heat treatment is performed in order to precipitate Co and P that are dissolved.
- the strength after the heat treatment depends on the size of the precipitated particles.
- the strength of the copper alloy hot forged product increases as the particle size of the precipitated particles decreases.
- the conditions for the precipitation heat treatment satisfy the relationship of 520 ⁇ T + 20 ⁇ t 1/2 ⁇ 615, where the heat treatment temperature is T ° C. and the holding time is t hours. In the above relational expression, T ° C. is 450 to 600 ° C., and t time is 0.2 to 10 hours.
- a more preferable range of the precipitation heat treatment is 530 ⁇ T + 20 ⁇ t 1/2 ⁇ 590, T ° C. is 470 to 570 ° C., and t time is 0.3 to 8 hours.
- the temperature range from the temperature after the predetermined precipitation heat treatment to 400 ° C. is cooled at a cooling rate of 3 ° C./min or less, the electrical / thermal conductivity is improved.
- the conductivity is improved by about 2% IACS. Note that this effect is almost saturated at a cooling rate of 0.3 ° C./min.
- the basis of the precipitation heat treatment is reheating after cooling as described above.
- the temperature range from 650 ° C. to 550 ° C. is passed, and then the region of 540 to 400 ° C.
- the cooling may be performed at a cooling rate of 2 ° C./min or less, or the temperature may be maintained. Co and P precipitates finely.
- the cooling time or holding time in the region of 540 to 400 ° C. is sufficiently effective when it is 10 to 200 minutes, and cooling that also serves as precipitation can be performed.
- Forged materials are not uniform during hot forging due to differences in the state of the metallographic structure, whether they are recrystallized grains or non-recrystallized grains, average grain size, residual processing strain, etc. It is in a state. However, this heat treatment performs a precipitation process and eliminates residual stress, so that the metal structure can be made uniform.
- ⁇ Cold working may be performed between the cooling after hot forging and the precipitation heat treatment.
- cold working for example, cold forging, improves proof stress and creep characteristics without impairing thermal conductivity and electrical conductivity.
- the average crystal grain size of the hot forged product is 0.05 mm or more in the thick part, preferably 0.08 mm or more, or the original average crystal grain size of the non-recrystallized part is coarsened to 0.1 mm. Therefore, even if the condition of hard brazing is a high temperature of 800 ° C., the re-solution of Co and P can be delayed for a short time. Further, when cold working is performed, recovery of the working strain is delayed, so that the proof stress and the creep characteristics after hard brazing are enhanced.
- the thermal conductivity and electrical conductivity deteriorate. This is because Co and P are dissolved again in a short time even at a high temperature of 800 ° C., but Co and P are dissolved, and it is necessary to reprecipitate Co and P. There is.
- the cooling process after brazing hold at a temperature of 500 to 650 ° C. for 5 to 100 minutes.
- Considering productivity hold at a temperature of 550 to 650 ° C. for 5 to 50 minutes, or a temperature range of 550 to 650 ° C. May be cooled over 5 to 50 minutes.
- This heat treatment after brazing is mainly for the purpose of improving the thermal conductivity and electrical conductivity, and is different from the precipitation heat treatment after hot forging that improves the yield strength, thermal conductivity and electrical conductivity.
- Example 2 shows the composition of the alloy that produced the hot forged product.
- pure copper C1220 and C1020 were also used.
- a copper alloy hot forged product was manufactured as follows. First, the raw materials were melted by an electric furnace in actual operation, the composition was adjusted, and a billet having an outer diameter of 240 mm and a length of 700 mm was manufactured. The billet was heated at 870 ° C. for 2 minutes, and a bar with an outer diameter of 36.5 mm was extruded with an indirect extruder.
- the extrusion capacity of the indirect extruder was 2750 tons.
- the average crystal grain size of the hot extruded material was 0.030 mm to 0.045 mm in all cases.
- a hot extruded material as a forged material, a copper alloy hot forged product was manufactured by a plurality of processes in which the heating temperature before forging, the forging temperature, the forging end temperature, the cooling rate after forging end, and the precipitation heat treatment conditions were changed.
- FIG. 3 shows the manufacturing conditions for each step.
- Steps A, A-1, A-2, C, E, F, G, H, and H-1 are steps suitable for the first manufacturing method described above.
- Steps D, I, and J are steps of a comparative example of the first manufacturing method.
- Step B was a step suitable for the above-described second production method, and after hot forging, it was immersed in a salt bath at 500 ° C. and held for 30 minutes.
- Process S is a process suitable for pure copper C1220 and
- FIG. 4 shows the shape of a hot-forged flat plate. The longitudinal direction of the flat plate corresponds to the extrusion direction of the hot extruded material. After heating before hot forging, the metal structure of the cross section was observed by water cooling. One of the forged products was directly subjected to a tensile test with an Amsler universal testing machine to determine the yield strength.
- One of the forged products is the thick part X part (two places), the thin part Y part, the thick and thin boundary part Z part cut out, X, Y part is Amsler universal testing machine
- Tensile tests were conducted to measure proof stress, elongation, and tensile strength. Two of the forgings were cut at any point, and the metal structure was observed at each of the X, Y, and Z parts of one forging, and the presence or absence of recrystallization, the average crystal of the recrystallized grains The particle size was determined.
- the thermal conductivity and electrical conductivity of the X and Y parts were measured. The average values of the X and Y parts were adopted for the thermal conductivity and electrical conductivity of the forged product.
- brazing equivalent test One X part was cut out from the forged product, applied with a stress of 50 N / mm 2 at 200 ° C., subjected to a creep test for 1000 hours, and the total creep deformation except the initial deformation was measured.
- two X parts were cut out from the forged product, a test corresponding to brazing, that is, heating for 300 seconds in a salt at 825 ° C. corresponding to the actual Ag brazing conditions, air-cooling, and again with a salt bath at 590 ° C. It was subjected to a heat treatment of immersion for 30 minutes and air cooled (hereinafter, this test is referred to as a brazing equivalent test).
- test 2 an ingot having a diameter of 240 mm and a length of 80 mm was heated to 950 ° C., and hot forging was repeated to obtain a hot forged piece having an outer diameter of about 300 mm, an inner diameter of about 90 mm, and a height of about 50 mm.
- the forging end temperature was 650 ° C., and air cooling was performed after forging.
- a hot forged product was produced by a plurality of processes with different production conditions.
- the forged material was reheated in a gas furnace and formed into a ring having an outer diameter of about 350 mm, an inner diameter of about 200 mm, and a height of about 50 mm by hot forging.
- the number of forgings is about 20 times. Some were further cold forged to a height of 44 mm. This processing corresponds to a cold working rate of 12%.
- the production conditions were such that the heating temperature before forging, forging temperature, forging end temperature, cooling rate after forging end, and precipitation heat treatment conditions were changed.
- FIG. 5 the manufacturing conditions of each process are shown. Steps K, K-1, L, and M are steps suitable for the first manufacturing method described above. Steps N, O, P, Q, and R are steps of a comparative example of the first manufacturing method.
- Process T is a process suitable for pure copper C1220 and C1020.
- a stress of 50 N / mm 2 was applied at 200 ° C.
- the one subjected to cold forging was applied with a stress of 100 N / mm 2 at 200 ° C. and subjected to a creep test for 1000 hours.
- the brazing equivalent test was heated in a salt bath at 825 ° C. for 300 seconds with or without cold forging. After air cooling, it was again immersed in a salt bath at 590 ° C. for 30 minutes, subjected to precipitation heat treatment mainly for recovery of thermal and electrical conductivity, and then air cooled. In addition, about the test using C1020 and C1220, this precipitation heat processing is not given. The proof stress, thermal conductivity, and electrical conductivity of this brazed equivalent specimen were measured. Furthermore, a brazing equivalent test piece was processed, a stress of 50 N / mm 2 was applied at 200 ° C., a 1000 hour creep test was performed, and the total amount of creep deformation except initial deformation was measured.
- the tensile test was performed as follows. For the ring forged product of the thick wall part (X part) and test 2, the test piece was cut out and tested according to the No. 4 test piece of the metal material tensile test piece of JIS Z 2201. However, the diameter of the parallel part was 10 mm, and the gauge distance was 4 ⁇ A 1/2 (A is the cross-sectional area of the parallel part). For the ring forged product of Test 2, a rectangular parallelepiped having a 20 mm ⁇ 20 mm cross section including the surface in the center in the width direction and cut into a length of 160 mm was used as a test piece. The thin part (Y part) cut out a test piece and tested it according to the No. 4 test piece of the metal material tensile test piece of JIS Z2201. However, the diameter of the parallel part was 5 mm, and the gauge distance was 4 ⁇ A 1/2 (A is the cross-sectional area of the parallel part).
- the recrystallized grain has a shape close to a regular hexagon.
- the ratio of (diameter of circumscribed circle of crystal grain) / (diameter of inscribed circle of crystal grain) is: Most recrystallized grains are less than 2.0. Therefore, a crystal grain having a ratio of (diameter of circumscribed circle of crystal grain) / (diameter of inscribed circle of crystal grain) of 2.0 or more is determined as an unrecrystallized grain.
- the recrystallized grain group and the method for measuring the average crystal grain size of the recrystallized grain group in this specification will be described.
- the average crystal grain size of the recrystallized grains is measured according to JIS H 0501.
- the metal structure is observed with a magnification of 75 and a visual field of 50 mm ⁇ 70 mm.
- the crystal grain size is 37.5 times in the case of coarse crystal grains with a boundary of 0.15 to 0.20 mm.
- a group of all the recrystallized grains in the visual field is set as a recrystallized grain group in the visual field.
- the recrystallized grains in the field of view are the recrystallized grain group in which the average crystal grain size of the recrystallized grains is amm.
- the metal structure of the observed visual field is non-recrystallized, all the visual fields are non-recrystallized grains. In this way, 10 visual fields are observed uniformly from the entire cross section of the metal to be observed, and it is determined for each visual field whether it is a recrystallized grain or an unrecrystallized grain. And when the observed visual field is a recrystallized grain, an average crystal grain diameter is measured.
- the proportion of the recrystallized grain group in which the average crystal grain size of the recrystallized grains falls within a predetermined range in the cross-sectional metal structure is calculated. For example, out of 10 fields, 1 field is unrecrystallized grains, 9 fields are recrystallized grains, and among 9 fields that are recrystallized grains, the average grain size of 8 fields is 0.050 to 0.00. It is assumed that the average crystal grain size in one field of view is 0.01 mm. In this case, the proportion of the recrystallized grain group in which the average crystal grain size of the recrystallized grain is 0.050 to 0.50 mm is 80%, and the proportion of the non-recrystallized grain is 10%.
- the observed visual field is a visual field in which unrecrystallized and recrystallized are mixed, unrecrystallized grains and recrystallized grains (including fine crystal grains) are separated, and the recrystallized portion is image processing software.
- WinROOF binarized by “WinROOF” and the area ratio is less than 20%, it is determined as a field of unrecrystallized grains, and when it is 80% or more, it is determined as a field of recrystallized grains. It was assumed that neither the recrystallized part nor the non-recrystallized part belonged.
- the recrystallized region and unrecrystallized depending on the degree of residual processing strain from the grain map by 200x EBSP (Electron Backscatter Diffraction Pattern).
- the areas were distinguished, and the area ratio of the areas was measured by image analysis (binarization with image processing software “WinROOF”).
- WinROOF image processing software
- the measurement of the particle size of the precipitated particles was performed as follows.
- the transmission electron image of a 750,000-fold TEM (transmission electron microscope) is binarized by image processing software “WinROOF” to extract precipitates, calculate the average value of the area of each precipitate, and calculate the average particle diameter. It was measured.
- the measurement positions were 2 points of 1h / 4 from both surfaces, where h is the thickness of the test piece, and the average value was taken. Further, the ratio of the number of precipitates having a particle size of 7 nm or less was measured from the particle size of each precipitate, but those having a particle size of less than 0.7 nm were judged to have a large error and excluded from the precipitated particles (recognition). Did not).
- the electrical conductivity was measured using a conductivity measuring device (SIGMATEST D2.068) manufactured by Nippon Ferster Co., Ltd. Electrical conductivity and conductivity are synonymous.
- the thermal conductivity was measured by measuring the thermal conductivity at 20 ° C. by the laser flash method.
- Creep characteristics were measured by the following creep test. Various test pieces were cut out and performed in accordance with a tensile test method for a metal material of JIS Z 2271. The test piece had a parallel part diameter of 8 mm and a gauge distance of 40 mm. In the creep test, for forged products and ring forged products (Test 2), a stress of 50 N / mm 2 was applied, and the total creep deformation amount at 200 ° C. for 1000 hours and the total creep deformation amount excluding the initial deformation were obtained. It was. For a ring forged product to which cold working (forging) was applied, a stress of 100 N / mm 2 was applied, and the total creep deformation amount at 200 ° C.
- the results of Test 1 are shown in FIGS. 6 to 13, the results of Test 2 are shown in FIGS. 14 to 15, and photographs of the metal structures in several tests are shown in FIG.
- the result of the X part of the test piece is shown in the row X of the part column
- the result of the Y part of the test piece is shown in the Y row.
- the average value of the measurement in the X, Y and Z parts is described in the item relating to the crystal grain size, and the items relating to the grain size of the precipitate, the thermal conductivity, and the conductivity.
- step A-O describes the mechanical properties after cooling in step A.
- a certain copper alloy hot forged product was excellent in strength, yield strength, thermal conductivity, electrical conductivity and the like.
- a copper alloy hot forging in which the total proportion of the recrystallized grains in which the average crystal grain size of the recrystallized grains is 0.080 to 0.30 mm and the ratio of the unrecrystallized grains is 80% or more
- the product was excellent in these properties including creep resistance.
- Both the process B including a simple continuous heat treatment process after forging, the process G including two forging processes, and the processes E and F having different forging temperatures exhibited good characteristics.
- it since it is hot forging which does not use the process which requires the cost of solution treatment etc., it becomes low cost (refer process A, B, C, E, F, G, H etc. of alloy No.11).
- the alloy of the third invention wherein the total proportion of the recrystallized grains in which the average crystal grain size of the recrystallized grains is 0.050 to 0.50 mm and the ratio of the non-recrystallized grains is 80% or more
- a certain copper alloy hot forged product was excellent in strength, proof stress, thermal conductivity, electrical conductivity, etc. as in the case of the first invention alloy (Steps A, B, E, F, and Alloy No. 31). (See G, H, etc.). 4).
- the average grain size of the precipitates in the recrystallized grains is 1.3 to 3.9 nm, or 90% or more of the precipitates is 0.7 to 7 nm, it has high yield strength, high thermal conductivity, and high electrical conductivity.
- the average crystal grain size of the forged material before forging does not become 0.1 mm or more. If the average crystal grain size is not 0.1 mm or more, the thin crystal part of the hot forged product becomes non-recrystallized grains or even if recrystallized, the average crystal grain size does not become 0.05 mm or more. Even in the thick-walled portion of the hot forged product, it is difficult to obtain a crystal grain having a small proportion of recrystallized grains with an average crystal grain size of 0.050 mm or more and an average crystal grain size larger than 0.08 mm.
- step E and step F the heating temperature of the forging material is the same, and the average crystal grain size of the material is 0.1 mm or more.
- the forging temperature and the end temperature are different, in the thick part, although both steps are recrystallized, there is a difference in the proportion of the crystal grain size of 0.08 mm or more.
- the process F is larger.
- the process E has slightly higher yield strength, electrical conductivity, and thermal conductivity.
- the process F is in an unrecrystallized state, so the precipitated particle size is slightly larger than that in the process E.
- the test results show that the yield strength is slightly high and the thermal conductivity and electrical conductivity are slightly low due to the unrecrystallized state of the process F.
- the temperature of the hot forging should be appropriately changed depending on the restrictions of the process / equipment, the shape of the forged product, the proof stress and the heat conductivity / electric conductivity. 8).
- the cooling rate to 400 ° C. is cooled at 0.8 ° C./min, there is almost no change in properties such as strength and heat resistance, and the conductivity is improved by about 2% IACS.
- Co, P, etc. are further finely precipitated by slowing down the cooling after the heat treatment. Even if the cooling rate is slowed, the strength and conductivity characteristics of the comparative example alloy are only slightly improved.
- step A-1 When precipitation heat treatment is performed with 525 ⁇ T + 20 ⁇ t 1/2 ⁇ 570, the strength increases.
- heat treatment is performed with 560 ⁇ T + 20 ⁇ t 1/2 ⁇ 605, the electrical / thermal conductivity increases.
- the temperature conditions are increased, the precipitated particles become slightly larger, but the average particle diameter is smaller than 3.9 nm, and 90% or more of the precipitates are 0.7 to 7 nm, so the strength is slightly reduced. It is considered that the electrical and thermal conductivity is increased because more Co and P can be deposited.
- Step I as in Step F, an unrecrystallized structure is formed.
- the ratio of the non-recrystallized structure is smaller than that in Step F, the conductivity after forging is high, and the precipitation margin is small. Is low and has poor electrical and thermal conductivity.
- Processes E, F, G, and H-1 have a lower forging temperature than Process A, but it is confirmed that the solid solution state of Co and P is maintained from the conductivity of the forged product and the precipitated particle size. it can.
- Step H-1 since the crystal grains of the forged material are large and the forging temperature is low, the forged product is in an unrecrystallized state at most sites.
- the forging temperature is low, the solid solution state of Co and P is maintained, and the strength is high due to the unrecrystallized structure and precipitation. Moreover, even if it is a non-recrystallized structure, there is little fall of ductility. If the forging conditions are appropriately selected according to the shape of the forged product, the application, and the power of the forging machine, a product with more excellent characteristics can be obtained. 10. The influence of the metal structure after hot forging will be described. If the average crystal grain size is 0.1 mm or more at the stage of heating the forged material before hot forging, the average crystal grain size is 0.05 mm or more in the thick part even after hot forging, and further 0 0.08 mm or more.
- the average crystal grain size of the hot forged product is large and fine precipitates are deposited, the heat resistance and strength are increased.
- the average crystal grain size is large, the diffusion of the constituent elements is delayed, creep deformation depending on the diffusion at the atomic level is difficult to occur, and the re-dissolution of the precipitate is delayed even when heated to a high temperature. As a result, even if a heat treatment equivalent to brazing is performed, high strength is maintained and it is resistant to creep deformation. 11. A portion to which a high processing rate is added during hot forging becomes an unrecrystallized state when the hot forging temperature is lowered. By setting the average crystal grain size to 0.1 mm or more in the heating stage before hot forging, the size of the precipitate after precipitation heat treatment becomes finer, and distortion due to the non-recrystallized state is added. Will have.
- the proof stress and thermal conductivity High electrical conductivity.
- the part (mainly X part) of only the recrystallized grains having an average crystal grain size of 0.05 mm or more the part of only non-recrystallized grains (mainly the Y part), and the whole part where these are mixed, Differences in yield strength, thermal conductivity and electrical conductivity are small.
- the average grain size is 0.1 to 5 mm at the stage of the forged material before forging, it can be forged regardless of the hot forging start temperature and end temperature (however, the end temperature is 700 ° C. or higher).
- the metal structure is mainly composed of a recrystallized grain structure with an average crystal grain size of 0.05 mm or more or a non-recrystallized grain structure, so that it exhibits excellent proof stress, thermal conductivity, and electrical conductivity. . 13.
- the influence of the cooling rate after hot forging is described. When the cooling rate from 650 ° C. to 550 ° C. after hot forging is slow, the yield strength, thermal conductivity and electrical conductivity after the precipitation heat treatment are lowered.
- the average crystal grain size after hot forging is increased to 0.08 mm or more, so the grain growth of precipitates is delayed.
- the precipitate becomes somewhat larger, or the re-dissolution of the precipitate is delayed.
- the average crystal grain size of the original hot forged product is small and the precipitates are large, and the precipitates are further coarsened or the re-dissolution of the precipitates is increased, so that the proof stress and heat conduction are increased. Poor property and electrical conductivity.
- the ring hot forged product according to the present invention has a high yield strength when subjected to 12% cold working after hot forging.
- the hot forged product according to the present invention has higher strength than the comparative example, and has a large average crystal grain size, so the diffusion rate is slow, so it has high heat resistance and the amount of creep deformation is small. .
- the one to which cold forging is added has a higher yield strength and a large amount of processing strain, so that the amount of creep deformation is small. 16.
- the precipitated particles of the forged product are large, so the yield strength is low and the heat resistance is poor, so the creep characteristics are also low.
- the Sn content is less than the composition range of the alloy according to the invention, all Co and P are not dissolved in a short time, so that coarse precipitates remain.
- the precipitates are partially coarsened during the hot forging, and the precipitates after the heat treatment increase as a whole, so that the yield strength, thermal conductivity, and electrical conductivity are lowered. 21.
- Copper alloy hot forgings include heat sinks (hybrid cars, electric vehicles, computer cooling, etc.), heat spreaders, motor rotor bars and end rings, power relays, power module members, battery terminals, electrical components (residues). Tools, fasteners, electrical wiring devices, electrodes, relays, connection terminals, male terminals, etc.), aircraft / rocket members, welding members, solar power generation, power modules and fusion equipment heat sinks It is.
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Abstract
Description
また、半導体素子の高集積化・大容量化に伴い、自動車の高出力モーター制御装置用の半導体素子等に使用され半導体に生じる熱を放出させるためのヒートシンクやヒートスプレッダには、フィン部等によりヒートシンクやヒートスプレッダ全体の表面積を広げて半導体で発生した熱を効率良く放出する高い熱伝導性が要求される。
更に、ヒートシンク等は、より多くの熱を放出させるために水冷方式によってその効率を更に高めて使用することが考えられるが、その場合、水圧に耐えうる強度、特に初期の変形強さ、すなわち耐力が大きいことが必要である。また、これらのヒートシンクには、優れた放熱性が必要であるが、組立工程時や実装時に加えられるはんだ付けや硬ろう付け時の温度によって強度や硬さが低下しないことが必要である。そして、使用中に温度上昇があっても、それに耐えることができる高いクリープ特性が必要である。
また、モーターに使われるエンドリングについては、ローターバーとの接合が硬ろう付けによって行われ、ろう付け後も高い強度と高い熱伝導性、電気伝導性が必要である。そして、使用中に100℃を超える温度上昇があるので、排熱(熱伝導)性に優れることが求められる。また、高速で運転すると大きな遠心力が生じるので、その遠心力に耐えうる高い強度、すなわち100℃を超える環境での高いクリープ特性が求められる。ヒートシンクやコネクター、電極等も同様であり、連続して長時間の使用に耐えうる高いクリープ特性が求められる。
このように、上記のような用途に用いられる銅合金には、高い強度、耐力、熱伝導性、電気伝導性、クリープ特性が求められる。
そのために、1つの工程でニアネットシェイプまで作る方法として熱間鍛造によって製造することが望ましい。熱間鍛造なら、小さなプレス能力の鍛造機でも複雑な形状に成形することができ、低コストである。
しかしながら、特許文献1に記載された銅合金は、特別な溶体化処理が必要であり、また、電気・熱伝導性が悪いという問題がある。
より好ましくは、耐力が、250N/mm2以上、20℃における熱伝導率が310W/m・K以上、又は導電率が77%IACS以上であり、耐力と熱伝導率との積が82000以上、又は、耐力と導電率との積が、20000以上である。最適には、純銅と同等の高熱伝導性、高電気伝導性を有し、耐力においては遥かに高い数値で、耐力が、260N/mm2以上、20℃における熱伝導率が320W/m・K以上、又は導電率が80%IACS以上であり、耐力と熱伝導率との積が85000以上、又は、耐力と導電率との積が、21000以上である。
そして、200℃で50N/mm2の応力を加え、クリープ試験を行った時、初期の変形を除いた全クリープ変形量が0.05%以下であることを特徴とする。後述するように、熱間鍛造後、析出熱処理前に、冷間加工を5~20%を施すと、200℃で100N/mm2の応力を加え、1000時間のクリープ試験を行ったとき、初期変形を除いた全クリープ変形量が0.15%以下であることを特徴とする。
すなわち、当該鍛造品をAgろう付け条件に相当する825℃のソルトバスで300秒間浸漬し、加熱した材料において、耐力が、125N/mm2以上、好ましくは130N/mm2以上、20℃における熱伝導率が280W/m・K以上、又は導電率が70%IACS以上であり、耐力と熱伝導率との積が38000以上、又は、耐力と導電率との積が、9600以上であることを特徴とする。そして、硬ろう付け相当の熱処理を行った熱間鍛造品に、200℃で50N/mm2の応力を加え、1000時間のクリープ試験を行ったとき、初期の変形を除いた全クリープ変形量が0.25%以下であることを特徴とする。更に、エンドリング等の平滑な面を有する熱間鍛造品は、熱間鍛造後、析出熱処理を行なう前に、冷間加工を5~20%を施すことにより、825℃のソルトバスで300秒間加熱した試験片において、耐力が、150N/mm2以上、20℃における熱伝導率が280W/m・K以上、又は導電率が70%IACS以上であり、耐力と熱伝導率との積が48000以上、又は、耐力と導電率との積が、12000以上であることを特徴とする。更に、硬ろう付け相当の熱処理を行った熱間鍛造品に、200℃で50N/mm2の応力を加え、1000時間のクリープ試験を行ったとき、初期変形を除いて、0.15%以下のクリープ変形量であることを特徴とする。なお、これらの特性値は、空冷後に、590℃のソルトバスで30分間の、主として熱・電気伝導度回復のための熱処理を施した後に測定している。これら硬ろう付けを施した材料においても、高い強度、高い熱伝導性、高い電気伝導性を有しているので、高速回転するエンドリングや、圧力の掛かるヒートシンク等には好適な熱間鍛造品となる。
尚、本明細書でいう鍛造材とは、鍛造が行われる前の材料と、鍛造が行われた後の材料との両方を意味する。
尚、熱間鍛造を700℃以上で実施するとは、鍛造直前の温度を700℃以上にすることを意味する。
第2の製造方法で製造された銅合金熱間鍛造品は、前記熱間鍛造後で前記熱処理前の導電率をX(%IACS)とすると、Xと、Pの含有量[P]mass%と、Coの含有量[Co]mass%と、Feの含有量[Fe]mass%と、Snの含有量[Sn]mass%と、Mgの含有量[Mg]mass%と、Niの含有量[Ni]mass%との間に、
(45-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])≦X≦(55-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])の関係を有することが望ましい。
尚、熱間鍛造を700℃以上で実施するとは、鍛造直前の温度を700℃以上にすることを意味する。
本発明に係る銅合金として、第1発明合金乃至第3発明合金を提案する。合金組成を表すのに本明細書において、[Cu]のように[ ]の括弧付の元素記号は当該元素の含有量値(mass%)を示すものとする。また、この含有量値の表示方法を用いて、本明細書において複数の計算式を提示するが、それぞれの計算式において、当該元素を含有していない場合は0として計算する。また、第1乃至第3発明合金を総称して発明合金とよぶ。
3.1≦([Co]+0.9×[Ni]+0.8×[Fe]-0.005)/([P]-0.006)≦4.9、及び0.010≦2×[Ni]+3×[Fe]≦0.75×[Co]の関係を有する。
加熱工程における加熱温度は、925~1025℃である。
熱間鍛造は、少なくとも1回行い、少なくとも鍛造直前の温度を700℃以上とする。
冷却工程では、熱間鍛造後から12℃/秒以上の冷却速度で400℃以下に冷却するか、又は650℃から550℃までの温度領域を12℃/秒以上の冷却速度で冷却する。
析出熱処理の条件は、熱処理温度が450~600℃で保持時間が0.2~10時間であり、熱処理温度をT℃、保持時間をt時間とすると520≦T+20×t1/2≦615の関係を充たす。当該熱処理後、好ましくは400℃に達するまで、0.1℃/分から3℃/分の冷却速度で冷却する
前記の冷却工程と析出熱処理工程との間に冷間加工を行ってもよい。
以上の製造方法を、第1製造方法とよぶ。
尚、本実施形態の銅合金熱間鍛造品の製造方法に供される鍛造材の製造履歴はどのようなものでもよい。例えば、鋳造後でも、押出後でも、熱間鍛造後でも、冷間加工後でもよい。
以上の製造方法を、第2製造方法とよぶ。
Coの単独の添加では高い強度・電気伝導性等は得られないが、P、Snとの共添加で熱伝導性・電気伝導性を損なわずに、高い強度、高い耐熱特性、高い延性が得られる。Coの単独の添加では、強度が多少向上する程度であり顕著な効果はない。発明合金の組成範囲の上限を超えると効果が飽和するばかりでなく、却って、熱伝導性・電気伝導性を損ない、鍛造時の変形抵抗が高くなる。また、Coはレアメタルであるので、高コストになる。Coの含有量が発明合金の組成範囲の下限より少ないと、Pと共添加しても目的とする高い耐力が得られない。Coの組成範囲の下限は、0.21mass%であって、好ましくは、0.24mass%であり、より好ましくは、0.27mass%であり、特に高い耐力が必要な場合は、0.35mass%である。Coの組成範囲の上限は、特に高い耐力を必要とする場合は0.44mass%であり、好ましくは、0.43mass%であり、耐力とコストとの兼ね合いで、0.40mass%以下が好ましい。
上記のようなSnの効果を発揮させるためには、Snの含有量は0.003mass%以上が必要であるが、よりその効果を発揮させるためには、0.005mass%以上が好ましく、最適には0.007mass%以上が好ましい。一方、Snの含有量が0.08mass%を超えるとその効果は飽和し、電気・熱伝導性が悪くなる。熱伝導性、電気伝導性がより必要とする場合は、0.06mass%以下が好ましく、強度、耐熱性との関係もあるが0.04mass%以下が好ましい。
3.1≦([Co]+0.9×[Ni]+0.8×[Fe]-0.005)/([P]-0.006)≦4.9、(好ましい範囲は、3.2~4.6、より好ましくは3.3~4.3、最適には、3.4~4.0)
0.010≦2×[Ni]+3×[Fe]≦0.75×[Co]、(好ましい範囲は、0.025~0.7×[Co]、より好ましくは0.040~0.6×[Co]、最適には、0.050~0.5×[Co])
[Ni]の0.9の係数と、[Fe]の0.8の係数は、CoとPとの結合の割合を1とした場合の、NiとFeがPと結合する割合を表したものである。なお、Co、Fe、NiとP等の配合比が関係式の範囲から外れていくと、析出物が減少し、析出物の微細化、均一分散が損なわれ、析出にあずからないCo、Fe、Ni又はP等がマトリックスに過分に固溶し、熱伝導性・電気伝導性が悪くなると同時に目標とする高い耐力が得られない。本発明で工業的に実施できるCo、Ni、FeとPの配合及び析出熱処理条件で析出熱処理すると、([Co]+0.9×[Ni]+0.8×[Fe])のうち概ね0.005mass%、Pは概ね0.006mass%は、析出物の形成にあたらず、マトリックスに固溶状態で存在する。従って、([Co]+0.9×[Ni]+0.8×[Fe])とPの質量濃度から、各々0.005mass%、0.006mass%を差引いて、Co等とPの質量比を決定する必要がある。そして、そのCo等とPとの析出物は、概ねCo:Pの質量濃度比が4.3:1から3.5:1になる、例えばCo2P、Co2.aP、又はCo1.bPを中心に、Coの一部がNi、Feに置き換わったCoxNiyFeZPA、CoxNiyPz、CoxFeyPz等が形成される必要がある。Co2P、又はCo2.xPyを基本とする微細析出物が形成されないと、本件の主題である高い耐力、高い熱伝導性・電気伝導性、更には硬ろう付け後の高い耐力やクリープ特性が得られない。
Fe、Niは、数式([Co]+0.9×[Ni]+0.8×[Fe]-0.005)/([P]-0.006)の値が3.1~4.9の中心値から外れても、導電性の低下を最小限に留める機能を持つ。しかし、Niを0.15mass%以上や、数式(2×[Ni]+3×[Fe])の値が0.8×[Co]を越えるように過剰に添加すると、析出物の組成が徐々に変化し、強度向上や耐熱性の向上に寄与しないばかりか、熱間鍛造時の熱間変形抵抗が増大し、熱伝導性・電気伝導性が低下する。
Feは、CoとPとの共添加のもと、微量の添加で強度を向上させ、また、動的再結晶を遅らせて未再結晶組織を増大させる。ただし、Feの含有量が0.10mass%を越えたり、数式(2×[Ni]+3×[Fe])の値が[Co]を越えるようにFeを過剰に添加すると、析出物の組成が徐々に変化し、強度向上や耐熱性が向上しないばかりか、熱間変形抵抗が増大し、熱伝導性・電気伝導性が低下する。
熱間鍛造品は、一般的に複雑な形状を有し、各部位により様々な加工率で熱間加工されている。また、熱間鍛造される鍛造材の加熱条件や、熱間鍛造の回数、熱間鍛造温度等の諸条件にもよるが、熱間鍛造で得られる金属組織は、熱間鍛造品の各部位により異なったものである。本願の高耐力、高熱伝導性、高電気伝導性を有する熱間鍛造品を得るためには、平均結晶粒径が0.050mmから0.50mmである再結晶粒群の占める割合と未再結晶の占める割合の合計で80%以上が必要である。本発明合金は、熱間鍛造中において、再結晶核の生成を抑制する性質を持つが、熱間鍛造温度が高く、熱間加工率が低い場合は、熱間鍛造品の金属組織は再結晶する。ところが再結晶粒の平均結晶粒径が0.050mm以下である再結晶粒群の占める割合が20%以上であると、次の析出熱処理時で生成するCo、Pの析出物の平均粒径が大きくなり、析出がやや不十分で、全体として高耐力が得られない。また、電気、熱の伝導性も悪くなる。再結晶粒の平均結晶粒径が、0.050mm以上であると、析出熱処理時で生成するCo、Pの析出物の平均粒径が小さくなり、全体として高耐力が得られる。そして、平均結晶粒径が0.050mm以上であると、Co、Pとの析出強化に加え、Co、P、Sn等の構成元素の拡散を遅らせるので、マトリックスの耐熱性が高められ、本願の使用環境である100~200℃における耐力とクリープ特性を高めることができる。また、平均結晶粒径が0.050mm以上であると、約800℃の硬ろう付け時において、Co、Pの再固溶を遅らせ、Co、Pの微細な析出物を残留させることができるので、硬ろう付け後もより高い耐力が得られる。また、熱間鍛造後に更に冷間加工を施している場合は、その加工ひずみが残存するので、より高い耐力が得られる。なお、平均結晶粒径が0.050mmから0.50mmである再結晶粒群であって、それらの平均結晶粒径は、0.070mm以上が好ましく、0.080mm以上であることが最も好ましい。一方、平均結晶粒径が、0.50mmを超えると、延性に問題が生じる。より好ましくは、0.30mm以下であり、最適には0.20mm以下である。
1.熱間鍛造品の中でも、加工率が全体的に低い場合
2.熱間鍛造前の鍛造材の結晶粒が粗大化している場合
3.熱間鍛造品が大きいため、静的再結晶が起こりやすく、結晶成長がし易い場合
4.熱間鍛造温度が高い場合
熱間鍛造品の平均結晶粒径のより好ましい条件として、平均結晶粒径が0.080mmから0.30mmである再結晶粒群の占める割合が、60%以上、又は、平均結晶粒径が0.050mmから0.50mmである再結晶粒群の占める割合が、80%以上、最適には、平均結晶粒径が0.080mmから0.20mmである再結晶粒群の占める割合が、80%以上である。これらの金属組織の状態にすることにより、すなわち、一般的な銅合金の平均結晶粒径より大きくすることにより、析出熱処理時で生成するCo、Pの析出物の平均粒径が小さくなり、高耐力が得られ、硬ろう付けを行っても析出粒子の再固溶を妨げ、更には鍛造品に冷間加工を施すと、その加工ひずみをより多く結晶粒内に蓄積できるので、より高い耐力を有することができる。結晶粒が大きいと、原子の拡散を遅らせる作用を有するので、使用環境である100~200℃での耐力とクリープ特性を高めることができる。なお、平均結晶粒径が、0.50mmを超えると、延性に問題が生じる。平均結晶粒径は、より好ましくは0.30mm以下であり、最適には0.20mm以下である。
なお、熱間鍛造後、析出熱処理前に平均結晶粒径が0.050mmから0.50mmである再結晶粒群の占める割合が60%以上である熱間鍛造品は、熱間鍛造後、析出熱処理前の時点で、耐力が60~130N/mm2、ビッカース硬さが50~85であり、かつ導電率が33~49%IACSである。析出熱処理前の強度が低いので、容易に矯正や目的とする形状に成形がし易い。また、熱間鍛造品の形状によっては熱間鍛造後、析出熱処理前に1~20%の軽冷間加工を施す場合がある。熱間鍛造後に軽冷間加工を施すことにより、熱処理後の熱間鍛造品の耐力は、著しく向上する。具体的には5~15%の冷間加工で280~390N/mm2の耐力となり、より好適なヒートシンクや、エンドリング用の熱間鍛造品となる。更には、使用環境である100~200℃の耐力とクリープ特性を高めることができる。具体的には、200℃で100N/mm2の応力を負荷し、1000時間のクリープ試験を行ったとき、初期変形を除いた全クリープ変形量が0.15%以下の耐クリープ変形に優れた熱間鍛造品になる。
1.熱間鍛造加工率が大きい場合
2.薄肉に鍛造される箇所等において、熱間鍛造中を含め温度低下が急で、動的・静的再結晶が生じる時間がない場合
3.熱間鍛造温度が低い場合
熱間鍛造温度が低く、熱間鍛造品の金属組織が未再結晶状態にあっても、鍛造材が、少なくとも一旦925℃以上に加熱されているので、析出熱処理後の析出物が微細であり、合金は強化されると同時に、熱間鍛造時に未再結晶状態に相当する蓄積されたひずみが熱処理後も残り、それが加算されるので、高耐力、高熱伝導性、高電気伝導性が得られる。更に、元の結晶粒が未再結晶状態であるので、硬ろう付けを行っても析出物の消滅が遅れ、使用環境である100~200℃における耐力とクリープ特性を高めることができる。未再結晶粒の占める割合が、60%以上であると、高耐力、高熱伝導性、高電気伝導性を有する熱間鍛造品が得られる。より好ましい条件としては、未再結晶粒の占める割合は、80%以上である。
鍛造前の加熱温度は、鍛造材を925℃以上(好ましくは940℃以上)に加熱する必要がある。925℃以上に加熱すると、Snの含有の効果もあってCo、Pはマトリックスに固溶し、Co、Pの析出物による結晶粒成長抑制作用が無くなるので、平均結晶粒径が0.10mm以上の粗大な金属組織となる。一旦、金属組織が粗大化する925℃以上に鍛造材を加熱すれば、その後に鍛造材を加熱するための加熱炉の中で温度低下があっても、炉から鍛造するまでに鍛造材が温度低下しても、複数回熱間鍛造する際に熱間鍛造品の温度が低下しても、Co、Pの固溶状態は維持される。例えば、ドーナツ状の大型エンドリングを作る時は、鍛造材を10回以上鍛造し、熱間鍛造開始から終了まで5分から15分掛かるが、最終の熱間鍛造温度が少なくとも700℃以上であれば、Co、Pのほとんどが溶体化状態にある。
そして、粗大化した結晶粒は、熱間鍛造中の再結晶核の生成を遅らせるので、その生成する平均結晶粒径を、0.050mm以上、更には0.080mm以上の大きなものとする、又は、熱間鍛造加熱時にできた平均結晶粒径0.1mm以上の結晶粒をひずんだ状態させる、すなわち未再結晶状態にさせる。そして熱間鍛造品の結晶粒が大きいと、約800℃の硬ろう付け時において、析出熱処理によって析出していたCo、Pの再固溶を遅らせる。
そして、高温で素材の結晶粒を粗大化させておくと、鍛造温度を意図的に低くしても(鍛造直前の温度が700℃以上)、複数回熱間鍛造して温度低下や、時間がかかってもCo、P等を固溶状態に保つことができる。粗大化した結晶粒は、850℃以下の温度で熱間鍛造すると金属組織を未再結晶状態にさせることができ、未再結晶状態であると、熱間鍛造品にひずみを蓄積させることができる。析出熱処理時において、Co、Pの析出物が、微細に析出し、かつ、熱間鍛造時に蓄積されたひずみが更に加算されるので、析出熱処理後の耐力をより高いものにすることができる。また、使用環境である100~200℃の耐力とクリープ特性を高めることができる。未再結晶粒にするための鍛造温度は、より好ましくは830℃以下であり、下限は変形抵抗が高くなるので好ましくは、720℃以上、より好ましくは750℃以上で鍛造し、400℃までの温度域を12℃/秒の冷却速度で冷却し、その後析出熱処理を行うと耐力が高く、熱伝導性・電気伝導性の優れたものができる。
Co、P等が固溶状態にあるかどうか、鍛造品に析出余力があるかどうかは、熱間鍛造後、析出熱処理前の鍛造品の導電率で判別できる。析出による合金の強化は、析出物の粒径の大きさと共に、析出余力があるかどうかがもう1つの大きなポイントである。本願の合金組成を満足しておれば、熱間鍛造後、熱処理前の導電率:%IACSの値が、(45-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])の式で表される値以上であり、(55-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])の式で表される値以下であることが好ましい。下限は、工業的に熱間鍛造にCo、P等が固溶状態にある理想の数値であり、上限側は、本願を達成する上で鍛造品に析出余力が残っている限界の数値である。上限側は、(52-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])であることが好ましい。Co、P等の含有量にもよるが、鍛造後の導電率は、33~49%IACS であり、熱処理後の導電率が75%IACS以上であるので、差が大きいほど、析出量が大きいことを示している。析出量の観点から、析出熱処理前後での導電率の差が、32%IACSが必要であり、好ましくは、36%IACS以上であり、最適には、40%IACS以上である。
700℃以上の温度で熱間鍛造後、400℃以下に12℃/秒以上、好ましくは20℃/秒以上の冷却速度で急冷するか、又は熱間鍛造後、650℃から550℃の温度領域を12℃/秒以上、好ましくは20℃/秒以上の冷却速度で通過することが、冷却時の絶対条件になる。
一般的には水冷が好ましいが、析出が開始する温度の650℃から550℃の領域を速く通過させることが必要である。この温度域を、ゆっくり通過すると、強度に寄与しない粗大な析出物が析出し、後の析出熱処理で熱処理しても析出する粒子は大きく、平均析出粒子径は、4nmを超える、又は0.7~7nmの大きさの析出物が90%未満となるので、耐力は必要とされる数値にまで達しない。
熱間鍛造後の冷却後に、固溶したCo、Pを析出させるために析出熱処理を行う。熱処理後の強度は析出粒子径に依存する。析出粒子の粒径が小さい方が銅合金熱間鍛造品の強度は高くなる。
析出熱処理の条件は、熱処理温度をT℃、保持時間をt時間とすると、520≦T+20×t1/2≦615の関係を充たすようにする。ただし、前記の関係式においてT℃は450~600℃であり、t時間は0.2~10時間である。
析出熱処理のより好ましい範囲は、530≦T+20×t1/2≦590であり、T℃は470~570℃であり、t時間は0.3~8時間である。所定の析出熱処理後の温度から、400℃までの温度域を、3℃/分以下の冷却速度で冷却すると、電気・熱伝導性が向上する。例えば、50℃/分で冷却するより、1℃/分で冷却したほうが、導電率が約2%IACS向上する。なお、0.3℃/分の冷却速度で概ねこの効果は飽和する。また、電気・熱伝導性と引張強さ、耐力との関係において、強度重視の場合、525≦T+20×t1/2≦570が好ましく、電気・熱伝導性を重視する場合、560≦T+20×t1/2≦605が好ましい。必要とされる特性に応じて、熱処理条件を適切に設定することが出来る。
上述した第1発明合金、第2発明合金、第3発明合金及び比較用の組成の銅合金を用いて、高性能熱間鍛造品を作成した。図2は、熱間鍛造品を作成した合金の組成を示す。また、比較用として、純銅のC1220とC1020も使用した。
試験1として、次のようにして銅合金熱間鍛造品を製造した。
最初に実操業の電気炉によって原材料を溶解し、組成を調整して、外径240mm、長さ700mmのビレットを製造した。ビレットを870℃で2分間加熱し、間接押出機で外径36.5mmの棒を押し出した。間接押出機の押出能力は2750トンであった。熱間押出材の平均結晶粒径は、いずれも0.030mmから0.045mmであった。
熱間押出材を鍛造材として、鍛造前の加熱温度、鍛造温度、鍛造終了温度、鍛造終了後の冷却速度、析出熱処理条件を変えた複数の工程によって銅合金熱間鍛造品を製造した。図3に各工程の製造条件を示す。
工程A,A-1,A-2,C,E,F,G,H,H-1は、上述した第1製造方法に適合した工程である。
工程D,I,Jは、第1製造方法の比較例の工程である。
工程Bは、上述した第2製造方法に適合した工程であり、熱間鍛造後に、500℃のソルトバスに浸漬し、30分間保持した。
工程Sは、純銅のC1220とC1020に適した工程である。
鍛造品の1つは、そのままアムスラー万能試験機で引張試験し、耐力を求めた。
鍛造品の1つは、厚肉部をX部(2か所)とし、薄肉部をY部とし、厚肉と薄肉の境界部をZ部として切り出し、X、Y部をアムスラー万能試験機で引張試験し、耐力、伸び、引張強さを測定した。
鍛造品の2つは、任意の個所を切断し、1つの鍛造品のX、Y、Z部の各々の10か所ずつ、金属組織を観察し、再結晶の有無、再結晶粒の平均結晶粒径を求めた。同時に、X、Y部の熱伝導率、電気伝導率を測定した。鍛造品の熱伝導率、電気伝導率は、X、Y部の平均値を採用した。
鍛造品からX部を1個切り出し、200℃で50N/mm2の応力を加え、1000時間のクリープ試験し、初期の変形を除く全クリープ変形を測定した。
また、鍛造品からX部を2個切り出し、ろう付け相当の試験、すなわち、実際のAgろう付け条件に相当する825℃のソルト中で300秒間加熱、空冷後、再び590℃のソルトバスで、30分間浸漬の熱処理を施し空冷した(以下、この試験をろう付け相当試験という)。なお、本試料を825℃のソルトバスに浸漬したところ、浸漬後、85秒から105秒間で、800℃に達した。よって、少なくとも、800℃~825℃で180秒以上高温に加熱されたことを意味する。ろう付け相当試験片を加工し、200℃で50N/mm2の応力を加え、1000時間のクリープ試験し、初期の変形を除く、全クリープ変形を測定した。
この熱間鍛造片を鍛造材として、製造条件を変えた複数の工程によって熱間鍛造品を製造した。鍛造材をガス炉で再加熱し、熱間鍛造により、外径約350mm、内径約200mm、高さ約50mmのリングにした。鍛造回数は約20回である。一部は更に冷間鍛造し、高さを44mmにした。この加工は冷間加工率12%に相当する。製造条件は、鍛造前の加熱温度、鍛造温度、鍛造終了温度、鍛造終了後の冷却速度、析出熱処理条件を変化させた。図5に、各工程の製造条件を示す。
工程K,K-1,L,Mは、上述した第1製造方法に適合した工程である。
工程N,O,P,Q,Rは、第1製造方法の比較例の工程である。
工程Tは、純銅のC1220とC1020に適した工程である。
厚肉部(X部)と試験2のリング鍛造品は、試験片を切り出し、JIS Z 2201の金属材料引張試験片の4号試験片にしたがって試験した。但し、平行部の径を10mmとし、標点距離を4×A1/2(Aは平行部の断面積)とした。試験2のリング鍛造品については、幅方向は中央で、表面を含んだ、20mm×20mmの断面を持ち、長さ160mmに切り出した直方体を試験片とした。
薄肉部(Y部)は、試験片を切り出し、JIS Z 2201の金属材料引張試験片の4号試験片にしたがって試験した。但し、平行部の径を5mmとし、標点距離を4×A1/2(Aは平行部の断面積)とした。
再結晶粒は、正6角形に近い形状を示し、結晶粒に外接円と内接円を描くと(結晶粒の外接円の径)/(結晶粒の内接円の径)の比は、ほとんどの再結晶粒が、2.0未満である。従って、(結晶粒の外接円の径)/(結晶粒の内接円の径)の比が2.0以上の結晶粒を未再結晶粒とする。
金属組織を、倍率を75倍とし、50mm×70mmの視野で観察する。但し、結晶粒径が、0.15~0.20mmを境にして粗大な結晶粒の場合は、37.5倍とした。そして、その観察した視野の金属組織が再結晶粒であるときには、その視野内にある全ての再結晶粒の集まりをその視野における再結晶粒群とする。そして、観察した視野の再結晶粒の平均結晶粒径がammであるとすると、その視野にあった再結晶粒は、再結晶粒の平均結晶粒径がammであった再結晶粒群とする。その観察した視野の金属組織が未再結晶の場合には、その視野は全て未再結晶粒とする。
このようにして、観察する金属断面の全体から、均一に10視野を観察し、視野毎に再結晶粒か未再結晶粒であるかを判定する。そして、観察した視野が再結晶粒であった場合には、平均結晶粒径を測定する。このようにして、10視野の観察結果から、その断面金属組織において、再結晶粒の平均結晶粒径が所定の範囲に入る再結晶粒群の占める割合を算出する。
例えば、10視野の内、1視野が未再結晶粒で、9視野が再結晶粒であり、再結晶粒であった9視野の内、8視野の平均結晶粒径が0.050~0.50mmであり、1視野の平均結晶粒径が0.01mmであったとする。この場合は、再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合が80%であり、未再結晶粒の占める割合が10%ということになる。
なお、観察した視野が、未再結晶と再結晶が混在する視野であった場合は、未再結晶粒と再結晶粒(微細な結晶粒を含む)を区分し、再結晶部を画像処理ソフト「WinROOF」によって2値化し、その面積率が20%未満の場合は、未再結晶粒の視野と判定し、また、80%以上の場合は再結晶粒の視野と判定し、それ以外は、再結晶部にも、未再結晶部にも属さないとした。さらに再結晶と未再結晶の判別が付き難い場合、200倍のEBSP(Electron Backscatter Diffraction Pattern、電子線後方散乱回折図形)による結晶粒マップから加工ひずみの残留の度合いによって再結晶域と未再結晶域を区別し、その領域の面積率を画像解析(画像処理ソフト「WinROOF」で2値化する)により測定した。EBSPを用いることにより、本発明での加工によるひずみが多く残留しているかどうか確かめることができている。
75万倍のTEM(透過電子顕微鏡)の透過電子像を、画像処理ソフト「WinROOF」によって2値化して析出物を抽出し、各析出物の面積の平均値を算出して、平均粒子径を測定した。測定位置は、試験片の肉厚をhとすると、両表面から1h/4の2点とし、その平均値を採った。また、それぞれの析出物の粒径から、7nm以下の析出物の個数の割合を測定したが、粒径0.7nm未満のものについては、誤差が大きいと判断し、析出粒子から除外した(認識しなかった)。
各種の試験片を切り出し、JIS Z 2271の金属材料の引張試験方法に準じて行った。試験片は、平行部の径を8mmとし、標点距離を40mmとした。クリープ試験は、鍛造品、リング鍛造品(試験2)については、50N/mm2の応力をかけ、200℃、1000時間での全クリープ変形量、および初期変形を除いた全クリープ変形量を求めた。冷間加工(鍛造)を加えたリング鍛造品については、100N/mm2の応力をかけ、200℃、1000時間での全クリープ変形量、および初期変形を除いた全クリープ変形量を求めた。そして、ろう付け相当試験後の試験片についても、50N/mm2の応力をかけ、200℃、1000時間での全クリープ変形量、および初期変形を除いた全クリープ変形量を求めた。
尚、試験1の結果の表で、部位の欄のXの行に、試験片のX部の結果を示し、Yの行に試験片のY部の結果を示した。そして、部位の欄のVの行においては、結晶粒径に関する項目には、X、Y、Z部での測定の平均値を記載し、析出物の粒径に関する項目と、熱伝導率、導電率の項目には、X、Y部での測定の平均値を記載し、引張試験に関する項目には試料全体を引っ張った結果を記載した。また、工程A-Oの行には、工程Aにおける冷却後の機械的性質を記載した。
試験の結果、次のことが分かった。
1.第1発明合金であって、再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上である銅合金熱間鍛造品は、強度、耐力、熱伝導性、電気伝導性等に優れていた。その中でも再結晶粒の平均結晶粒径が0.080~0.30mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上である銅合金熱間鍛造品は、耐クリープ性を含めたこれらの諸特性に優れていた。鍛造後の簡易的な連続熱処理工程を入れた工程B、2回の鍛造工程を入れた工程G、鍛造温度が異なった工程E、Fともにいずれも、良好な諸特性を示した。また、溶体化処理等のコストがかかる工程を用いない熱間鍛造なので、低コストになる(合金No.11の工程A、B,C,E,F,G,H等参照)。さらに熱間鍛造後の冷却速度が速い方が、強度、耐力、熱伝導性、電気伝導性、クリープ特性等に優れていた(工程A、B,C等参照)。
2.第2発明合金であって、再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上である銅合金熱間鍛造品は、更に強度が強くなっている(合金No.21の工程A、E,F,G,H等参照)。
3.第3発明合金であって、再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上である銅合金熱間鍛造品は、第1発明合金の場合と同様に、強度、耐力、熱伝導性、電気伝導性等に優れていた(合金No.31の工程A、B,E,F,G,H等参照)。
4.再結晶粒における析出物の平均粒径が1.3~3.9nm、又は析出物の90%以上が0.7~7nmであると、高耐力、高熱伝導性、高電気伝導性を有し、また使用環境である100~200℃において高いクリープ特性を有することができる(合金No.11の工程A、B,C,E,F,H等参照)
5.再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合が60%以上、若しくは未再結晶粒の占める割合が60%以上であると、使用環境である100~200℃において高いクリープ特性を有することができる(合金No.11の工程F,G等参照)。
6.825℃で300秒間加熱され、冷却後の耐力が、125N/mm2以上であり、前記冷却後の20℃における熱伝導率が280W/m・K以上、又は前記冷却後の20℃における導電率が70%IACS以上であり、前記冷却後の耐力をL(N/mm2)、前記冷却後の20℃における熱伝導率をM(W/m・K)、前記冷却後の20℃における導電率をN(%IACS)としたとき、(L×M)の値が38000以上、又は、(L×N)の値が、9600以上である銅合金熱間鍛造品を得ることができた。そして、熱間鍛造後に加工率12%の冷間加工を施すことにより、さらに耐力と200℃におけるクリープ特性に優れることができる(合金No.11の工程K,L,M等参照)。
7.熱間鍛造前の加熱温度が低いと、鍛造前の鍛造材の平均結晶粒径は、0.1mm以上にならない。平均結晶粒径が、0.1mm以上にならないと、熱間鍛造品の薄肉部では、未再結晶粒になるか、再結晶しても、平均結晶粒径が、0.05mm以上にならない。熱間鍛造品の厚肉部においても、平均結晶粒径が0.050mm以上の占める再結晶粒の割合が少ない、また、平均結晶粒径が0.08mmより大きな結晶粒を得ることは難しい。工程Eと工程Fは、鍛造材の加熱温度が同じで、素材の平均結晶粒径は0.1mm以上になっている。しかし、鍛造温度、終了温度が異なるため、厚肉部においては、両工程共にほとんどが再結晶しているものの、結晶粒径0.08mm以上の占める割合に差があるため、析出物の粒径が、工程Fの方が大きくなっている。その結果、工程Eの方が、耐力、電気伝導性、熱伝導性が少し高い。薄肉部においては、工程Fは、未再結晶状態になるので、析出粒子径が、工程Eに比べ少し大きい。試験結果は、工程Fが未再結晶状態により、耐力が少し高く、熱伝導性・電気伝導性は少し低い。工程Aと合わせて考えれば、工程・設備の制約、鍛造品形状、耐力と熱伝導性・電気伝導性のどちらに主眼を置くか、によって適宜熱間鍛造の温度を変えるとよいことが分かる。
8.熱間鍛造後に行う析出熱処理後、400℃までの冷却速度を0.8℃/分で冷却すると、強度、耐熱特性等の諸特性にほとんど変化なく、導電率が約2%IACS向上する。熱処理後の冷却を遅くすることによって、Co、P等がさらに微細に析出するためと考えられる。冷却速度を遅くしても、比較例合金は、強度・導電率特性は僅かに向上する程度である。(工程A-1参照)
525≦T+20×t1/2≦570で析出熱処理すると、強度が高くなる。560≦T+20×t1/2≦605で熱処理すると、電気・熱伝導性が高くなる。温度条件等を上げると、析出粒子が、少し大きくなるが、平均粒子径が3.9nmより小さく、析出物の90%以上が0.7~7nmであるので、強度等の低下を僅かなものとし、より多くのCo、Pを析出できたために電気・熱伝導性が高くなったと考えられる。(工程A-1、工程A-2参照)
熱間鍛造後で析出熱処理前の導電率:%IACSが、(45-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])から、(55-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])の間にあると、析出余力があるので、合金は析出によって強化される。特に、(52-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])より数値が小さいか、または、析出熱処理後の導電率の差が、36%IACS以上、さらには、40%IACS以上あると、さらに強度、耐熱特性等の特性がよくなる。
9.工程Iは、工程Fと同様に、未再結晶組織が形成されるが、未再結晶組織の割合が工程Fより少ないことと、鍛造後の導電率が高く、析出余力が小さいために、強度が低く、電気・熱伝導性が悪い。
工程E、F、G、H-1は、工程Aに比べ、鍛造温度が低いが、鍛造品の導電率、および析出粒子径からCo、Pの固溶状態が、維持されていることが確認できる。
工程H-1は、鍛造材の結晶粒が大きくなっていることと、鍛造温度が低いために、鍛造品のほとんどの部位で未再結晶状態になる。また鍛造温度が低くても、Co、Pの固溶状態が維持されており、未再結晶組織と析出によって強度が高くなっている。また、未再結晶組織であっても、延性の低下が少ない。鍛造品の形状、用途、鍛造機のパワーによって、適宜鍛造条件を選択すると、より特性の優れたものが得られる。
10.熱間鍛造後の金属組織の影響について述べる。
熱間鍛造前の鍛造材の加熱の段階で平均結晶粒径が0.1mm以上になっていると、熱間鍛造後も、厚肉部では平均結晶粒径が0.05mm以上、さらには0.08mm以上になる。平均結晶粒径が大きいほど、後の析出熱処理後の析出物の粒径が小さくなり、高い耐力が得られ、また高い熱伝導性・電気伝導性が得られる。これは、鍛造前の鍛造材の段階で、結晶粒径を大きくすることにより、Co、Pのほとんどが固溶するので、析出熱処理を行うと、析出する析出物が小さくなり、またほとんどが析出するので、熱伝導性・電気伝導性が高くなる。さらに、熱間鍛造品の平均結晶粒径が大きく、細かい析出物が析出しているので、耐熱性及び強度が高くなる。そして、平均結晶粒径が大きいので構成元素の拡散が遅れ、原子レベルでの拡散に依存するクリープ変形を起こり難くし、高温に加熱しても析出物の再固溶を遅らせる。このことにより、ろう付け相当の熱処理を行っても、高い強度が維持され、クリープ変形にも耐える。
11.熱間鍛造時に高い加工率を加えられた部分は、熱間鍛造温度が低くなると未再結晶状態になる。熱間鍛造前の加熱の段階で、平均結晶粒径を0.1mm以上にすることによって、析出熱処理後の析出物の大きさが細かくなり、未再結晶状態によるひずみが加わるので、高い耐力を持つようなる。再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上を占めると、耐力、熱伝導性・電気伝導性が高くなる。また、平均結晶粒径が0.05mm以上の再結晶粒のみの部分(主としてX部)と、未再結晶粒のみの部分(主としてY部)と、これらの混在する全体部分との間における、耐力、熱伝導性・電気伝導性の差は小さい。
12.鍛造前の鍛造材の段階で、0.1~5mmの平均結晶粒径にしておくと、熱間鍛造の開始温度、終了温度に関わらず(但し、終了温度が700℃以上)、鍛造で出来る金属組織は、平均結晶粒径が0.05mm以上の再結晶粒の組織か、未再結晶粒の組織のいずれかが主体となるので、良好な、耐力、熱伝導性・電気伝導性を示す。
13.熱間鍛造後の冷却速度の影響について述べる。熱間鍛造後における650℃から550℃への冷却速度が遅いと、析出熱処理後の耐力、熱伝導性・電気伝導性が低くなる。これは、冷却時に粗大な析出物が析出したためと思われる。また、クリープ変形量も多くなる。
14.試験2のリング鍛造について述べる。熱間鍛造前の鍛造材の加熱温度が低いと、熱間鍛造温度の低下に伴って、Co、Pの固溶状態が崩れ、粗大な析出物が多くなるため、析出熱処理後の耐力が低く、熱伝導性・電気伝導性も悪い。熱間鍛造前の鍛造材の加熱が適正であっても、最終熱間鍛造温度が低いと、Co、Pの粗大な析出物が多くなるため、析出熱処理後の耐力が低く、熱伝導性・電気伝導性も悪い。
15.リング熱間鍛造品を、825℃、300秒のソルトバスに浸漬し、熱処理すると、熱間鍛造後の平均結晶粒径が0.08mm以上に大きくなっているので、析出物の粒成長が遅れ、析出物が多少大きくなる、または、析出物の再固溶が遅れる。しかしながら、耐力に寄与する細かい析出物が充分にあるので、良好な、耐力、熱伝導性・電気伝導性を示す。比較例では、元の熱間鍛造品の平均結晶粒径が小さくて析出物が大きいうえに、さらに析出物が粗大化する、または、析出物の再固溶が多くなるので、耐力、熱伝導性・電気伝導性が悪い。
本発明に係るリング熱間鍛造品は、熱間鍛造後に、12%の冷間加工を加えると、耐力が高くなる。これは、熱間鍛造品の平均結晶粒径が0.08mm以上なので、825℃に加熱されても、冷間加工により導入された加工ひずみが残留するためと考えられる。さらに、クリープ変形に関しては、本発明に係る熱間鍛造品は、比較例に比べ強度が高く、平均結晶粒径が大きいため拡散速度が遅いので、高い耐熱性を有し、クリープ変形量が少ない。冷間鍛造を加えたものは、さらに耐力が高く、加工ひずみが多く残留しているので、クリープ変形量は少ない。
16.Fe、Niの含有量が発明合金の組成範囲外であると、析出物の構成が変わり、析出物が大きくなるため、耐力、熱伝導性・電気伝導性が低く、クリープ特性も低い。
17.Snの含有量が発明合金の組成範囲よりも多いと、熱伝導性・電気伝導性が低い。また、析出物がやや大きいために、Snの固溶強化が相殺され、耐力も少し低い。
18.Co、Pの含有量が発明合金の組成範囲よりも少ないと、熱伝導性・電気伝導性はよいが、耐力が低く、クリープ特性も悪い。
19.Coが0.21~0.44mass%であり、Pが0.06~0.13mass%であっても、3.1≦([Co]-0.005)/([P]-0.006)≦4.9の関係式を満足しないと、余分なCo、Pがマトリックスに固溶し、又は、析出物の構成が変わって析出物が大きくなるために、耐力、熱伝導性・電気伝導性が低く、また、クリープ特性も悪い。特に、鍛造回数の多い試験2の熱間鍛造品は、熱間鍛造中に析出物が粗大化し、熱処理後も析出物の平均粒径が大きいので、耐力、熱伝導性・電気伝導性、クリープ特性が低い。さらに、825℃で熱処理すると、鍛造品の析出粒子が大きいので、耐力が低くなり、耐熱性に劣るので、クリープ特性も低い。
20.Snの含有量が発明合金の組成範囲よりも少ないと、短時間ですべてのCo、Pが固溶しないので、粗大な析出物が残留する。また、熱間鍛造中に一部で析出物が粗大化し、全体としても熱処理後の析出物が大きくなるので、耐力、熱伝導性・電気伝導性が低くなる。
21.工程A-Oから、熱間鍛造後の引張強さ、耐力が低く、伸び値が高いので、析出処理前に、冷間矯正が容易に行われ、より精度の高いニアネットシェイプまで作れることが示唆される。
20.C1020、C1220は、熱間鍛造すると、耐力は著しく低く、耐熱性にも劣るのでクリープ特性も低い。
Claims (12)
- 0.21~0.44mass%のCoと、0.06~0.13mass%のPと、0.003~0.08mass%のSnと、0.00003~0.0030mass%のOとを含有し、残部がCu及び不可避不純物からなる合金組成であり、Coの含有量[Co]mass%とPの含有量[P]mass%との間に、
3.1≦([Co]-0.005)/([P]-0.006)≦4.9の関係を有し、
断面金属組織において、再結晶粒の平均結晶粒径が0.050~0.50mmである再結晶粒群の占める割合と、未再結晶粒の占める割合との合計が80%以上であることを特徴とする銅合金熱間鍛造品。 - 0.001~0.3mass%のZn、0.002~0.2mass%のMg、0.001~0.3mass%のAgのいずれか1種以上を更に含有することを特徴とする請求項1に記載の
銅合金熱間鍛造品。 - 0.005~0.15mass%のNi、0.003~0.10mass%のFeのいずれか1種以上を更に含有し、
Coの含有量[Co]mass%と、Niの含有量[Ni]mass%と、Feの含有量[Fe]mass%と、Pの含有量[P]mass%との間に、
3.1≦([Co]+0.9×[Ni]+0.8×[Fe]-0.005)/([P]-0.006)≦4.9、及び0.010≦2×[Ni]+3×[Fe]≦0.75×[Co]の関係を有することを特徴とする請求項1に記載の銅合金熱間鍛造品。 - 0.005~0.15mass%のNi、0.003~0.10mass%のFeのいずれか1種以上を更に含有し、
Coの含有量[Co]mass%と、Niの含有量[Ni]mass%と、Feの含有量[Fe]mass%と、Pの含有量[P]mass%との間に、
3.1≦([Co]+0.9×[Ni]+0.8×[Fe]-0.005)/([P]-0.006)≦4.9、及び0.010≦2×[Ni]+3×[Fe]≦0.75×[Co]の関係を有することを特徴とする請求項2に記載の銅合金熱間鍛造品。 - 耐力が、230N/mm2以上であり、
20℃における熱伝導率が300W/m・K以上、又は20℃における導電率が75%IACS以上であり、
前記耐力をL(N/mm2)、前記熱伝導率をM(W/m・K)、前記導電率をN(%IACS)としたとき、(L×M)の値が77000以上、又は、(L×N)の値が、19000以上であることを特徴とする請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品。 - 前記再結晶粒における析出物の平均粒径が1.3~3.9nm、又は析出物の90%以上が0.7~7nmであること特徴とする請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品。
- 前記再結晶粒の平均結晶粒径が0.050~0.50mmである前記再結晶粒群の占める割合が60%以上、若しくは前記未再結晶粒の占める割合が60%以上であることを特徴とする請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品。
- 825℃で300秒間加熱され、冷却後の耐力が、125N/mm2以上であり、
前記冷却後の20℃における熱伝導率が280W/m・K以上、又は前記冷却後の20℃における導電率が70%IACS以上であり、
前記冷却後の耐力をL(N/mm2)、前記冷却後の20℃における熱伝導率をM(W/m・K)、前記冷却後の20℃における導電率をN(%IACS)としたとき、(L×M)の値が38000以上、又は、(L×N)の値が、9600以上であることを特徴とする請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品。 - 請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品の製造方法であって、
熱間鍛造が施される鍛造材の熱間鍛造前の加熱温度が925~1025℃であり、前記鍛造材の前記加熱終了時の平均結晶粒径が0.10~5.0mmであることを特徴とする銅合金熱間鍛造品の製造方法。 - 請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品の製造方法であって、
熱間鍛造が施される鍛造材の少なくとも一回の熱間鍛造を700℃以上で実施し、
前記熱間鍛造後に前記鍛造材を12℃/秒以上の冷却速度で400℃以下に冷却、又は650℃から550℃までの温度領域を12℃/秒以上の冷却速度で冷却し、
前記冷却後に前記鍛造材に冷間加工を行った後又は冷間加工を行わずに、450~600℃の熱処理温度で0.2~10時間の保持時間であり、前記熱処理温度をT℃、前記保持時間をt時間とすると520≦T+20×t1/2≦615の関係を充たす熱処理を行うことを特徴とする銅合金熱間鍛造品の製造方法。 - 請求項10に記載の銅合金熱間鍛造品の製造方法で製造された銅合金熱間鍛造品であって、
前記熱間鍛造後で前記熱処理前の導電率をX(%IACS)とすると、Xと、Pの含有量[P]mass%と、Coの含有量[Co]mass%と、Feの含有量[Fe]mass%と、Snの含有量[Sn]mass%と、Mgの含有量[Mg]mass%と、Niの含有量[Ni]mass%との間に、
(45-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])≦X≦(55-25[P]-20[Co]-10[Fe]‐5[Sn]-3[Mg]-2[Ni])の関係を有することを特徴とする銅合金熱間鍛造品。 - 請求項1乃至請求項4のいずれか一項に記載の銅合金熱間鍛造品の製造方法であって、
熱間鍛造が施される鍛造材の少なくとも一回の熱間鍛造を700℃以上で実施し、
前記熱間鍛造後に前記鍛造材を650℃から550℃までの温度領域を12℃/秒以上の冷却速度で冷却し、前記冷却後に400~540℃の温度領域で10~200分保持することを特徴とする銅合金熱間鍛造品の製造方法。
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| JP2016157887A (ja) * | 2015-02-26 | 2016-09-01 | 京セラ株式会社 | 圧接型半導体装置用電極部材の製造方法 |
| JP2017009033A (ja) * | 2015-06-22 | 2017-01-12 | オイレス工業株式会社 | 静圧気体軸受用の円筒状複合部材及びこの円筒状複合部材の製造方法並びにこの円筒状複合部材を具備した静圧気体軸受 |
| CN112593114A (zh) * | 2020-12-22 | 2021-04-02 | 中北大学 | 一种高性能Cu-Cr-Zr-Mg-Si合金板带制备方法 |
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| WO2004079026A1 (ja) * | 2003-03-03 | 2004-09-16 | Sambo Copper Alloy Co.,Ltd. | 耐熱性銅合金材 |
| WO2009107586A1 (ja) * | 2008-02-26 | 2009-09-03 | 三菱伸銅株式会社 | 高強度高導電銅棒線材 |
| JP2010212164A (ja) * | 2009-03-11 | 2010-09-24 | Mitsubishi Shindoh Co Ltd | 電線導体の製造方法、電線導体、絶縁電線及びワイヤーハーネス |
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| WO2004079026A1 (ja) * | 2003-03-03 | 2004-09-16 | Sambo Copper Alloy Co.,Ltd. | 耐熱性銅合金材 |
| WO2009107586A1 (ja) * | 2008-02-26 | 2009-09-03 | 三菱伸銅株式会社 | 高強度高導電銅棒線材 |
| JP2010212164A (ja) * | 2009-03-11 | 2010-09-24 | Mitsubishi Shindoh Co Ltd | 電線導体の製造方法、電線導体、絶縁電線及びワイヤーハーネス |
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| JP2016157887A (ja) * | 2015-02-26 | 2016-09-01 | 京セラ株式会社 | 圧接型半導体装置用電極部材の製造方法 |
| JP2017009033A (ja) * | 2015-06-22 | 2017-01-12 | オイレス工業株式会社 | 静圧気体軸受用の円筒状複合部材及びこの円筒状複合部材の製造方法並びにこの円筒状複合部材を具備した静圧気体軸受 |
| CN112593114A (zh) * | 2020-12-22 | 2021-04-02 | 中北大学 | 一种高性能Cu-Cr-Zr-Mg-Si合金板带制备方法 |
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