WO2009119222A1 - 高強度高導電銅合金管・棒・線材 - Google Patents
高強度高導電銅合金管・棒・線材 Download PDFInfo
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- WO2009119222A1 WO2009119222A1 PCT/JP2009/053216 JP2009053216W WO2009119222A1 WO 2009119222 A1 WO2009119222 A1 WO 2009119222A1 JP 2009053216 W JP2009053216 W JP 2009053216W WO 2009119222 A1 WO2009119222 A1 WO 2009119222A1
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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
- C22C9/02—Alloys based on copper with tin 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Definitions
- the present invention relates to a high-strength, high-conductivity copper alloy tube / bar / wire made by a process including hot extrusion.
- copper has been used for connectors, relays, electrodes, contacts, trolley wires, connection terminals, welding tips, rotor bars used in motors, wire harnesses, robots and aircraft, taking advantage of its excellent electrical and thermal conductivity. It is used as a wiring material in various industrial fields. For example, although it is used also for the wire harness of a motor vehicle, in order to improve a fuel consumption regarding global warming, the weight reduction of a vehicle body is calculated
- the use weight of wire harnesses tends to increase due to advanced information technology, electronics, and hybridization of automobiles. Further, copper is an expensive metal, and there is a request from the automobile industry to reduce the amount used. For this reason, if a copper wire material for wire harness having high strength and high conductivity, and excellent in bending resistance and ductility is used, the amount of copper used can be reduced, and weight reduction and cost reduction can be achieved. it can.
- wire harnesses There are several types of wire harnesses, ranging from power systems to signal systems where only weak current flows. In the former, conductivity close to that of pure copper is first required as a first condition, and in the latter, particularly high strength is required. Therefore, a copper wire having a balance between strength and conductivity is required depending on the application. In addition, distribution lines for robots, aircraft, etc. are required to have high strength and high conductivity and bend-resistant. For these distribution lines, in order to further increase the bending resistance, the copper wire is often used as a stranded wire composed of several or several tens of fine wires.
- a wire refers to a product having a diameter or an opposite side distance of less than 6 mm, and is referred to as a wire even if the wire is cut into a rod shape.
- a bar means a product having a diameter or opposite side distance of 6 mm or more, and is called a bar even if the bar is coiled.
- a material having a large outer diameter is cut into a rod shape, and a thin material is shipped in a coil shape.
- the diameter or the opposite side distance is 4 to 16 mm, they are mixed and defined here.
- a rod and a wire are generically called a rod and wire.
- the connector and bus bar are becoming thinner on the male side due to the miniaturization of the connector, the connector and the bus bar are required to have strength and conductivity that can withstand insertion and removal of the connector. Since there is a temperature rise during use, stress relaxation resistance is also required. Relays, electrodes, connectors, bus bars, motors, and the like through which a large current flows are naturally required to have high conductivity, and high strength is required for compactness and the like.
- Wire cut (electric discharge machining) wires are required to have high conductivity, high strength, wear resistance, high temperature strength, and durability.
- the trolley wire requires high conductivity and high strength, and durability, wear resistance, and high temperature strength during use are also required.
- a trolley wire most of them have a diameter of 20 mm and fall within the category of a rod in this specification.
- the welding tip is required to have high conductivity, high strength, wear resistance, high temperature strength, durability, and high thermal conductivity.
- brazing material include 56Ag-22Cu-17Zn-5Sn alloy brazing such as Bag-7 described in JIS Z 3261, and a brazing temperature of 650 to 750 ° C. is recommended.
- the rotor bar, end ring, relay, electrode and the like used in the motor are required to have a heat resistance of 700 ° C., which is a brazing temperature, for a short time.
- high conductivity is desired even after brazing.
- the rotor bar used in the motor needs to be strong enough to withstand the increased centrifugal force due to the higher speed.
- relays, contacts, and electrodes that are used in hybrid vehicles, electric vehicles, solar cells, and the like and that flow high currents also require high conductivity and high strength even after brazing.
- Electrical parts such as fasteners, welding tips, terminals, electrodes, relays, power relays, connectors, connection terminals and the like are manufactured from rods by cutting, pressing, or forging, and are required to have high conductivity and high strength.
- the welding tip, electrode, and power relay are further required to have wear resistance, high-temperature strength, and high thermal conductivity. Since these electric parts often use brazing as a means for joining, they need heat resistance characteristics that maintain high strength and high conductivity even after high-temperature heating at 700 ° C., for example.
- the heat resistant property means that recrystallization is difficult even when heated to a high temperature of 500 ° C. or higher, and the strength after heating is excellent.
- pure copper including C1100, C1020, and C1220, which are excellent in conductivity, has low strength, so that the use weight increases in order to increase the cross-sectional area of the used part.
- a solution-aging / precipitation type alloy such as Cr-Zr copper (1% Cr-0.1% Zr-Cu).
- Cr-Zr copper 1% Cr-0.1% Zr-Cu
- the material is heated again to 950 ° C. (930-990 ° C.), immediately followed by quenching and aging, and the bar is made. Further processed into shape.
- the extruded bar is heated or subjected to a heat treatment process of heating to 950 ° C. after plastic working such as cold forging, rapid cooling, and aging.
- a heat treatment process of heating to 950 ° C. after plastic working such as cold forging, rapid cooling, and aging.
- passing through a high temperature process of 950 ° C. not only requires a large amount of energy, but also when heated in the atmosphere, oxidation loss occurs, and diffusion is easy because of the high temperature. Stickiness occurs and a pickling process is required.
- heat treatment is performed at 950 ° C. in an inert gas or vacuum, but this increases the cost and also requires extra energy.
- the oxidation loss can be prevented, the problem of stickiness cannot be solved.
- Cr—Zr copper requires a special management because it has a narrow solution temperature condition and a high cooling rate sensitivity.
- it since it contains a lot of active Zr and Cr, it is restricted by melt casting. As a result, the characteristics are excellent, but the cost is high.
- a copper material having an alloy composition containing Sn and In in a total amount of 0.15 to 0.8 mass% and the balance of Cu and inevitable impurities is known (for example, Japanese Patent Application Laid-Open No. 2004-137551). reference).
- a copper material has insufficient strength.
- the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a high-strength, high-conductivity copper alloy tube / bar / wire that has high strength, high conductivity, and low cost.
- the present invention provides a high-strength, high-conductivity copper alloy tube / rod / wire with 0.13-0.33 mass% Co, 0.044-0.097 mass% P, 0.005 to 0.80 mass% of Sn and 0.00005 to 0.0050 mass% of O, and between the Co content [Co] mass% and the P content [P] mass%, 2.9 ⁇ ([Co] ⁇ 0.007) / ([P] ⁇ 0.008) ⁇ 6.1, with the balance being an alloy composition of Cu and inevitable impurities, hot extrusion It is made by a process including
- the strength and electrical conductivity of high-strength, high-conductivity copper alloy tubes / rods / wires are improved by the uniform precipitation of Co and P compounds and the solid solution of Sn, and hot extrusion. Since it is manufactured by, it becomes low cost.
- high-conductivity copper alloy tube / rod / wire 0.13-0.33 mass% Co, 0.044-0.097 mass% P, and 0.005-0.80 mass% Sn , 0.00005 to 0.0050 mass% O, and 0.01 to 0.15 mass% Ni, or 0.005 to 0.07 mass% Fe, and Co.
- 0.003-0.5 mass% Zn 0.002-0.2 mass% Mg, 0.003-0.5 mass% Ag, 0.002-0.3 mass% Al, 0.002-0. It is desirable to further contain at least one of 2 mass% Si, 0.002 to 0.3 mass% Cr, and 0.001 to 0.1 mass% Zr. This makes S mixed in the recycling process of copper material harmless by Zn, Mg, Ag, Al, Si, Cr, Zr, prevents intermediate temperature brittleness, and further strengthens the alloy. Improves ductility and strength of pipes, bars and wires.
- the billet Before the hot extrusion, the billet is heated to 840 to 960 ° C., the average cooling rate from 840 ° C. after the hot extrusion, or from the extrusion material temperature to 500 ° C. is 15 ° C./second or more, and the hot extrusion
- the temperature In the case where cold drawing / drawing is performed after or after hot extrusion, the temperature is set at 375 to 630 ° C. before and after the cold drawing / drawing or between the cold drawing / drawing at 0 ° C. to 375 ° C. It is desirable to perform heat treatment TH1 for 5 to 24 hours. Thereby, since the average crystal grain size is small and precipitates are finely precipitated, the strength of the high-strength and high-conductivity copper alloy tube / rod / wire is improved.
- Substantially circular or elliptical fine precipitates are uniformly dispersed, and the average particle size of the precipitates is 1.5 to 20 nm, or 90% or more of all the precipitates are 30 nm or less. The size is desirable. Thereby, since fine precipitates are uniformly dispersed, strength and heat resistance are high, and conductivity is good.
- the average crystal grain size after hot extrusion is 5 to 75 ⁇ m. Thereby, since the average crystal grain size is small, the strength of the high-strength and high-conductivity copper alloy tube / rod / wire is improved.
- the recrystallization rate of the matrix is 45% or less in the metal structure after the heat treatment TH1.
- the average crystal grain size of the recrystallized part is preferably 0.7 to 7 ⁇ m.
- Ratio of (minimum tensile strength / maximum tensile strength) due to variation in tensile strength within an extrusion production lot is 0.9 or more, and ratio of (minimum conductivity / maximum conductivity) due to variation in conductivity is It is desirable that it is 0.9 or more. Thereby, since the dispersion
- the conductivity is 45 (% IACS) or more, the conductivity is R (% IACS), the tensile strength is S (N / mm 2 ), and the elongation is L (%), (R 1/2 ⁇ S ⁇
- the value of (100 + L) / 100) is desirably 4300 or more.
- the value of (R 1/2 ⁇ S ⁇ (100 + L) / 100) is 4300 or more, and the balance between strength and conductivity is excellent, so the diameter of the tube / bar / wire is reduced or the thickness is reduced. The cost can be reduced.
- the tensile strength at 400 ° C. is 200 (N / mm 2 ) or more. Thereby, since high temperature strength is high, it can be used in a high temperature state.
- the Vickers hardness (HV) after heating at 700 ° C. for 120 seconds is 90 or more, or 80% or more of the value of Vickers hardness before heating, and the average particle size of precipitates in the metal structure after heating is 1. It is desirable that 90% or more of 5 to 20 nm or all precipitates is 30 nm or less, and the recrystallization rate in the metal structure after the heating is 45% or less. Thereby, since it is excellent in heat resistance, it can be processed and used in an environment exposed to a high temperature state. Further, since there is little decrease in strength after processing in a high temperature state for a short time, the diameter of the tube, rod, or wire can be reduced, or the thickness can be reduced and the cost can be reduced.
- Cold forging or pressing can be easily performed, and the fine precipitates are uniformly dispersed and work hardening increases the strength and improves the conductivity. Also, this press product and forged product retain high strength even when exposed to high temperatures.
- Cold drawing or pressing is performed, and heat treatment is performed at 200 to 700 ° C. for 0.001 second to 240 minutes during cold drawing or pressing and / or after cold drawing or pressing. It is desirable to be manufactured by applying TH2. Thereby, the bending resistance and conductivity of the wire are excellent. In particular, when the cold working rate is increased by wire drawing, pressing, or the like, ductility, flex resistance, and conductivity are inferior, but by performing heat treatment TH2, ductility, flex resistance, and conductivity are improved.
- excellent bending resistance means, for example, that the number of repeated bending is 18 or more in the case of a wire having an outer diameter of 1.2 mm.
- the flowchart of the manufacturing process K of the high-performance copper pipe / rod / wire according to the embodiment of the present invention.
- the flowchart of the manufacturing process T of the same high performance copper tube / rod / wire The metal structure photograph of the deposit in process K3 of the same high performance copper tube / rod / wire. A metal structure photograph of precipitates after heating at 700 ° C. for 120 seconds in the compression processed material of step K0 of the same high performance copper tube / rod / wire.
- the high performance copper tube / rod / wire according to the embodiment of the present invention will be described.
- the present invention proposes a first invention alloy, a second invention alloy, and a third invention alloy having an alloy composition in the high-performance copper pipe, rod, and wire according to claims 1 to 4.
- an element symbol in parentheses such as [Co] indicates the content value (mass%) of the element to represent the alloy composition.
- the first to third invention alloys are collectively referred to as invention alloys.
- the first invention alloy comprises 0.13-0.33 mass% (preferably 0.15-0.32 mass%, more preferably 0.16-0.29 mass%) Co and 0.044-0.097 mass%. (Preferably 0.048 to 0.094 mass%, more preferably 0.051 to 0.089 mass%) and 0.005 to 0.80 mass% (preferably 0.005 to 0.70 mass%, particularly large) When strength is not required and high electrical / thermal conductivity is required, 0.005 to 0.095 mass% is more preferable, and 0.01 to 0.045 mass% is even more preferable.
- X1 ([Co] ⁇ 0.007) / ([P] ⁇ 0.008) X1 has a relationship of 2.9 to 6.1, preferably 3.1 to 5.6, more preferably 3.3 to 5.0, and most preferably 3.5 to 4.3, And the balance is an alloy composition consisting of Cu and inevitable impurities.
- the third invention alloy is composed of 0.003 to 0.5 mass% Zn, 0.002 to 0.2 mass% Mg, 0.003 to 0.5 mass% in the composition of the first invention alloy or the second invention alloy. Ag, 0.002 to 0.3 mass% Al, 0.002 to 0.2 mass% Si, 0.002 to 0.3 mass% Cr, 0.001 to 0.1 mass% Zr
- the alloy composition further contains more than seeds.
- the manufacturing process for high performance copper pipes, rods and wires will be described.
- the billet is heated and subjected to hot extrusion to produce a round bar, pipe (tube), bus bar, polygon, or a bar having a complicated cross section.
- the rod or tube is further drawn by drawing to make the rod and tube thin, and is drawn into a wire by drawing (the drawing for drawing this rod and the drawing for drawing the wire are collectively referred to as drawing / (Drawn as wire drawing). Only hot extrusion may be performed without performing the drawing / drawing step.
- the heating temperature of the billet is 840 to 960 ° C.
- the average cooling rate from 840 ° C. after extrusion or from the temperature of the extruded material to 500 ° C. is set to 15 ° C./second or more.
- heat treatment TH1 may be performed at 375 to 630 ° C. for 0.5 to 24 hours.
- This heat treatment TH1 is mainly intended for precipitation, and may be performed during the drawing / drawing process, after the drawing / drawing process, or may be performed a plurality of times.
- the heat treatment TH1 may be performed after the bar is pressed or forged. Further, after the drawing / drawing step, heat treatment TH2 may be performed at 200 to 700 ° C.
- This heat treatment TH2 is primarily intended for heat treatment for recovery of ductility and bending resistance, which corresponds to TH1 such as fine wires and thin rods, or is damaged by high cold working. Secondly, the purpose is to recover the heat treatment for recovering the conductivity that is damaged by high cold working, and it may be performed a plurality of times. Moreover, you may perform a drawing / drawing process again after this heat processing.
- Co is preferably 0.13 to 0.33 mass%, preferably 0.15 to 0.32 mass%, and optimally 0.16 to 0.29 mass%.
- Co cannot obtain high strength, high conductivity, etc. by adding it alone, but high strength and high heat resistance can be obtained by co-addition with P and Sn without impairing thermal and electrical conductivity.
- the strength is slightly improved and there is no remarkable effect.
- the upper limit is exceeded, the effect is saturated.
- electroconductivity is impaired. If the amount is less than the lower limit, the strength and heat resistance characteristics are not enhanced even when co-added with P, and the target metal structure is not formed after the heat treatment TH1.
- P is preferably 0.044 to 0.097 mass%, preferably 0.048 to 0.094 mass%, and most preferably 0.051 to 0.089 mass%.
- P is co-added with Co and Sn, so that high strength and high heat resistance can be obtained without impairing thermal and electrical conductivity. P alone improves the flowability and strength of hot water and refines the crystal grains. If the upper limit is exceeded, the above effects (high strength, high heat resistance) are saturated, and the thermal and electrical conductivity is impaired. In addition, cracks are likely to occur during casting and extrusion. In addition, ductility, particularly repetitive bending workability is deteriorated. If the amount is less than the lower limit, the strength and heat resistance are not improved, and the target metal structure is not formed after the heat treatment TH1.
- Co and P are improved in strength, heat resistance, high temperature strength, wear resistance, hot deformation resistance, deformability, and conductivity by co-addition within the above composition range.
- the composition of Co and P is low on the other hand, none of the above-described characteristics exhibits a remarkable effect.
- problems such as a decrease in hot deformability, an increase in hot deformation resistance, hot working cracks, and bending cracks occur as in the case of each addition.
- Both Co and P elements are indispensable elements for achieving the object of the present invention. Under proper blending ratio of Co, P and the like, strength, heat resistance characteristics, Improves high temperature strength and wear resistance. Within this composition range, as the amounts of Co and P increase, the precipitates of Co and P increase, and these characteristics are improved.
- Co: 0.13% and P: 0.044% are the minimum necessary amounts for obtaining sufficient strength, heat resistance and the like.
- Both Co and P elements suppress the growth of recrystallized grains after hot extrusion, and due to a synergistic effect with Sn that dissolves in the matrix described later, despite the high temperature from the front end to the rear end of the extrusion, Maintain fine crystal grains.
- the formation of fine precipitates of Co and P precedes the recrystallization of the matrix whose heat resistance is enhanced by Sn, and greatly contributes to both strength and conductivity characteristics.
- the effect exceeds Co: 0.33% and P: 0.097% almost no improvement in the characteristics is recognized, and the above-described defects start to occur.
- Sn is required to have the above-mentioned composition range (0.005 to 0.80 mass%).
- 0.005 to 0.095 mass% is good, and 0.01 to 0.045 mass% is optimal.
- Particularly high electric conductivity means that the electric conductivity of pure aluminum is higher than 65% IACS, and in this case, 65% IACS or more.
- 0.1 to 0.70 mass% is better, and 0.32 to 0.65 mass% is even better.
- Sn can be added in a small amount to improve the heat resistance characteristics and to refine the crystal grains in the recrystallized portion, while at the same time improving strength, bending workability, bending resistance, and impact resistance.
- the blending ratio of Co, Ni, Fe, and P and the size and distribution of precipitates are very important.
- the precipitate particle size of Co, Ni, Fe and P for example, a spherical or elliptical precipitate particle size such as Co x P y , Co x Ni y P z , and Co x Fe y P z is changed to several nm.
- 1.5 to 20 nm, or 90%, preferably 95% or more of the precipitates is 0.7 to 30 nm or 2.5 to 30 nm.
- the precipitated particles of 0.7 and 2.5 nm have a particle size that can be measured with high accuracy when observed at 750,000 times or 150,000 times using a general transmission electron microscope: TEM and dedicated software. It is the lower limit. Accordingly, if a precipitate having a particle size of less than 0.7 or 2.5 nm can be observed, the preferred ratio of the precipitate having a particle size of 0.7 to 30 nm or 2.5 to 30 nm also changes. In addition, precipitates such as Co and P improve the high-temperature strength at 300 ° C. or 400 ° C. required for welding tips and the like.
- X2 ([Co] + 0.85 ⁇ [Ni] + 0.75 ⁇ [Fe] ⁇ 0.007) / ([P] ⁇ 0.008)
- X2 should be 2.9 to 6.1, preferably 3.1 to 5.6, more preferably 3.3 to 5.0, and most preferably 3.5 to 4.3.
- X1 and X2 exceed the upper limit, the thermal and electrical conductivity is lowered, the heat resistance and strength are lowered, the crystal grain growth cannot be suppressed, and the hot deformation resistance is also increased.
- X1 and X2 are lower than the lower limit, heat / electric conductivity is lowered, heat resistance is lowered, and hot / cold ductility is impaired. In particular, the necessary balance between high thermal and electrical conductivity, strength, and ductility is deteriorated.
- the Co and P precipitates 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.b P or the like Unless fine precipitates centering on Co 2 P, Co 2.a P, Co 1.b P, and the like are formed, high strength and high electrical conductivity, which are the subject of the present invention, cannot be obtained.
- 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, high strength and high electrical conductivity, which are the subject of the present invention, cannot be obtained.
- the conductivity 80% IACS is almost the same as the pure copper C1220 added with 0.03% of P, and is 15% IACS higher than the conductivity 65% IACS of pure aluminum.
- the thermal conductivity of the invention alloy is also 355 W / m ⁇ K at a maximum at 20 ° C., and substantially 349 W / m ⁇ K or less. is there.
- FE and Ni partially replace the Co function. It also serves to make Co and P bond more effectively.
- the addition of Fe and Ni alone decreases the conductivity and does not contribute much to the improvement of various properties such as heat resistance and strength.
- Ni alone improves the stress relaxation resistance required for connectors and the like.
- Ni has a function of substituting Co under the co-addition of Co and P, and the decrease in conductivity due to Ni is small. Therefore, the value of the above formula ([Co] + 0.85 ⁇ [Ni] + 0.75 ⁇ [Fe] ⁇ 0.007) / ([P] ⁇ 0.008) is the center of 2.9 to 6.1. Even if it deviates from the value, it has a function of minimizing the decrease in conductivity.
- Ni is a Sn-plated connector or the like, and has an effect of suppressing Sn diffusion even when the temperature during use increases.
- the value of the formula X3 1.5 ⁇ [Ni] + 3 ⁇ [Fe] exceeds [Co]
- the composition of the precipitate gradually changes. Not only does it not contribute to improving the strength and heat resistance, but also increases the hot deformation resistance and lowers the electrical conductivity.
- Ni should be in a preferable range in the amount of Ni added or the formula of X3 as described above.
- Zn, Mg, Ag, Al, and Zr detoxify S mixed in the copper recycling process, reduce intermediate temperature brittleness, and improve ductility and heat resistance.
- Zn, Mg, Ag, and Al improve the strength of the alloy by solid solution strengthening, and Zr improves the strength of the alloy by precipitation hardening.
- Zn further improves solder wettability and brazing.
- Zn or the like has an action of promoting uniform precipitation of Co and P. Ag further improves heat resistance.
- Zn, Mg, Ag, Al, Si, Cr, and Zr are less than the lower limit of the composition range, the above-described effects cannot be exhibited.
- the upper limit is exceeded, not only the above-described effect is saturated, but also the conductivity starts to decrease, the hot deformation resistance increases, and the deformability deteriorates.
- Zn is used when the manufactured high-performance copper alloy rod, wire or press-formed product thereof is brazed in a vacuum melting furnace or the like, when used under vacuum, when used at high temperature, etc.
- the heating temperature of the billet in the hot extrusion needs to be 840 ° C. in order to sufficiently dissolve Co, P and the like.
- 960 degreeC the crystal grain of an extrusion material will coarsen.
- the start of extrusion exceeds 960 ° C.
- the temperature decreases during the extrusion, so that a difference in crystal grain size occurs between the extrusion start portion and the extrusion end portion, and a uniform material cannot be obtained. If it is less than 840 ° C., the solution (solid solution) of Co and P is insufficient, and precipitation hardening is insufficient even if an appropriate heat treatment is performed in the subsequent step.
- the billet heating temperature is preferably 850 to 945 ° C, more preferably 865 to 935 ° C, and most preferably 875 to 925 ° C.
- the temperature is 870 to 910 ° C.
- the temperature is 880 to 920 ° C.
- it exceeds 33 mass%, it is 890-930 ° C. That is, the optimum temperature shifts with a slight temperature difference depending on the amount of Co + P. This is because Co, P, etc.
- the billet temperature corresponding to the latter half of the extrusion should be 20-30 ° C. higher than the tip and center by induction heating such as a billet heater. .
- the container temperature is naturally preferably higher, preferably 250 ° C. or higher, and more preferably 300 ° C. or higher.
- the temperature of the dummy block on the rear end side of the extrusion is preferably preheated to 250 ° C. or higher, preferably 300 ° C. or higher.
- the alloy according to the present invention is much less susceptible to solution solution than Cr—Zr copper or the like, and therefore, for example, a cooling rate exceeding 100 ° C./second is not particularly required.
- a cooling rate exceeding 100 ° C./second is not particularly required.
- the extruded material is air cooled until it reaches the forced cooling device. Naturally, it is better to shorten the time during this period.
- the smaller the extrusion ratio H (the cross-sectional area of the billet / the total cross-sectional area of the extruded material), the longer it takes to reach the cooling facility, so it is desirable to increase the moving speed of the ram, that is, the extrusion speed.
- the strain rate is increased, the crystal grains of the extruded material become smaller.
- the cooling rate becomes slower as the material diameter is larger.
- atoms that are dissolved at high temperature are difficult to precipitate even when the cooling rate is low during cooling. This is called "high solution sensitivity".
- the ram moving speed (the speed at which the billet is extruded) is 30 ⁇ H ⁇ 1/3 mm / second or more, more preferably 45 ⁇ H, in relation to the extrusion ratio H. -1/3 mm / second or more, optimal 60 ⁇ H -1/3 mm / second or more.
- the cooling rate of the extruded material with easy atomic diffusion is such that the material temperature immediately after extrusion or the average cooling rate from 840 ° C. to 500 ° C. is 15 ° C./second or more, preferably 22 ° C./second or more, more preferably 30 It is necessary to satisfy at least one of the conditions.
- hot extrusion finish means a state where cooling after hot extrusion is completed. Further, by shortening the air cooling state to the cooling device, Co and P can be dissolved as much as possible, and crystal grain growth can be suppressed. Therefore, the distance from the extrusion equipment to the cooling device is short, and the cooling method is preferably a method with a high cooling rate such as water cooling.
- the crystal grain size after hot extrusion can be reduced.
- the crystal grain size is preferably 5 to 75 ⁇ m, preferably 7.5 to 65 ⁇ m, more preferably 8 to 55 ⁇ m.
- the smaller the crystal grain size the better the mechanical properties at room temperature.
- the crystal grain size exceeds 75 ⁇ m, not only the strength is not sufficiently obtained, but also the fatigue (repetitive bending) strength is lowered, the ductility is insufficient, and a rough skin phenomenon occurs when bending is performed.
- Optimum production conditions include extruding at an optimal temperature, increasing the extrusion speed (making the speed at which the billet is extruded 30 ⁇ H ⁇ 1/3 mm / sec or more) to destroy the structure of the casting and generating recrystallized nuclei. Increase the number of sites and shorten the air cooling time to suppress the growth of crystal grains.
- the cooling is rapid cooling by, for example, water cooling.
- the crystal grain size is also greatly affected by the extrusion ratio H. The larger the extrusion ratio H, the smaller the crystal grain size.
- Basic heat treatment TH1 conditions are 375 to 630 ° C. and 0.5 to 24 hours.
- the temperature is 450 to 630 ° C. for 0.5 to 24 hours, preferably 475 to 550 ° C. for 2 to 12 hours.
- a two-step heat treatment at 525 ° C. for 2 hours and 500 ° C. for 2 hours is effective.
- the number of precipitation sites increases.
- the optimum heat treatment conditions shift to a low temperature of 10 to 20 ° C.
- Better conditions are 420 to 600 ° C. for 1 to 16 hours, preferably 450 to 530 ° C. for 2 to 12 hours.
- the temperature, time, and processing rate are made clearer.
- the temperature T (° C.), the time t (hour), and the processing rate RE (%), and the value of (T ⁇ 100 ⁇ t ⁇ 1/2 ⁇ 50 ⁇ Log ((100 ⁇ RE) / 100)) is the heat treatment index TI
- 400 ⁇ TI ⁇ 540 is preferable, preferably 420 ⁇ TI ⁇ 520, and most preferably 430 ⁇ TI ⁇ 510.
- Log is a natural logarithm.
- the heat treatment time becomes long, the temperature shifts to a low temperature side, but the influence on the temperature is given approximately by the reciprocal of the square root of time.
- the processing rate RE means (1- (cross-sectional area of the tube rod wire after processing) / (cross-sectional area of the tube rod wire before processing)) ⁇ 100%.
- RE applies the total cold working rate from the extruded material.
- heat treatment TH1 When heat treatment TH1 is performed between the drawing / drawing steps, in order to have higher conductivity and ductility, it is desirable that the processing rate from after extrusion to heat treatment TH1 exceeds the processing rate after heat treatment TH1. . Multiple precipitation heat treatments may be performed, and in this case as well, it is desirable that the total cold working rate until the final precipitation heat treatment exceeds the working rate after the heat treatment TH1.
- the cold working after the extrusion facilitates the movement of atoms such as Co and P and promotes the precipitation of Co and P in the heat treatment TH1.
- the higher the processing rate the lower the temperature of heat treatment. In the cold working after the heat treatment TH1, the strength is improved by work hardening, but the ductility is lowered.
- the decrease in conductivity is significant. Considering the balance of overall conductivity, ductility, and strength, the processing rate after the heat treatment TH1 should be smaller than the processing rate before the heat treatment. In addition, after extruding, if a strong working process in which the total cold working rate up to the final line exceeds 90% is performed, the ductility becomes poor. Considering ductility, the following more preferable precipitation heat treatment is required.
- fine crystal grains having a low dislocation density or recrystallized grains are generated in the metal structure of the matrix to recover the ductility of the matrix.
- the fine crystal grains and the recrystallized grains are collectively referred to as recrystallized grains. If these particle sizes are large, or if their proportion is large, the matrix becomes too soft. In addition, the precipitate grows, the average particle size of the precipitate increases, and the strength of the final wire decreases. Accordingly, the ratio of the recrystallized grains in the matrix during the precipitation heat treatment is 45% or less, preferably 0.3 to 30%, more preferably 0.5 to 15% (the remainder is an unrecrystallized structure).
- the average particle size of the grains is 0.7 to 7 ⁇ m, preferably 0.7 to 5 ⁇ m, more preferably 0.7 to 4 ⁇ m.
- the fine crystal grains described above are too fine and may be difficult to distinguish from a rolled structure with a metallographic microscope.
- EBSP Electro Back Scattering Diffraction Pattern
- fine crystal grains with random orientation, low dislocation density, and low strain are observed, mainly around the original grain boundaries extending in the rolling direction. it can.
- fine crystal grains or recrystallized grains are generated by cold working with a processing rate of 75% or more and precipitation heat treatment. Due to the fine recrystallized grains and the like, the ductility of the work-cured material is improved without impairing the strength.
- this heat treatment of TH1 may be performed at the stage of the bar, or this heat treatment may be performed after the press and forging. Further, when exceeding the final temperature condition of 630 ° C. or heat treatment TH1, for example, when brazing, TH1 may be unnecessary.
- the heat treatment conditions are the same whether or not heat treatment is performed at the bar stage, and the total cold working rate from the extruded material is applied to RE.
- the two-dimensional observation surface has a substantially circular or substantially elliptical shape, and the average particle diameter is 1.5 to 20 nm, or 90% or more of the precipitates are 0.7 to 30 nm, or 2.5 to Fine precipitates of 30 nm (30 nm or less) are obtained by uniformly dispersing. Precipitates are uniformly and finely distributed and have a uniform size. The smaller the particle size, the smaller the recrystallized particle size, and the higher the strength and heat resistance.
- the average particle size of the precipitate is preferably 1.5 to 20 nm, and preferably 1.7 to 9.5 nm.
- the strength mainly depends on precipitation hardening.
- the precipitate is optimally 2.5 to 9 nm, and at the expense of precipitation hardening, the ductility and conductivity are improved and balanced.
- the deposit of 30 nm or less is preferably 90% or more, preferably 95% or more, and optimally 98% or more.
- the size of precipitates such as Co and P is effective for strength, high-temperature strength, formation of an unrecrystallized structure, refinement of the recrystallized structure, and ductility.
- the precipitate does not include a crystallized product generated in the casting stage.
- an arbitrary 1000 nm ⁇ 1000 nm region at a microscopic observation position (excluding special parts such as the extreme surface layer) described later when observed with a 150,000 or 750,000 times TEM
- the distance between the adjacent precipitation particles of at least 90% or more of the precipitation particles is defined as 150 nm or less, preferably 100 nm or less, and optimally within 15 times the average particle diameter.
- at least 25 or more, preferably 50 or more, and optimally 100 or more precipitated particles are present. Even if this portion is taken, it can be defined that there is no large precipitation-free zone that affects the characteristics, that is, there is no non-uniform precipitation zone.
- heat treatment TH2 When a high cold working rate is imparted after precipitation heat treatment like a thin wire, a material subjected to hot extrusion with an alloy according to the invention is subjected to heat treatment TH2 at a temperature below the recrystallization temperature in the course of wire drawing, and ductility is achieved.
- wire drawing is performed after improving the strength, the strength is improved.
- the heat treatment TH2 is performed after the wire drawing, the ductility such as the bending resistance is remarkably improved although the strength is slightly lowered.
- the cold working rate exceeds 30% or 50% after the heat treatment of TH1
- precipitates such as Co and P are fine, and thus the phenomenon of decreasing electrical conductivity may occur. Occurs and the conductivity is reduced by 2% IACS or more, or 3% IACS or more.
- the conductivity further decreases.
- the cold processing rate is 90% or more
- the conductivity decreases from 4% IACS to 10% IACS.
- the degree of the decrease in conductivity is 2 to 5 times greater than that of copper, Cu—Zn alloy, Cu—Sn alloy or the like. Therefore, the effect of TH2 on conductivity is greater when a high processing rate is imparted.
- heat treatment TH1 is preferably performed.
- the wire diameter is 3 mm or less, it is preferable to heat-treat with a continuous annealing equipment at 350 to 700 ° C. for 0.001 seconds to several seconds from the viewpoint of productivity due to winding.
- the final cold working rate is 60% or more and importance is placed on ductility, bending resistance and conductivity, it is better to lengthen the time, and it is preferable to hold at 200 to 375 ° C. for 10 to 240 minutes.
- the heat treatment TH2 may be finally applied to the bar material and the cold forging / press material as well as the wire material as recovery of ductility / conductivity or stress removal annealing. This heat treatment TH2 improves conductivity and ductility. In the case of a bar or a pressed product, since the material temperature does not rise in a short time, it is preferable to hold at 250 to 550 ° C. for 1 to 240 minutes.
- the characteristics of the high performance copper tube / bar / wire according to this embodiment will be described.
- a structure control mainly composed of aging / precipitation hardening, solid solution hardening and crystal grain refinement, and various elements are added for the structure control.
- conductivity when an additive element is dissolved in the matrix, the conductivity is generally inhibited, and depending on the element, the conductivity is remarkably inhibited.
- Inventive alloys Co, P, and Fe are elements that significantly impede conductivity. For example, only adding 0.02 mass% of Co, Fe, and P to pure copper will impair the conductivity by about 10%.
- the invention alloy is characterized in that if the constituent elements Co, P, etc. are added according to the above formula, most of the solid solution, such as Co, P, etc. can be precipitated in the subsequent heat treatment. Can be secured.
- Corson alloy (Ni, Si addition) and titanium copper which are well known as age-hardening copper alloys other than Cr-Zr copper, are Ni, Si, Alternatively, a large amount of Ti remains in the matrix. As a result, there is a drawback that although the strength is high, the conductivity is lowered. In general, when a solution treatment at a high temperature necessary for the complete solution-aging precipitation process (for example, heating at a typical solution temperature of 800 to 950 ° C. for several minutes or more) is performed, the crystal grains become coarse. Grain coarsening adversely affects various mechanical properties. Further, since the solution treatment is subjected to quantitative restrictions in production, it leads to a significant cost increase.
- the solution is sufficiently dissolved in the hot extrusion process, and the microstructure control of crystal grain refinement is performed at the same time. It has been found that P and the like are finely precipitated.
- the diameter of a typical billet is 150 to 400 mm and the length is about 400 to 2000 mm. is there.
- the billet is charged into the container of the extruder, the container and the billet come into contact with each other, and the billet temperature decreases.
- a die for extruding to a predetermined size is provided in front of the container, and a steel block called a dummy block is provided in the rear, thereby removing heat from the billet.
- it depends on the length of the billet and the extrusion size it takes about 20 to 200 seconds to complete the extrusion.
- the temperature of the billet decreases, and the billet temperature decreases significantly after the remaining billet length is extruded to 250 mm or less, particularly 125 mm or less, or to the length corresponding to the diameter of the billet, particularly the radius.
- the extruded material is in an air-cooled state with a slow cooling rate for about 10 seconds from immediately after extrusion to cooling.
- the extrusion is performed in a state where the temperature decrease is small and the cooling after the extrusion is fast.
- the precipitation rate of Co, P, etc. is slow, so that it is sufficient within the range of normal extrusion conditions. It is characterized by being able to form a solution.
- the distance from the extrusion to the cooling facility is preferably about 10 m or less, for example.
- the combination of the composition of Co, P, etc. and the hot extrusion process, the Co, P, etc. are dissolved in the hot extrusion process, and the fine Recrystallized grains are formed.
- Co, P, etc. are finely precipitated, and high strength and high conductivity can be obtained.
- higher strength can be obtained without impairing conductivity by work hardening.
- high conductivity and high ductility can be obtained by applying an appropriate heat treatment TH1.
- an aging precipitation type copper alloy is completely solutionized, and then has a high strength and high conductivity through a process of precipitation.
- the material made by the process of the present embodiment in which solutionization is simplified generally has poor performance.
- the tube rod wire according to the present embodiment has the same or better performance than that of the high-cost complete solution-precipitation hardening process, and has excellent strength, ductility, and conductivity. The greatest feature is that it can be obtained in a balanced state. Since it is manufactured by hot extrusion, the cost is low.
- Cr-Zr copper which is the only high-strength and high-conductivity copper, which is a solution-aging / precipitation type alloy.
- Cr—Zr copper is poor in hot deformability at a temperature of 960 ° C. or higher, the upper limit temperature for solution treatment is greatly restricted.
- the solid solubility limit of Cr and Zr decreases rapidly with a slight decrease in temperature, the lower limit temperature side of solution treatment is also restricted, and the range of temperature conditions for solution treatment is narrow. Even if it is in a solution state at the initial stage of extrusion, sufficient solution cannot be achieved in the middle and later stages of extrusion due to a decrease in temperature.
- a performance index I is defined as follows as an index for evaluating the strength, elongation, and conductivity of tubes, rods, and wires.
- conductivity R (% IACS)
- tensile strength S (N / mm 2 )
- elongation L (%)
- I R 1/2 ⁇ S ⁇ (100 + L) / 100
- the figure of merit I is preferably 4300 or higher. Since the thermal conductivity and the electrical conductivity have a strong correlation, the figure of merit I also indicates the level of thermal conductivity.
- the electrical conductivity which is a premise of the rod, is 45% IACS or more and the figure of merit I is 4600 or more, preferably 4800 or more, optimally 5000 or more.
- the conductivity is preferably 50% IACS or more, more preferably 60% IACS or more.
- 65% IACS or more is good, preferably 70% IACS or more, more preferably 75% IACS or more.
- the performance index I is preferably 4600 or more, preferably 4900 or more, more preferably, on the condition that the electrical conductivity as a precondition is 45% IACS or more. 5100 or more, optimally 5400 or more.
- the conductivity is preferably 50% IACS or more, more preferably 60% IACS or more.
- high conductivity it is preferably 65% IACS or more, more preferably 70% IACS or more, and most preferably 75% IACS or more.
- the wire material needs to be flexible or ductile, it is preferable that the figure of merit I is 4300 or more and the elongation is 5% or more.
- Extruded pipes, rods, and wires are made of extruded materials from the same billet. Mechanical properties and electrical conductivity in the length direction of extrusion (hereinafter referred to as the extrusion production lot) It is desirable that the inner variation is small. Due to the variation in the extrusion production lot, the ratio of (minimum tensile strength / maximum tensile strength) of the material after heat treatment or the final processed rod / wire / tube is 0.9 or more and the conductivity is (minimum conductivity). Ratio / maximum conductivity) is preferably 0.9 or more.
- the ratio of (minimum tensile strength / maximum tensile strength) and the ratio of (minimum conductivity / maximum conductivity) are preferably 0.925 or more, more preferably 0.95 or more, respectively.
- the ratio of (minimum tensile strength / maximum tensile strength) and the ratio of (minimum conductivity / maximum conductivity) can be increased, and the quality is improved.
- Cr-Zr copper having high solution sensitivity has a large variation when the ratio of (minimum tensile strength / maximum tensile strength) is 0.7 to 0.8 when it is produced by the manufacturing process of this embodiment.
- the most popular copper alloy C3604 (60Cu-37Zn-3Pb) produced by hot extrusion of a copper alloy, for example, due to extrusion temperature difference, extrusion metal flow, etc. Then, it is normal that the intensity ratio is about 0.9. Further, pure copper: tough pitch C1100 that does not undergo precipitation hardening also takes a value close to 0.9 due to the difference in crystal grain size. In general, the temperature at the front end (head) immediately after extrusion is 30 to 180 ° C. higher than the temperature at the rear end (tail).
- the strength at 400 ° C. is 200 N / mm 2 or more, there is no practical problem, but in order to obtain a high temperature strength or a long life, it is preferably 220 N / mm 2 or more, more preferably 240 N / mm 2. As described above, optimally, it is 260 N / mm 2 or more. Since the high performance copper tube / rod / wire of this embodiment is 200 N / mm 2 or more at 400 ° C., it can be used in a high temperature state. Precipitates such as Co and P are hardly re-dissolved at 400 ° C.
- the crystal grain size is 5 to 75 ⁇ m.
- the crystal grain size is preferably 7.5 to 65 ⁇ m, and optimally 8 to 55 ⁇ m.
- the composition and process are determined by the balance of high-temperature strength, wear resistance (generally proportional to strength), and conductivity required on the premise of high strength and high conductivity.
- wear resistance generally proportional to strength
- conductivity required on the premise of high strength and high conductivity.
- cold drawing is performed before and / or after heat treatment, and the higher the total cold working rate, the higher the strength material, but the balance with ductility must also be emphasized.
- the total drawing rate is preferably 60% or less, or the drawing rate after heat treatment is 30% or less.
- the high-performance copper tube / bar / wire according to this embodiment is suitable for applications such as a trolley wire, a welding tip, and an electrode.
- the high performance copper tube / rod / wire according to the present embodiment has high heat resistance, and has a Vickers hardness (HV) of 90 or more after heating at 700 ° C. for 120 seconds, or 80% of the value of Vickers hardness before heating. That's it.
- the precipitate in the metal structure after heating has an average particle size of 1.5 to 20 nm, or 90% or more of all the precipitates is 30 nm or less, or the recrystallization rate in the metal structure is 45% or less.
- More preferable conditions are 3 to 15 nm in average particle diameter, or 95% or more of all precipitates is 30 nm or less, or the recrystallization rate in the metal structure is 30% or less.
- the brazing material is, for example, silver brazing BAg-7 (40-60% Ag, 20-30% Cu, 15-30% Zn, 2-6% Sn) as shown in JIS Z 3261, and the solidus temperature is 600 to 650 ° C., and the liquidus temperature is 640 to 700 ° C.
- BAg-7 40-60% Ag, 20-30% Cu, 15-30% Zn, 2-6% Sn
- the solidus temperature 600 to 650 ° C.
- the liquidus temperature is 640 to 700 ° C.
- the high performance copper tube / bar / wire material according to the present embodiment is excellent in bending resistance, and is therefore suitable for wire harnesses, connector wires, robot wiring, aircraft wiring, and the like.
- the electrical conductivity is 65% IACS or higher, preferably 70% IACS or higher, even if the strength is increased to 50% IACS or higher, or even slightly reduced in strength, or Optimally, it is divided into two parts, 75% IACS or more.
- the composition and process conditions are determined according to the application.
- the high-performance copper pipe, rod, and wire according to this embodiment are optimal for electrical applications such as relays, terminals, and power distribution components that are made by forging or pressing.
- forging and pressing are collectively referred to as compression processing.
- nuts and faucet fittings have utility value because there is no risk of stress corrosion cracking by taking advantage of high strength and ductility.
- the processing rate of the cold drawing of the material is appropriately determined depending on the press capability and the product shape.
- the pressing capability is small or a compression process with a very high processing rate is applied, the drawing is limited to a drawing rate of about 20%, for example, without heat treatment after hot extrusion.
- the material after drawing is soft, it can be formed into a cold and complex shape by compression, and heat treatment is performed after forming. Even processing equipment with low power can be easily molded because the material strength before heat treatment is low and the moldability is good.
- heat treatment is performed after cold forging or pressing, the conductivity becomes high, so that a high-power facility is not required and the cost is reduced.
- after forging or press molding when brazing at a temperature higher than the heat treatment temperature of TH1, for example, 700 ° C. is performed, it is not particularly necessary to perform HT1 treatment with a raw material rod, tube, or wire. Co and P in solution form are precipitated, and the heat resistance of the matrix is enhanced by the solid solution of Sn, so that the formation of recrystallized grains in the matrix is delayed and the conductivity is increased.
- the heat treatment conditions after compression processing are preferably lower than the heat treatment conditions performed after hot extrusion, before and after drawing / drawing processing. This is because, in the compression processing, if cold processing is locally performed at a high processing rate, heat treatment is performed based on that portion. Therefore, when the processing rate is high, the heat treatment condition moves to the low temperature side.
- Preferred conditions are 380 to 630 ° C. and 15 to 240 minutes.
- the total processing rate from the hot extruded material to the compression processed material is applied to RE.
- the heat treatment index TI 400 ⁇ TI ⁇ 540 is preferable, and preferably 420 ⁇ TI ⁇ . 520 and optimally 430 ⁇ TI ⁇ 510.
- the heat treatment is not necessarily required, but the main purpose is to restore ductility, further improve conductivity, and remove residual stress.
- preferable conditions are 300 to 550 ° C. and 5 to 180 minutes.
- Example 2 Using the above-described first invention alloy, second invention alloy, third invention alloy, and copper alloy having a composition for comparison, a high performance copper tube / bar / wire was prepared.
- Table 1 shows the composition of the alloy that produced the high performance copper tube / rod / wire.
- the alloy is alloy No. 1 of the first invention alloy. 11 to 13 and alloy No. 2 of the second invention alloy. 21 to 24, and alloy No. 3 of the third invention alloy. Nos. 31 to 36 and 371 to 375, and alloy Nos. Having compositions similar to the invention alloys as comparative alloys. Nos. 41 to 49 and C1100 alloy no. 51 and conventional Cr—Zr copper alloy no.
- a high-performance copper tube / bar / wire was prepared by using a plurality of processes for any alloy.
- FIGS. 1 to 9 show the flow of the manufacturing process of the high performance copper tube / rod / wire, and Tables 2 and 3 show the conditions of the manufacturing process.
- FIG. 1 shows the structure of the manufacturing process K.
- raw materials were melted by an actual electric furnace, 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 900 ° C. for 2 minutes, and a bar having an outer diameter of 25 mm was extruded with an indirect extruder.
- the extrusion capacity of the indirect extruder was 2750 tons (the same applies to the indirect extruder in the following steps).
- the temperature of the container of the extruder was 400 ° C., and the temperature of the dummy block was preheated to 350 ° C. In this embodiment, including the subsequent steps, the container temperature and the dummy block temperature are the same.
- the extrusion speed (ram movement speed) was 12 mm / second, and cooling was carried out by water cooling in a coil winder separated from the extrusion die by about 10 m (the series of steps from dissolution to this step is referred to as step K0. Hereinafter, the same applies). ).
- the material temperature at the extrusion tip (head) was 870 ° C
- the temperature at the extrusion center was 840 ° C
- the extrusion rear end The temperature of (tail) was 780 ° C.
- the front end and the rear end are the most distal part, 3 m from the rear end.
- the average cooling rate from 840 ° C. to 500 ° C. after hot extrusion was about 30 ° C./second.
- step K01 the film was drawn by cold drawing to an outer diameter of 22 mm (step K01), subjected to heat treatment TH1 at 500 ° C. for 4 hours (step K1), and then drawn to an outer diameter of 20 mm (step K2). Further, after step K0, heat treatment TH1 was performed at 520 ° C. for 4 hours (step K3), and then drawn to an outer diameter of 22 mm (step K4). Further, after step K0, heat treatment TH1 was performed at 500 ° C. for 12 hours (step K5). In C1100, the heat treatment was performed at 150 ° C. for 2 hours in step K1, but no heat treatment TH1 was performed because there was no element to be deposited (the same applies to other manufacturing steps described later).
- FIG. 2 shows the configuration of the manufacturing process L.
- the manufacturing process L differs from the manufacturing process K1 in the heating temperature of the billet.
- the heating temperature was 825 ° C. in Step L1, 860 ° C. in Step L2, 925 ° C. in Step L3, and 975 ° C. in Step L4.
- FIG. 3 shows the configuration of the manufacturing process M.
- the manufacturing process M differs from the manufacturing process K1 in the temperature condition of the heat treatment TH1.
- the temperature conditions are as follows: Step M1 is 360 ° C. for 15 hours, Step M2 is 400 ° C. for 4 hours, Step M3 is 475 ° C. for 12 hours, Step M4 is 590 ° C. for 4 hours, and Step M5 is 620 ° C. for 0.3 hours. Step M6 was carried out at 650 ° C. for 0.8 hour.
- FIG. 4 shows the configuration of the manufacturing process N.
- the manufacturing process N differs from the manufacturing process K1 in terms of hot extrusion conditions and heat treatment TH1.
- Step N1 the billet was heated at 900 ° C. for 2 minutes, and a bar having an outer diameter of 35 mm was extruded using an indirect extruder.
- the extrusion speed was 16 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 21 ° C./second.
- the film was drawn to an outer diameter of 31 mm by cold drawing, and heat treatment TH1 was carried out continuously at 500 ° C. for 2 hours and at 480 ° C. for 4 hours.
- Step N1 a heat treatment TH1 was performed in which 515 ° C. was continued for 2 hours and 500 ° C. for 6 hours (step N11).
- the billet was heated at 900 ° C. for 2 minutes, and a bar having an outer diameter of 35 mm was extruded directly by an extruder.
- the extrusion capacity of the direct extruder was 3000 tons (same in the direct extruder of the following steps).
- the extrusion speed was 18 mm / second, and cooling was performed by shower water cooling. The cooling rate was about 17 ° C./second.
- the film was drawn to an outer diameter of 31 mm by cold drawing, and heat treatment TH1 was carried out continuously at 500 ° C.
- Step N21 a heat treatment TH1 was carried out for 2 hours at 515 ° C. and 6 hours at 500 ° C.
- Step N3 the billet was heated at 900 ° C. for 2 minutes, and a bar having an outer diameter of 17 mm was extruded by an indirect extruder. The extrusion speed was 10 mm / second, and cooling was performed by water cooling. The cooling rate was about 40 ° C./second. Then, the outer diameter was drawn to 14.5 mm by cold drawing, and heat treatment TH1 was performed at 500 ° C. for 4 hours. Further, after water cooling in the step N3, heat treatment TH1 was performed at 530 ° C. for 3 hours (step N31).
- FIG. 5 shows the structure of the manufacturing process P.
- the manufacturing process P differs in the cooling conditions after extrusion compared to the manufacturing process K1.
- Step P1 the billet was heated at 900 ° C. for 2 minutes, and a bar having an outer diameter of 25 mm was extruded by an indirect extruder.
- the extrusion speed was 20 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 50 ° C./second.
- the film was drawn to an outer diameter of 22 mm by cold drawing, and heat treatment TH1 was performed at 500 ° C. for 4 hours.
- or P4 changed process P1, the conditions of extrusion and cooling.
- the extrusion speed was 5 mm / second, and cooling was performed by water cooling. The cooling rate was about 13 ° C./second.
- the extrusion speed was 12 mm / second, and cooling was performed by forced air cooling. The cooling rate was about 18 ° C./second.
- the extrusion speed was 12 mm / second, and cooling was performed by air cooling. The cooling rate was about 10 ° C./second.
- FIG. 6 shows the configuration of the manufacturing process Q.
- the manufacturing process Q differs from the manufacturing process K1 in cold drawing conditions.
- step Q1 the billet was heated at 900 ° C. for 2 minutes, and a bar with an outer diameter of 25 mm was extruded with an indirect extruder.
- the extrusion speed was 12 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 30 ° C./second.
- the outer diameter was drawn to 20 mm by cold drawing, and heat treatment TH1 was performed at 490 ° C. for 4 hours.
- Step Q2 was drawn to an outer diameter of 18.5 mm by cold drawing after heat treatment TH1 in step Q1.
- step Q3 after water cooling in step Q1, the outer diameter was drawn to 18 mm by cold drawing, and heat treatment TH1 was performed at 475 ° C. for 4 hours.
- FIG. 7 shows the configuration of the manufacturing process R.
- the manufacturing process R manufactures a pipe material.
- the billet is heated at 900 ° C. for 2 minutes, and a tube having an outer diameter of 65 mm and a wall thickness of 6 mm is extruded by a 3000-ton direct extruder.
- the extrusion speed was 17 mm / second, and cooling was performed by rapid water cooling.
- the cooling rate was about 80 ° C./second.
- heat treatment TH1 was performed at 520 ° C. for 4 hours.
- the film was drawn by cold drawing to an outer diameter of 50 mm and a wall thickness of 4 mm, and then heat treatment TH1 was performed at 460 ° C. for 6 hours.
- FIG. 8 shows the configuration of the manufacturing process S.
- the manufacturing process S manufactures a wire.
- the billet was heated at 910 ° C. for 2 minutes, and a bar having an outer diameter of 11 mm was extruded using an indirect extruder.
- the extrusion speed was 9 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 30 ° C./second.
- the outer diameter was drawn to 8 mm by cold drawing
- heat treatment TH1 was performed at 480 ° C. for 4 hours, and the outer diameter was drawn to 2.8 mm by cold drawing.
- heat treatment TH2 was performed at 325 ° C. for 20 minutes (step S2).
- step S1100 when the same heat treatment TH2 is performed, recrystallization occurs, so that heat treatment is performed at 150 ° C. for 20 minutes. Further, after step S1, cold drawing was performed to an outer diameter of 1.2 mm (step S3). Further, after step S1, heat treatment TH2 is performed at 350 ° C. for 10 minutes, followed by cold drawing to an outer diameter of 1.2 mm (step S4), and further heat treatment TH2 at 420 ° C. for 0.3 minutes. Performed (step S5). In addition, after water cooling in step S1, heat treatment TH1 is performed at 520 ° C.
- step S6 cold drawing / drawing is performed in order to obtain an outer diameter of 8 mm and 2.8 mm, and heat treatment TH2 is performed at 375 ° C. for 5 minutes.
- step S6 water cooling in step S1
- step S7 heat treatment TH1 is performed at 490 ° C. for 4 hours
- step S7 heat treatment TH1 for a time was performed.
- step S1 After water cooling in step S1, the wire is drawn to an outer diameter of 4 mm by cold drawing, heat-treated TH1 for 4 hours at 470 ° C., and further drawn to an outer diameter of 2.8 mm and 1.2 mm in order, Heat treatment TH1 was performed at 425 ° C. for 1 hour (step S8). Further, after the drawing to the outer diameter of 1.2 mm in step S8, heat treatment TH2 was performed at 360 ° C. for 50 minutes (step S9).
- FIG. 9 shows the configuration of the manufacturing process T.
- the manufacturing process T is a manufacturing process of a bar and a wire having a solution-precipitation process, and was performed for comparison with the manufacturing method of the present embodiment.
- the billet was heated at 900 ° C. for 2 minutes, and a bar with an outer diameter of 25 mm was extruded with an indirect extruder.
- the extrusion speed was 12 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 30 ° C./second.
- heating was performed at 900 ° C. for 10 minutes, and water cooling was performed at a cooling rate of about 120 ° C./second to form a solution.
- heat treatment TH1 was performed at 520 ° C. for 4 hours (process T1), and the film was drawn to an outer diameter of 22 mm by cold drawing (process T2).
- the billet was heated at 900 ° C. for 2 minutes, and a bar having an outer diameter of 11 mm was extruded by an indirect extruder.
- the extrusion speed was 9 mm / second, and cooling was performed by water cooling.
- the cooling rate was about 30 ° C./second.
- heating was performed at 900 ° C. for 10 minutes, followed by water cooling at a cooling rate of about 150 ° C./second to form a solution.
- heat treatment TH1 is performed at 520 ° C. for 4 hours, drawn to an outer diameter of 8 mm by cold drawing, drawn to an outer diameter of 2.8 mm by cold drawing, and heat treated TH2 at 350 ° C. for 10 minutes. Performed (step T3).
- Evaluation of high performance copper tubes, rods and wires made by the methods described above include tensile strength, Vickers hardness, elongation, Rockwell hardness, number of repeated bends, conductivity, heat resistance, 400 ° C high temperature tensile strength, after cold compression The Rockwell hardness and conductivity were measured. In addition, the metal structure was observed to measure the crystal grain size and the ratio of precipitates having a size of 30 nm or less.
- the measurement of tensile strength was performed as follows.
- the shape of the test piece was a 14A test piece in which the gauge distance of JIS Z 2201 was (the square root of the cross-sectional area of the test piece parallel part) ⁇ 5.65.
- a 9B test piece having a gauge distance of JIS Z 2201 of 200 mm was used.
- a 14C test piece having a gauge distance of JIS Z 2201 (square root of the cross-sectional area of the parallel part of the test piece) ⁇ 5.65 was used.
- the measurement of the number of repeated bendings was performed as follows.
- the radius RA of the bent portion was set to 2 ⁇ RB (outer diameter of the wire rod), 90 ° bending was performed, and the time when the bent portion was returned to the original position was set to once, and further bent to the opposite side by 90 ° and repeated until breaking.
- a conductivity measuring device (SIGMATEST D2.068) manufactured by Nippon Ferster Co., Ltd. was used in the case of a bar having a diameter of 8 mm or more and in the case of a cold compression test piece.
- measurement was performed according to JIS H 0505.
- a double bridge was used for measurement of electric resistance.
- the terms “electric conduction” and “conduction” are used in the same meaning. Further, since there is a strong correlation between thermal conductivity and electrical conductivity, the higher the conductivity, the better the thermal conductivity.
- the heat-resistant characteristics are as follows: a test piece obtained by cutting a bar material after each process into a length of 35 mm (however, 300 mm for a tensile test in Table 10 described later), and a height of 7 mm obtained by cold-compressing the bar material after each process.
- Prepare a compression test piece immerse it in a 700 ° C. salt bath (mixed NaCl and CaCl 2 in about 3: 2) for 120 seconds, and after cooling (water cooling), Vickers hardness, recrystallization rate, conductivity, precipitation
- the average particle size of the product and the proportion of precipitates having a particle size of 30 nm or less were measured.
- Steps K1, K2, K3, and K4 heat resistance characteristics were tested using a bar specimen, and in Steps K0 and K01, heat resistance characteristics were tested using a compression specimen. Note that heat treatment after compression was not performed for both products.
- the measurement of 400 ° C high temperature tensile strength was performed as follows. After holding at 400 ° C. for 10 minutes, a high temperature tensile test was conducted. The gauge distance was 50 mm, and the test part was machined to a 10 mm outer diameter with a lathe.
- the crystal grain size was measured from a metal micrograph according to the comparison method of the JIS H 0501 copper grain size test method.
- the average recrystallized grain size and the recrystallization rate were measured using metal microscope photographs of 500 times, 200 times, 100 times, and 75 times by appropriately selecting the magnification according to the size of the crystal grains.
- the average recrystallized grain size was basically measured by a comparative method.
- the recrystallization rate is measured by classifying non-recrystallized grains and recrystallized grains (including fine crystal grains), binarizing the recrystallized portion with image processing software “WinROOF”, and calculating the area ratio as the recrystallized ratio. did. Those difficult to judge from a metallographic microscope were determined by the FE-SEM-EBSP method.
- the crystal grain having a crystal grain boundary having an orientation difference of 15 ° or more is filled with magic, and binarized by the image analysis software “WinROOF”, and the recrystallization rate was calculated.
- the measurement limit is approximately 0.2 ⁇ m, and even if there are recrystallized grains of 0.2 ⁇ m or less, they are not included in the measured values.
- the particle size of the precipitates is obtained by binarizing a transmission electron image of a TEM (transmission electron microscope) at 150,000 times and 750,000 times with image processing software “WinROOF”, and extracting the precipitates. The average value was calculated and the average particle size was measured. The measurement positions were 2 points at 1r / 2 and 6r / 7 from the center of the bar wire, where r is the radius, and the average value was taken. In the pipe material, assuming that the wall thickness is h, two points of 1h / 2 and 6h / 7 from the inner surface of the pipe material were taken, and the average value was taken.
- the size of the precipitate is difficult to measure if there is dislocation in the metal structure, the size of the precipitate was measured with a bar wire obtained by subjecting the extruded material to heat treatment TH1, for example, a bar wire after the process K3.
- a bar wire obtained by subjecting the extruded material to heat treatment TH1
- a bar wire after the process K3 For a sample subjected to a heat resistance test at 700 ° C. for 120 seconds, measurement was performed on the recrystallized portion. Further, the ratio of the number of precipitates of 30 nm or less was measured from the particle diameters of the respective precipitates. However, in the transmission electron image of 150,000 times TEM, the error is large for those having a particle diameter of less than 2.5 nm. And excluded from the precipitated particles (not included in the calculation).
- the proportion of precipitates of 30 nm or less accurately refers to 0.7 to 30 nm, or 2.5 to 30 nm.
- Wear resistance was measured as follows. A rod-shaped test piece having an outer diameter of 19.5 mm and a thickness (axial direction length) of 10 mm was obtained by subjecting a rod having an outer diameter of 20 mm to cutting and drilling. Next, the test piece was fitted and fixed to the rotating shaft, and a SUS304 roll (outer diameter 60.5 mm) made of 18 mass% Cr, 8 mass% Ni, and remaining Fe was applied to the outer peripheral surface of the ring-shaped test piece. Rotating shaft while rolling with the load applied and dropping multi oil on the outer peripheral surface of the test piece (at the beginning of the test, the test surface is excessively wetted and then 10 mL is replenished per day) was rotated at 209 rpm.
- the rotation number of the test piece reached 100,000 times, the rotation of the test piece was stopped, and the weight difference before and after the rotation of the test piece, that is, the weight loss (mg) was measured. It can be said that the smaller the wear loss is, the more excellent the copper alloy is.
- Tables 4 and 5 show the results of step K0.
- the inventive alloy has a smaller average grain size than the comparative alloy and Cr—Zr copper.
- the tensile strength and hardness are slightly higher than those of the comparative alloy, but the elongation value is clearly high and the conductivity is low.
- Tubes, rods, and wires are rarely used in an extruded state, and are used after being subjected to various processes. Therefore, the tube, rod, and wire are preferably soft in the extruded state and may have a low electrical conductivity. And after cold compression, when heat treatment is performed, the hardness becomes higher than that of the comparative alloy, and the Sn.
- the conductivity is 70% IACS or higher.
- the conductivity is 65% IACS or more, which is an improvement of about 25% IACS compared to before heating. Further, it has a Vickers hardness of 110 or more and a recrystallization rate of about 20%, which is lower than that of the comparative alloy. Since many of Co, P, etc., which were in a solid solution state, were precipitated, the conductivity was high, and the average particle size of the precipitate was fine at about 5 nm, so it is considered that recrystallization was prevented.
- Tables 6 and 7 show the results of step K01.
- C1100 has a large average crystal grain size as a result of extrusion, and a crystallized product of Cu 2 O is generated.
- the alloy according to the invention has a slightly higher tensile strength and hardness than the comparative alloy and C1100, and the difference is slightly larger than that of the process K0. Similar to the process K0, there is no significant difference in the figure of merit I at this stage. However, as in the process K0, when cold treatment is performed after cold compression, the hardness becomes higher than that of the comparative alloy, and the conductivity becomes 70% IACS or higher. In a high-temperature test at 700 ° C.
- the electrical conductivity is 65% IACS or more, which is improved by about 25% IACS compared to before heating.
- the Vickers hardness is about 120, and the recrystallization rate is as low as about 20%. Precipitation improves the conductivity, and the average particle size of the precipitate is fine at about 5 nm, which is considered to prevent recrystallization.
- Tables 8 and 9 show the results of step K1.
- the alloy according to the invention has a smaller average crystal grain size after extrusion than the comparative alloy and C1100, and has good results in tensile strength, Vickers hardness, and Rockwell hardness. Also, the elongation is higher than C1100. The conductivity is almost 70% or more of C1100 in most invention alloys.
- the invention alloy shows much higher values than the comparative alloy and C1100 even in Vickers hardness after heating at 700 ° C. and high temperature tensile strength at 400 ° C. Inventive alloys also exhibit higher values than the comparative alloys and C1100 in Rockwell hardness after cold compression.
- the alloy is much lower than the comparative alloy and C1100, and among them, the invention alloy having a large amount of Sn and Ag added is preferable.
- the alloy according to the invention is a high-strength and high-conductivity copper alloy, and it is better that it is in the center of the range as much as possible in the formula, the range of X1, X2, and X3 and the composition range.
- Table 10 shows the tensile strength, elongation, Vickers hardness, and conductivity of the bar after heating at 700 ° C. for 120 seconds after Step K1 and Step K01.
- the process K01 in which the heat treatment TH1 is not performed has the same tensile strength, elongation, Vickers hardness, and conductivity as the process K1 in which the heat treatment TH1 is performed.
- Step K01 has a low recrystallization rate even when heated to 700 ° C. This is presumably because precipitation of Co, P, etc. occurred and recrystallization was prevented. Further, from this result, when the material of the invention alloy not subjected to the precipitation treatment is heated at 700 ° C. for about 120 seconds by brazing or the like, the precipitation treatment is not required.
- Tables 11 and 12 show the results of Steps K2, K3, K4, and K5 together with the results of Step K1.
- Inventive alloys have good results in tensile strength, Vickers hardness, etc. also in steps K3 and K5 where only heat treatment TH1 is performed after extrusion.
- the elongation is low in the processes K2 and K4 in which the drawing process is performed after the heat treatment TH1, but the tensile strength and the Vickers hardness are further increased.
- the alloy according to the invention has a smaller average particle size of precipitates in the process K3 and a proportion of precipitates of 30 nm or less compared to the comparative alloy.
- the inventive alloy has better results in mechanical properties such as tensile strength and Vickers hardness than the comparative alloy and C1100 in the processes K2, K3, and K4.
- 10 shows alloy no. 11 is a transmission electron image of the eleventh step K3.
- the precipitated particles are fine and uniformly distributed with an average particle diameter of 3 nm.
- This alloy No. In the tube / bar / wire material in which the invention alloy was manufactured in the manufacturing process of the present embodiment as well as the sample of the process K3 of 11, the particle size of the precipitate was measured in Table 11 and Tables 21, 24, 25, and 31 described later.
- All the samples describing the data have a distance between the adjacent precipitation particles of 90% or more in an arbitrary 1000 nm ⁇ 1000 nm region of 150 nm or less, and in an arbitrary 1000 nm ⁇ 1000 nm region, There were 25 or more precipitated particles. That is, it can be said that the precipitates are uniformly distributed.
- the invention alloy has a fine average particle diameter of about 5 nm after heating at 700 ° C. for 120 seconds regardless of the presence or absence of heat treatment TH1 and regardless of the bar material or compression processed material. It is thought that recrystallization is prevented.
- 11 shows alloy no. 11 is a transmission electron image after heating at 700 ° C. for 120 seconds to the compression processed material in Step K0 of No. 11.
- the precipitated particles are fine with an average particle diameter of 4.6 nm, and there are almost no coarse precipitated particles of 30 nm or more, and they are uniformly distributed. In addition, in the case of heating at 700 ° C.
- the precipitated particles remain fine and many of the precipitated particles are present without being re-dissolved, so that compared with the state after the heat treatment TH1.
- the decrease in conductivity remains below 10% IACS (see Test Nos. 1, 32, etc. in Tables 11 and 12).
- Tables 13 and 14 show the results of Steps L1 to L4 together with the results of Step K1.
- or the process L4 differ in the process K1 and the heating temperature of a billet.
- the heating temperature is in an appropriate range (840 to 960 ° C.)
- the tensile strength, the Vickers hardness, and the like are high as in the process K1.
- the process L1 lower than the appropriate temperature there is an unrecrystallized part due to extrusion, and the tensile strength and Vickers hardness after the final processing are low.
- the heating temperature is higher than the appropriate temperature
- the average crystal grain size after extrusion is large, and the tensile strength, Vickers hardness, elongation, and conductivity after the final processing are low. Further, it is considered that the higher the heating temperature, the higher the strength because more Co, P, etc. are dissolved.
- Tables 15 and 16 show the results of Steps P1 to P4 together with the results of Step K1.
- the extrusion rate and the cooling rate after extrusion are different from those in the step K1.
- the average crystal grain size after the extrusion is smaller than the result in the process K1, and the tensile strength and Vickers hardness after the final processing are improved.
- the average crystal grain size after the extrusion is larger than the result in the step K1, and the tensile strength after the final processing Vickers hardness, etc. are reduced.
- the cooling rate is faster than an appropriate rate, so that the tensile strength and Vickers hardness after the final processing are favorable. From this result, in order to obtain high strength in the final bar, it is better that the cooling rate is high. It seems that the higher the cooling rate, the higher the strength because more Co, P, etc. are dissolved. Moreover, it is better that the cooling rate is fast also in heat resistance.
- the cooling method is water cooling, and the processes K, L, M, N, Q, and R have an extrusion speed of 45 ⁇ in the relationship between the extrusion speed (ram movement speed, billet extrusion speed) and the extrusion ratio H.
- P2 has an extrusion speed smaller than the value of 30 ⁇ H ⁇ 1/3 mm / sec, while it is between H ⁇ 1/3 mm / sec and 60 ⁇ H ⁇ 1/3 mm / sec.
- P1 has an extrusion speed greater than a value of 60 ⁇ H ⁇ 1/3 mm / sec.
- Tables 17 and 18 show the results of Steps M1 to M6 together with the results of Step K1.
- the conditions of the step K1 and the heat treatment TH1 are different.
- the processes M1 and M2 in which the heat treatment index TI is smaller than the appropriate condition the processes M4 and M6 in which the heat treatment index TI is larger than the appropriate condition, and the process M5 in which the heat treatment holding time is shorter than the appropriate time, the processes M3 and K1 in the appropriate conditions are Tensile strength, Vickers hardness, etc. after final processing are reduced. Also, the balance of tensile strength, conductivity and elongation (the product of these, performance index I) is poor. Moreover, heat resistance also deteriorates if it deviates from appropriate conditions.
- Tables 19 and 20 show the results of Steps Q1, Q2, and Q3 together with the results of Step K1.
- Processes Q1 and Q3 differ from process K1 in the drawing rate after extrusion.
- a drawing process is further performed after the process Q1.
- the temperature of the heat treatment TH1 is lowered according to the drawing rate. The higher the drawing rate after extrusion, the higher the tensile strength and Vickers hardness after final processing, and the lower the elongation. Further, by adding a drawing process after the heat treatment TH1, the elongation is reduced, but the tensile strength and Vickers hardness are improved.
- Tables 21 and 22 show the results of steps N1, N11, N2, N21, N3, and N31.
- step N1 heat treatment TH1 is performed in two stages
- step N11 heat treatment TH1 is performed after extrusion.
- steps K1 and K3 good results are shown as in steps K1 and K3.
- the extrusion is direct extrusion
- the two-stage heat treatment TH1 is performed in the same manner as the processes N1 and N11. Even in the case of direct extrusion, good results are shown as in steps K1 and K3.
- the bar of the process N1 has better conductivity than the bar of the process K1.
- Steps N3 and N31 are the same steps as steps K1 and K3, and the cooling rate after extrusion is fast.
- the average crystal grain size after extrusion is small, and the tensile strength and Vickers hardness after final processing are good.
- Steps N2 and N21 since the cooling rate is a little slow, the average particle size of the precipitate is increased, and the tensile strength and Vickers hardness after final processing are slightly low.
- Steps S1 to S9 are wire manufacturing steps, and the alloys according to the invention have a smaller average crystal grain size after extrusion than the comparative alloys and C1100 in Steps S1 to S2, and good results in tensile strength and Vickers hardness. ing. Further, in step S2 in which heat treatment TH2 is performed, the number of repeated bendings is improved compared to step S1, and in steps S4, S5, S6, and S9 in which heat treatment TH2 is performed, the number of repeated bendings is also increased. . In particular, S9 having a long holding time of heat treatment TH2 has a slightly low strength, but has a large number of repeated bending.
- Inventive alloys also show good tensile strength and Vickers hardness in Steps S3 to S6 in which the heat treatment TH1, TH2 and the wire drawing step are variously combined.
- the heat treatment TH1 was increased in the last step or the heat treatment TH1 was performed in a step close to the final, a material having low strength but particularly excellent bending resistance was obtained.
- steps S7 and S8 in which the heat treatment TH1 is performed twice the number of repeated bendings is particularly improved.
- the total wire drawing ratio before heat treatment TH1 is high at 75% or more, when heat treatment TH1 is applied, recrystallization is about 15%, but the size of the recrystallized grains is small at about 3 ⁇ m. For this reason, the strength is slightly reduced, but the bending resistance is improved.
- Steps R1 and R2 are tube manufacturing steps, and the alloys according to the invention have a high cooling rate after extrusion in steps R1 and R2, so that the size of precipitates is small, and good tensile strength and Vickers hardness are exhibited. Yes.
- Tables 27 and 28 show the results of Steps T1 and T2 together with the results of Steps K3 and K4.
- Steps T1 and T2 involve solution-aging and precipitation.
- steps T1 and T2 the average crystal grain size after extrusion is very large compared to steps K1 and K2.
- the tensile strength, the Rockwell hardness, and the conductivity are the same in the steps T1 and T2 and the steps K3 and K4.
- the steps T1 and T2 are performed with Cr—Zr copper
- the average crystal grain size after extrusion is very large as compared with the case where the steps K3 and K4 are performed with the alloy according to the invention.
- Well hardness is a little low and conductivity is a little high.
- Step T3 is a manufacturing step of a wire material that is subjected to solution-aging / precipitation.
- step T3 the average crystal grain size after extrusion is much larger than in step S6.
- tensile strength, Vickers hardness, and electrical conductivity are equivalent in process T3 and process S6, elongation and repeated bending exceed process S6.
- step T3 the precipitation effect itself is greater than step S6, but the amount of coarsening of the crystal grains is negatively offset and becomes equivalent strength.
- elongation and repeated bending are bad because the crystal grains are coarse.
- Tables 31 and 32 show data at the head, the center, and the tail in the same extrusion in the processes K1 and K3 of the invention alloy and Cr—Zr copper.
- Cr-Zr copper had a difference in average crystal grain size due to extrusion and a large difference in mechanical properties such as tensile strength between the head and the tail in both steps K1 and K3.
- Inventive alloys had little difference in average crystal grain size due to extrusion, and mechanical properties such as tensile strength were uniform between the head, the center, and the tail in both steps K1 and K3.
- Inventive alloys have small variations in mechanical production of extrusion production lots.
- fine precipitates having a substantially circular or substantially elliptical shape are uniformly dispersed, and the average particle size of the precipitates is 1.5 to 20 nm, or all of the precipitates 90% or more is a tube, rod, or wire having a size of 30 nm or less, and most of the precipitates have a preferable average particle size of 1.5 to 20 nm, and 90% of all the precipitates.
- the above obtained tubes, rods and wires having a size of 30 nm or less see Test Nos. 32 and 34 in Tables 11 and 12 and the transmission electron microscope image in FIG. 10).
- a tube, rod, or wire having an average crystal grain size of 5 to 75 ⁇ m after hot extrusion was obtained (see Test Nos. 1, 2, and 3 in Tables 8 and 9).
- the total cold drawing / drawing rate after hot extrusion to heat treatment TH1 exceeds 75%, and the recrystallization rate of the matrix is 45% or less in the metal structure after heat treatment TH1.
- a tube / bar / wire having an average crystal grain size of 0.7 to 7 ⁇ m in the recrystallized part was obtained (see Test Nos. 321 and 322 in Tables 23 and 24).
- Ratio of (minimum tensile strength / maximum tensile strength) due to variation in tensile strength within an extrusion production lot is 0.9 or more, and ratio of (minimum conductivity / maximum conductivity) due to variation in conductivity is Tubes, rods, and wire rods of 0.9 or more were obtained (see Test Nos. 231, 1, 232, etc. in Tables 31 and 32).
- Pipes, rods and wires having a conductivity of 45 (% IACS) or higher and a figure of merit I of 4300 or higher were obtained (Test Nos. 1 to 3 in Tables 8 and 9 and Test Nos. 171 to 188 and Test Nos. 321 to 337, and Test Nos. 201 to 206 and 313 in Tables 25 and 26). Furthermore, pipes / bars / wires having a conductivity of 65 (% IACS) or more and a figure of merit I of 4300 or more were obtained (tests Nos. 1 and 2 in Tables 8 and 9, and tests in Tables 23 and 24). No. 171 to 188 and Test Nos. 321 to 337, and Test Nos. 201 to 206 and 313 in Tables 25 and 26).
- a tube, rod, or wire having a tensile strength at 400 ° C. of 200 (N / mm 2 ) or more was obtained (see Test No. 1 in Tables 8 and 9).
- a tube / bar / wire having a Vickers hardness (HV) of 90 or more after heating at 700 ° C. for 120 seconds or 80% or more of the value of Vickers hardness before heating was obtained (Test No. 1 in Tables 11 and 12). , 31, 32, etc.). Further, the precipitate in the metal structure after heating is larger than that before heating, but the average particle size is 1.5 to 20 nm, or 90% or more of all precipitates are 30 nm or less, and The recrystallization rate was 45% or less, and excellent heat resistance was exhibited.
- HV Vickers hardness
- a heat treatment was performed at 200 to 700 ° C. for 0.001 second to 240 minutes to obtain a wire having excellent bending resistance (Test Nos. In Tables 23 and 24). 172, 174, 175, 176, etc.).
- a wire having an outer diameter of 3 mm or less and excellent bending resistance was obtained (see Tables 23 and 24).
- C1100 has crystallized particles of Cu 2 O, its particle size is as large as about 2 ⁇ m, so it does not contribute to strength and has little influence on the metal structure. Therefore, since the high temperature strength is low and the particle size is large, it cannot be said that the repeated bending workability is good (see Test No. G15 in Tables 6 and 7 and Test No. 23 in Tables 8 and 9).
- the comparative alloy has low hardness even after cold compression (see Test Nos. 14 to 18 in Tables 8 and 9).
- Inventive alloys have a small recrystallized grain size.
- the solid solution of Co, P, etc. is finely precipitated and high strength is obtained, and most of it is precipitated. High conductivity is obtained.
- the precipitate is small, it is excellent in repeated bendability (Test Nos. 1 to 13 in Tables 8 and 9, Test Nos. 31 to 47 in Tables 11 and 12, and Test Nos. 171 to 188 in Tables 23 and 24). Etc.).
- Inventive alloys have finely precipitated Co, P, etc., preventing the movement of atoms, and the heat resistance of the matrix is also improved by Sn. There is little change and high strength is obtained (see Test Nos. 1, 4 etc. in Tables 8 and 9).
- the invention alloy has high tensile strength and hardness, so it has high wear resistance and low wear loss (see Test Nos. 1 to 6 in Tables 8 and 9).
- the strength of the final material is improved by subjecting the alloy according to the invention to heat treatment at a low temperature during the process. This is thought to be caused by the rearrangement of atoms at the atomic level because it was performed after high-level plastic working. When heat treatment is finally performed at a low temperature, the strength is slightly reduced, but excellent bending resistance is exhibited. This phenomenon is not seen in the conventional C1100. This is extremely useful in fields where bending resistance is required.
- the strength after aging of the extruded head and the tail is significantly different, the strength of the tail is extremely low, and the strength ratio is about 0.8. Also, the heat resistance and other characteristics of the tail are very low. In contrast, the inventive alloy has a uniform property of about 0.98 (see Tables 31 and 32).
- the high performance copper tube / rod / wire according to the present invention has high strength and high conductivity, and therefore, connectors, bus bars, bus bars, relays, heat sinks, air conditioner tubes, and electrical components (clasps, fasteners).
- wire cutting electric discharge machining
- trolley wire welding tip, spot welding tip, spot welding electrode, stud welding Base point, EDM electrode, electric motor rotor bar, and electrical parts (clasp, fastener, electrical wiring device, electrode, relay, power relay, connection terminal, male terminal, commutator piece, rotor bar, end ring, etc.) Ideal for air conditioner tubes, refrigerator refrigerator tubes, etc.
- EDM electrode electric motor rotor bar
- electrical parts clasp, fastener, electrical wiring device, electrode, relay, power relay, connection terminal, male terminal, commutator piece, rotor bar, end ring, etc.
- it is excellent in workability such as forging and pressing, it is most suitable for hot forging products, cold forging products, rolling screws, bolts, nuts, electrodes, relays, power relays, contacts and piping parts.
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Abstract
Description
コネクタ、バスバーは、コネクタの小型化によりオス側の細線化が進んでいるので、コネクタの抜き差しに耐えられる強度と導電性が求められる。使用中の温度上昇もあるので、耐応力緩和特性も必要である。
大電流が流れるリレー、電極、コネクタ、ブスバー、モータ等には、当然高い導電性が要求され、また、コンパクト化等のために高い強度が必要である。
ワイヤカット(放電加工)用線には、高導電、高強度、耐摩耗性、高温強度、耐久性が求められる。
トロリ線には、高導電、高強度が必要であり、使用中の耐久性、耐摩耗性、高温強度も求められる。一般にトロリ線と称されるが、直径20mmのものが多く、本明細書では棒の範疇に入る。
溶接用チップには、高導電、高強度、耐摩耗性、高温強度、耐久性、及び高い熱伝導性が求められる。
X1=([Co]-0.007)/([P]-0.008)
として、X1が2.9~6.1、好ましくは、3.1~5.6、より好ましくは3.3~5.0、最適には3.5~4.3の関係を有し、かつ残部がCu及び不可避不純物からなる合金組成である。
X2=([Co]+0.85×[Ni]+0.75×[Fe]-0.007)/([P]-0.008)
として、X2が2.9~6.1、好ましくは、3.1~5.6、より好ましくは3.3~5.0、最適には3.5~4.3の関係を有し、かつ、
X3=1.5×[Ni]+3×[Fe]
として、X3が0.015~[Co]、好ましくは、0.025~(0.85×[Co])、より好ましくは0.04~(0.7×[Co])の関係を有し、かつ、残部がCu及び不可避不純物からなる合金組成である。
X1=([Co]-0.007)/([P]-0.008)
として、X1が2.9~6.1、好ましくは、3.1~5.6、より好ましくは3.3~5.0、最適には3.5~4.3でなければならない。また、Ni、Fe添加の場合には、
X2=([Co]+0.85×[Ni]+0.75×[Fe]-0.007)/([P]-0.008)
として、X2が2.9~6.1、好ましくは、3.1~5.6、より好ましくは3.3~5.0、最適には3.5~4.3でなければならない。X1、X2が上限を越えると、熱・電気伝導性の低下を招き、耐熱特性、強度が低下し、結晶粒成長を抑制できず、熱間変形抵抗も増す。X1、X2が下限より低いと、熱・電気伝導性の低下を招き、耐熱特性が低下し、熱間・冷間での延性が損なわれる。特に必要な、高度な熱・電気伝導性と強度、さらには延性とのバランスが悪くなる。
I=R1/2×S×(100+L)/100
とする。導電率が45%IACS以上であることを条件として、性能指数Iが4300以上であることが良い。なお、熱伝導性と電気伝導性とは強い相関があるので、性能指数Iは熱伝導性の高低も表している。
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、高性能銅管・棒・線材を作成した。表1は、高性能銅管・棒・線材を作成した合金の組成を示す。
Claims (14)
- 0.13~0.33mass%のCoと、0.044~0.097mass%のPと、0.005~0.80mass%のSnと、0.00005~0.0050mass%のOとを含有し、Coの含有量[Co]mass%とPの含有量[P]mass%との間に、2.9≦([Co]-0.007)/([P]-0.008)≦6.1の関係を有し、かつ残部がCu及び不可避不純物からなる合金組成であり、熱間押出を含む工程によって造られたことを特徴とする高強度高導電銅合金管・棒・線材。
- 0.003~0.5mass%のZn、0.002~0.2mass%のMg、0.003~0.5mass%のAg、0.002~0.3mass%のAl、0.002~0.2mass%のSi、0.002~0.3mass%のCr、0.001~0.1mass%のZrのいずれか1種以上をさらに含有したことを特徴とする請求項1に記載の高強度高導電銅合金管・棒・線材。
- 0.13~0.33mass%のCoと、0.044~0.097mass%のPと、0.005~0.80mass%のSnと、0.00005~0.0050mass%のOとを含有し、かつ0.01~0.15mass%のNi、又は0.005~0.07mass%のFeのいずれか1種以上を含有し、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、2.9≦([Co]+0.85×[Ni]+0.75×[Fe]-0.007)/([P]-0.008)≦6.1、及び0.015≦1.5×[Ni]+3×[Fe]≦[Co」の関係を有し、かつ、残部がCu及び不可避不純物からなる合金組成であり、熱間押出を含む工程によって造られたことを特徴とする高強度高導電銅合金管・棒・線材。
- 0.003~0.5mass%のZn、0.002~0.2mass%のMg、0.003~0.5mass%のAg、0.002~0.3mass%のAl、0.002~0.2mass%のSi、0.002~0.3mass%のCr、0.001~0.1mass%のZrのいずれか1種以上をさらに含有したことを特徴とする請求項3に記載の高強度高導電銅合金管・棒・線材。
- 前記熱間押出前にビレットが840~960℃に加熱され、熱間押出後の840℃、又は押出材料温度から500℃までの平均冷却速度が15℃/秒以上であり、かつ、熱間押出後に、又は熱間押出後に冷間抽伸/伸線加工が行なわれる場合には前記冷間抽伸/伸線加工の前後、又は前記冷間抽伸/伸線加工の間に375~630℃で0.5~24時間の熱処理TH1を施された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高強度高導電銅合金管・棒・線材。
- 略円形、又は略楕円形の微細な析出物が均一に分散しており、
前記析出物の平均粒径が1.5~20nmであるか、又は全ての析出物の90%以上が30nm以下の大きさ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高強度高導電銅合金管・棒・線材。 - 前記熱間押出上がりでの平均結晶粒径が5~75μm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高強度高導電銅合金管・棒・線材。
- 前記熱間押出後から前記熱処理TH1までのトータルの冷間抽伸/伸線加工の加工率が75%を超える場合、該熱処理TH1後の金属組織において、マトリックスの再結晶率が45%以下であり、再結晶部の平均結晶粒径が、0.7~7μmであることを特徴とする請求項5に記載の高強度高導電銅合金管・棒・線材。
- 押出製造ロット内の引張強度のバラツキでの(最小引張強度/最大引張強度)の比が0.9以上であり、かつ、導電率のバラツキでの(最小導電率/最大導電率)の比が0.9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高強度高導電銅合金管・棒・線材。
- 導電率が45(%IACS)以上で、導電率をR(%IACS)、引張強度をS(N/mm2)、伸びをL(%)、としたとき、(R1/2×S×(100+L)/100)の値が4300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高強度高導電銅合金管・棒・線材。
- 400℃での引張強度が200(N/mm2)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高強度高導電銅合金管・棒・線材。
- 700℃で120秒加熱後のビッカース硬度(HV)が90以上、又は前記加熱前のビッカース硬度の値の80%以上であり、該加熱後の金属組織中の析出物の平均粒径が1.5~20nm又は全ての析出物の90%以上が30nm以下であり、該加熱後の金属組織中の再結晶化率が45%以下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高強度高導電銅合金管・棒・線材。
- 冷間鍛造用途、又はプレス用途に使われ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高強度高導電銅合金管・棒・線材。
- 冷間伸線加工又はプレス加工が行なわれ、冷間伸線加工又はプレス加工の間、及び/又は冷間伸線加工又はプレス加工の後に200~700℃で0.001秒~240分の熱処理TH2を施されることにより製造された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高強度高導電銅合金線材。
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US12/808,564 US9163300B2 (en) | 2008-03-28 | 2009-02-23 | High strength and high conductivity copper alloy pipe, rod, or wire |
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EP09725275.3A EP2258882B1 (en) | 2008-03-28 | 2009-02-23 | High-strength and high-electroconductivity copper alloy pipe, bar, and wire rod |
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KR20160013025A (ko) | 2013-05-24 | 2016-02-03 | 미쓰비시 마테리알 가부시키가이샤 | 구리 합금선 |
US10584400B2 (en) | 2013-05-24 | 2020-03-10 | Mitsubishi Materials Corporation | Copper alloy wire |
JP2018507326A (ja) * | 2015-02-02 | 2018-03-15 | イザベレンヒュッテ ホイスラー ゲー・エム・ベー・ハー ウント コンパニー コマンデイトゲゼルシャフト | 接続要素、特にネジまたはナット |
US10357813B2 (en) | 2016-05-13 | 2019-07-23 | Miyoshi Gokin Kogyo Co., Ltd. | Copper alloy tube with excellent high-temperature brazeability and manufacturing method therefor |
Also Published As
Publication number | Publication date |
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CA2706199A1 (en) | 2009-10-01 |
CA2706199C (en) | 2014-06-10 |
JPWO2009119222A1 (ja) | 2011-07-21 |
MY152076A (en) | 2014-08-15 |
CN101960028B (zh) | 2013-03-13 |
EP2258882B1 (en) | 2016-05-25 |
TWI422691B (zh) | 2014-01-11 |
US20110174417A1 (en) | 2011-07-21 |
CN101960028A (zh) | 2011-01-26 |
JP5051927B2 (ja) | 2012-10-17 |
BRPI0905381A2 (pt) | 2016-07-05 |
TW201006940A (en) | 2010-02-16 |
EP2258882A1 (en) | 2010-12-08 |
EP2258882A4 (en) | 2014-07-02 |
KR101213801B1 (ko) | 2013-01-09 |
KR20100060024A (ko) | 2010-06-04 |
US9163300B2 (en) | 2015-10-20 |
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