WO2006109801A1 - Alliage de cuivre et procédé servant à produire celui-ci - Google Patents

Alliage de cuivre et procédé servant à produire celui-ci Download PDF

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Publication number
WO2006109801A1
WO2006109801A1 PCT/JP2006/307658 JP2006307658W WO2006109801A1 WO 2006109801 A1 WO2006109801 A1 WO 2006109801A1 JP 2006307658 W JP2006307658 W JP 2006307658W WO 2006109801 A1 WO2006109801 A1 WO 2006109801A1
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Prior art keywords
precipitates
inclusions
copper
copper alloy
alloy
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PCT/JP2006/307658
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English (en)
Japanese (ja)
Inventor
Tsuneaki Nagamichi
Yasuhiro Maehara
Naotsugu Yoshida
Mitsuharu Yonemura
Keiji Nakajima
Takuji NAKAHATA
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Sumitomo Metal Industries, Ltd.
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Publication of WO2006109801A1 publication Critical patent/WO2006109801A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to a copper alloy and a method for producing the same without using an element that adversely affects the environment such as Be.
  • Applications of this copper alloy include electrical and electronic parts and safety tools.
  • Examples of electrical and electronic parts include the following. In the electronics field, PC connectors, semiconductor sockets, optical pickups, coaxial connectors, and IC checker pins are listed. In the field of communications, mobile phone parts (connectors, knottery terminals, antenna parts), submarine repeater housings, exchange connectors, etc. are listed. In the automotive field, there are various electrical components such as relays, various switches, micromotors, diaphragms, and various terminals. In the aerospace field, landing gears for aircraft are listed. Medical / analytical instruments include medical connectors and industrial connectors. In the field of home appliances, relays for home appliances such as air conditioners, optical pickups for game machines, card media connectors, etc.
  • Safety tools include, for example, drilling rods, spanners, chain blocks, hammers, drivers, pliers, and -padpers used in places where there is a risk of explosion from sparks, such as ammunition stores and coal mines. There are tools.
  • Patent Document 1 proposes a copper alloy in which Ni Si is deposited, which is called a Corson series.
  • This Corson alloy has a tensile strength of 750 to 820 MPa and an electrical conductivity of about 40%. Among alloys that do not contain elements harmful to the environment such as Be, the balance between tensile strength and electrical conductivity is relatively high. It's a thing.
  • this alloy has limitations in both strength enhancement and high electrical conductivity, and there remains a problem in terms of product noirishment as described below.
  • This alloy is Ni Si
  • Ni and Si contents are reduced to increase the conductivity, the tensile strength decreases significantly.
  • Ni and Si contents are reduced to increase the conductivity, the tensile strength decreases significantly.
  • Ni and Si precipitation Ni and
  • the electrical resistance of the alloy (or its reciprocal conductivity) is determined by electron scattering, and varies greatly depending on the type of element dissolved in the alloy. Ni dissolved in the alloy remarkably increases the electrical resistance (remarkably decreases the electrical conductivity), so in the above-mentioned Corson alloy, the electrical conductivity decreases when the Ni content is increased.
  • the tensile strength of the copper alloy is obtained by age hardening. The tensile strength increases as the amount of precipitate increases and as the precipitate is finely dispersed. In the case of a Corson alloy, since the precipitated particles are only Ni Si, there is a limit to increasing the strength in terms of both precipitation and dispersion.
  • Patent Document 2 discloses a copper alloy having a good wire-bonding property, which includes elements such as Cr and Zr, and defines surface hardness and surface roughness. As described in the examples, this copper alloy is manufactured on the premise of hot rolling and solution treatment.
  • the material for the safety tool is required to have mechanical properties comparable to tool steel, for example, high strength and wear resistance, and no sparks that cause an explosion are generated. It is required to be excellent in generation.
  • copper alloys with high thermal conductivity, especially Cu-Be alloys aimed at strengthening by aging precipitation of Be, have been frequently used as safety tool materials.
  • Cu-Be alloy is a material with many environmental problems. Nevertheless, Cu-Be alloy has been widely used as a safety tool material for the following reasons.
  • FIG. 1 is a graph showing the relationship between the electrical conductivity [IACS (%)] and the thermal conductivity [TC (WZm′K)] of a copper alloy. As shown in Fig. 1, the two are in a 1: 1 relationship, and increasing the conductivity [IACS (%;)] increases the thermal conductivity [TC (W / mK)]. In other words, it is nothing other than increasing the spark resistance. When a sudden force is applied when using a tool, a spark is generated because a specific component in the alloy is burned by the heat generated by the impact. As described in Non-Patent Document 1, since the thermal conductivity of steel is as low as 1Z5 or less than that of copper, local temperature rise is likely to occur. Steel contains C, so “c + o ⁇
  • FIG. 1 shows the data shown in Non-Patent Document 1.
  • Patent Document 1 Japanese Patent No. 2572042
  • Patent Document 2 Japanese Patent No. 2714561
  • Non-patent document 1 Industrial heating, Vol.36, No.3 (1999), published by Japan Industrial Furnace Association, page 59 Disclosure of invention
  • the first object of the present invention is a copper alloy that does not contain elements harmful to the environment such as Be, has abundant product nomination, is excellent in high-temperature strength, ductility, and bending workability.
  • An object of the present invention is to provide a high-strength, high-workability copper alloy that is excellent in performance required for a material for safety tools, that is, thermal conductivity, wear resistance and spark resistance.
  • the second object of the present invention is to provide a method for producing a copper alloy having the same components as described above, but having superior ductility and bending caloricity as compared with conventional production methods.
  • TS in equation (a) means tensile strength (MPa), and IACS means conductivity (%).
  • the copper alloy is required to have a certain degree of high-temperature strength in addition to the above-described tensile strength and conductivity characteristics. This is also the force that, for example, connector materials used in automobiles and computers can be exposed to environments above 200 ° C.
  • the room temperature strength decreases significantly and the desired spring characteristics can no longer be maintained.
  • the above Cu-Be alloys and Corson alloys are heated to 400 ° C. Even after this, the room temperature strength hardly decreases.
  • the level be equal to or higher than that of Cu-Be alloys.
  • the heating temperature at which the rate of decrease in hardness before and after the heating test is 50% is defined as the heat resistance temperature, and when the heat resistance temperature exceeds 350 ° C or higher The strength is excellent. More preferably, the heat resistant temperature is 400 ° C or higher.
  • the target of bending cacheability is to be equal to or higher than that of Cu-Be alloys.
  • bending deformation in the 0-degree direction is relatively easy (good way), and bending deformation in the 90-degree direction is relatively difficult (bad way).
  • the good range of bending workability is when B ⁇ 3.0 in the 0 degree direction and B ⁇ 6.0 in the 90 degree direction. Since R varies depending on the plate thickness, in the present invention, the bending calorability was evaluated based on the test at 0.20 mm thickness.
  • the target is to have the same level of wear resistance as tool steel.
  • the wear resistance is excellent when the hardness at room temperature is 250 or more in terms of Vickers hardness.
  • the gist of the present invention is a method for producing the copper alloys shown in the following (A) to (C) and the copper alloy shown in the following (D).
  • N means the total number of precipitates and inclusions per unit area (pieces Zmm 2 )
  • X means the grain size ( ⁇ m) of the precipitates and inclusions.
  • Weight 0/0, Cr contains 0.01 to 5%, more, Zn, Sn, Ag, Mn , Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta,
  • the medium strength of W, Ge, Te, and Se is also selected, including 0.01 to 20% in total of one or more selected, with the balance consisting of copper and impurities, and the aspect ratio of the crystal grains of the copper-based matrix
  • the total number of precipitates and inclusions and the total number of precipitates and inclusions is represented by the above formula (1).
  • a copper alloy characterized by satisfying the relationship.
  • the copper alloys (A) to (C) described above are replaced with a part of copper, and a total of 0.001 to 2% by mass of Mg, Li, Ca and rare earth elements are also selected.
  • two or more, or Z and, in total 0.0001 mass 0/0 of P, B, Bi, Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, in, Pd, Po, Sb , Au, Ga, S, Cd, As and Pb may contain one or more selected ones.
  • the crystal grain size of these copper alloys is preferably 0.01 to 35 m.
  • (D) A piece obtained by melting and producing a copper alloy having the chemical composition described in any one of (A) to (C) above, and producing at least a piece immediately after forging.
  • the aspect ratio of the crystal grains of the copper-based matrix phase is characterized by performing solution treatment and Z or hot rolling after cooling at a cooling rate of l ° CZs or higher in the temperature range from temperature to 900 ° C.
  • N means the total number of precipitates and inclusions per unit area (pieces Zmm 2 )
  • X means the grain size ( ⁇ m) of the precipitates and inclusions.
  • solution treatment and Z or hot rolling it is desirable to perform heating in a temperature range of 600 ° C or lower, or further, heat treatment for holding in a temperature range of 150 to 750 ° C.
  • Solution treatment and Z or hot rolling processing at temperatures below 600 ° C, and 150-750 The heat treatment held in the temperature range of ° C may be performed a plurality of times.
  • solution treatment and Z or hot rolling processing in a temperature range of 600 ° C or less, and heat treatment holding in a temperature range of 150 to 750 ° C need not be performed in this order.
  • processing in a temperature range of 600 ° C or lower and heat treatment in a temperature range of 150 to 750 ° C may be performed. After the last step, you may carry out processing in the temperature range below 600 ° C! /.
  • the precipitate is a metal or a compound of copper and an additive element, or a compound of additive elements, for example, Cu Ti for a Ti additive, Cu Zr for a Zr additive, Ma
  • metallic Cr precipitates. Further, the inclusion is a metal oxide, a metal carbide, a metal nitride or the like.
  • the copper alloy of the present invention contains Zn, Sn, Ag, Mn, Fe, Co, Al, Ni, Si, Mo, V, Nb, Ta, W, Ge, Te and Se (hereinafter, these elements are referred to as “first Medium strength (referred to as “group element”) 0.1 to 20% of each one selected, or a total of 0.1 to 20% of two or more, with the balance being a chemical composition consisting of copper and impurities.
  • group element 0.1 to 20% of each one selected, or a total of 0.1 to 20% of two or more, with the balance being a chemical composition consisting of copper and impurities.
  • These elements are elements having an effect of improving corrosion resistance and heat resistance while maintaining a balance between strength and electrical conductivity. This effect is exhibited when these elements contain a total of 0.1% or more. However, when these contents are excessive, the conductivity decreases. Therefore, when these elements are contained, the total content of one or more kinds needs to be in the range of 0.1 to 20%. Ag and Sn, in particular, contribute to high strength through fine precipitation, and are therefore preferably used positively. When the following second element is included, the strength can be secured by the second element, so the lower limit of the first element can be lowered to 0.01%.
  • any one of these elements may be contained in the copper alloy of the present invention.
  • the effect of improving the strength becomes significant when the content of these elements is 0.01% or more.
  • the content of any one of Ti, Zr and Hf is preferably 0.01 to 5%. In order to obtain a state where the balance between tensile strength and electrical conductivity is extremely good, it is more desirable to contain these elements in an amount of 0.1% or more.
  • Cr is an element effective for improving the tensile strength without increasing the electrical resistance. In order to obtain the effect, it is desirable to contain 0.01% or more. In particular, in order to obtain a state in which the balance of tensile strength and electrical conductivity is about the same as or higher than that of the Cu—Be alloy, it is desirable to contain 0.1% or more. On the other hand, if the Cr content exceeds 5%, metal Cr precipitates coarsely and adversely affects ductility, bending workability, fatigue properties, and the like. Therefore, when Cr is contained, its content is preferably 0.01 to 5%.
  • the copper alloy of the present invention instead of a part of copper, 0.001 to 2% of one selected from among Mg, Li, Ca and rare earth elements, respectively, or It is desirable to include two or more kinds in a total of 0.001 to 2%. These are hereinafter referred to as “Group 3 elements”.
  • Mg, Li, Ca and rare earth elements are elements that increase the high-temperature strength by combining with oxygen atoms in the copper matrix to form fine oxides. The effect becomes significant when the total content of these elements is 0.001% or more. However, if its content exceeds 2%, the above effects are saturated, and the force also has problems such as a decrease in electrical conductivity and a deterioration in ductility and bending workability. Therefore, the total content when Mg, Li, Ca and one or more selected rare earth elements are included is preferably 0.001 to 2%.
  • rare earth elements mean Sc, Y and lanthanoids, and each element may be added alone, or misch metal may be added.
  • the copper alloy of the present invention is intended to increase the width ( ⁇ ) of the liquidus and solidus at the time of alloy penetration. Therefore, P, B, Bi ⁇ Tl, Rb, Cs, Sr, Ba, Tc, Re, Os, Rh, In, Pd, Po, Sb, Au, Ga, S, Cd It is desirable to include 0.0001 to 3% of the selected one of As and Pb, or 0.0001 to 3% in total of 2 or more. As, Pd and Cd are harmful elements and should not be used as much as possible. These are hereinafter referred to as “Group 4 elements”. Note that ⁇ ⁇ is a force that increases due to the so-called supercooling phenomenon in the case of rapid solidification. Here, we consider ⁇ T in a thermal equilibrium state as a guide.
  • ⁇ is preferably in the range of 50 to 200 ° C.
  • C, N and O are elements usually contained as impurities. These elements form carbides, nitrides and oxides with the metal elements in the alloy. If these precipitates or inclusions are fine, they have the effect of strengthening the alloy, particularly the high-temperature strength, in the same manner as the precipitates of the compounds of metals or copper and additive elements described later, or compounds of additive elements. Therefore, you may add actively.
  • O has the effect of increasing the high temperature strength by forming an acid oxide. This effect is easily obtained in alloys containing elements that easily form oxides such as Mg, Li, Ca and rare earth elements, Al, and Si. In this case, however, it is necessary to select conditions so that no solid solution O remains. Residual solute oxygen causes H 2 O gas during heat treatment in a hydrogen atmosphere, causing a steam explosion, causing a so-called hydrogen disease, blistering, etc.
  • each of these elements exceeds 1%, coarse precipitates or inclusions are formed, and ductility and bending workability are reduced. Therefore, it is preferable to limit each to 1% or less. More preferred is 0.1% or less. If H is contained as an impurity in the alloy, H
  • the content is preferably as low as possible.
  • Be is another impurity element. Be may be mixed in a copper alloy when scrap is used in large quantities as a raw material. This content should be as low as possible However, it is acceptable if it is less than 0.1%.
  • the particle size of particles having a particle size force of m or more and the total number of precipitates and inclusions satisfy the following formula (1). is required.
  • N means the total number of precipitates and inclusions per unit area (pieces Zmm 2 )
  • X means the grain size m of the precipitates and inclusions.
  • the strength is improved without lowering the conductivity by finely depositing a precipitate of a metal or a compound of copper and an additive element, or a compound of the same additive element. Can be made. These increase the strength by precipitation hardening. Solid solution of Cr, Ti, and Zr decreases by precipitation, and the conductivity of the copper matrix approaches that of pure copper
  • the particle size of those having a particle size of Lm or more, the total number of precipitates and inclusions, and the above formula (1) Satisfaction is defined as an essential requirement.
  • the desirable total number of precipitates and inclusions is when the following equation (2) is satisfied, and more desirably when the following equation (3) is satisfied.
  • these The particle size of each and the total number of precipitates and inclusions can be determined by the method shown in the examples.
  • N means the total number of precipitates and inclusions per unit area (pieces Zmm 2 )
  • X means the grain size ( ⁇ m) of the precipitates and inclusions.
  • the mechanical properties are, for example, in the rolling direction (direction parallel to the rolling direction: here defined as the 0 degree direction) and in the direction perpendicular to the rolling (perpendicular to the rolling direction).
  • the width direction (defined here as the 90-degree direction) is different, that is, the anisotropy of the characteristics increases, which causes problems such as restrictions on the molding direction and sampling direction.
  • the bending workability itself deteriorates. Therefore, the crystal structure aspect ratio was set to 5 or less. Smaller aspect ratio is better 4 or less is preferred. If it is 3 or less, it is more preferable. If the aspect ratio is close to 1, the value is even better.
  • the aspect ratio defined in the present invention is the average value of the (maximum diameter) / (minimum diameter) values of the crystal grains of the copper-based matrix, regardless of the direction of the structure observation. .
  • the “maximum diameter” of a crystal grain is the longest diameter of the crystal grain, and the “minimum diameter” of the crystal grain is the shortest of the crystal grain!
  • SEM scanning electron microscope
  • the crystal grain size of the copper alloy is made fine, it is advantageous for increasing the strength and also improves the ductility and the bending workability.
  • the crystal grain size is desirably 0.01 to 35 m.
  • a more desirable particle size is 0.05 to 30 / ⁇ ⁇ . Most preferred is 0.1 to 25 ⁇ .
  • the average crystal grain size of the copper matrix is, for example, an optical microscope or a scanning electron microscope (S This is a value obtained by multiplying the average section length measured by the linear cutting method using this tissue photograph by a number of fields by 1.13.
  • inclusions such as metal oxides, metal carbides, and metal nitrides that prevent fine precipitation of a metal or a compound of copper and an additive element, or a compound of additive elements, are solidified in a piece. Easy to generate immediately after. In order to suppress the formation of these inclusions, it is most important to adjust the cooling rate after solidification. As will be described later, solution treatment and Z or hot rolling are necessary to reduce the aspect ratio of the crystal grains of the copper base matrix to 5 or less in order to ensure isotropic properties. There is. However, as a result of research by the present inventors, it is clear that the formation and coarsening of the inclusions can be suppressed even if such a hot process is performed if the temperature of the flake is cooled to some extent. became
  • a copper alloy having the above chemical composition is melted, and the piece obtained by forging is at least from the piece temperature immediately after forging.
  • a temperature range up to 900 ° C after cooling at a cooling rate of 1 ° CZs or higher, solution treatment and Z or hot rolling are performed, so that the aspect ratio of the crystal grains of the copper base matrix is 5 or less.
  • the particle size of the particles having a particle size of Lm or more and the total number of precipitates and inclusions satisfy the following formula (1): did.
  • N means the total number of precipitates and inclusions per unit area (pieces Zmm 2 )
  • X means the grain size ( ⁇ m) of the precipitates and inclusions.
  • Precipitates such as a compound of metal or copper and an additive element, or a compound of additive elements are formed in a temperature range of 280 ° C or higher.
  • inclusions such as metal oxides, metal carbides, and metal nitrides are coarsely formed, and the particle size is 20 m. In addition, it may reach several hundreds / zm.
  • the above precipitates also become coarser than 20 m. In the state where such coarse precipitates and inclusions are formed, the precipitation hardening action of the precipitates in the aging process, which is not only likely to cause cracks and breaks during subsequent processing, is impaired. High strength cannot be achieved.
  • the cooling rate in this temperature range is preferably 100 ° C / s or less, more preferably 90 ° C / s or less. More desirable is 80 ° C / s or less.
  • Solution treatment and Z or hot rolling are effective for isotropic, homogenizing, and fine graining of crystal structures.
  • high strength and excellent workability of the final product can be obtained uniformly and stably, and both the strength and the anisotropy of the characteristics can be reduced.
  • bending workability can be improved and bending workability anisotropy can be reduced.
  • the solution treatment and Z or hot rolling are preferably performed in a temperature range of 600 ° C or higher and 1060 ° C or lower. If it is less than 600 ° C, the crystal structure may not be isotropic, homogeneous or fine grained, and the aspect ratio of the crystal grain of the copper base matrix in the final product cannot be reduced to 5 or less. In some cases, good characteristics cannot be obtained uniformly and the anisotropy of characteristics increases. On the other hand, if the temperature of the solution treatment and Z or hot rolling exceeds 1060 ° C, the grain boundaries melt and cracks occur during processing, or the coarsening of the grains causes the final product. Characteristics There is a possibility that problems such as reduction and anisotropy of characteristics increase.
  • the solution treatment and Z or hot rolling are preferably performed in a temperature range of 600 ° C or higher and 1060 ° C or lower.
  • they are 650 degreeC or more and 1000 degrees C or less, More preferably, they are 700 degreeC or more and 900 degrees C or less.
  • the temperature range of 900 to 1,060 ° C. coarse precipitation of the inclusions and coarsening of the crystal grains of the copper base matrix are remarkable.
  • the solution treatment time or the heating time before hot rolling is less than 3.0 seconds, the desired crystal structure cannot be obtained even if the solution treatment temperature or the heating temperature before hot rolling is set high. Accordingly, it is desirable that the solution treatment in the temperature range of 600 to 160 ° C. or the heating before hot rolling be performed for 3.0 seconds or more. This time is preferably 1 minute or longer and more preferably 5 minutes or longer. More desirable is 10 minutes or more.
  • the upper limit of these times is not particularly defined, coarse precipitation of inclusions such as metal or a compound of copper and an additive element, a compound of additive elements, or a metal oxide, metal carbide, or metal nitride It is desirable to suppress it, suppress coarsening of crystal grains, and reduce the heating cost for 24 hours or less.
  • the heating time can be shortened. It is desirable to hold for a short time in the temperature range of 900 to 160 ° C on the high temperature side.
  • the rolling reduction in hot rolling is not particularly defined, but is preferably 20% or more as the total rolling reduction from the viewpoints of isotropic, homogenizing, and refinement of the crystal structure. More preferred is 50% or more.
  • Solution treatment and cooling after Z or hot rolling are preferably performed at a cooling rate of 1 ° C Zs or more in order to suppress precipitation of the inclusions and precipitates.
  • the larger the cooling rate the more preferable the cooling rate is 2 ° CZs or more, and the more preferable is 5 ° CZs or more.
  • Solution treatment and heating prior to Z or hot rolling are preferably performed in a reducing atmosphere, in an inert gas atmosphere, or in a vacuum of 20 Pa or less in order to prevent generation of scale due to surface oxidation. . Excellent mating properties are also ensured by the treatment under such an atmosphere.
  • Solution treatment and Z or hot rolling may be performed after "processing in a temperature range of 600 ° C or lower” or “aging treatment holding in a temperature range of 150 to 750 ° C” described later. .
  • the solution solution treatment and Z or hot After rolling it is desirable to further perform “processing in a temperature range of 600 ° C. or lower” or “aging treatment maintained in a temperature range of 150 to 750 ° C.”.
  • Processing such as rolling and drawing may be performed at 600 ° C or lower.
  • these processes may be performed in the cooling process after solidification. If processing is performed in a temperature range exceeding 600 ° C, strain during processing cannot be accumulated sufficiently, so that precipitation of a compound of a metal or copper and an additive element, or a compound of additive elements, etc. is performed during subsequent aging treatment. The product cannot be finely precipitated, and the strength of the copper alloy becomes insufficient.
  • the preferred cache temperature is 600 ° C. or lower, and more preferably 450 ° C. or lower. Most preferred is 300 ° C or lower. It may be 25 ° C or less.
  • the processing in the above temperature range is desirably performed at a processing rate (cross-sectional reduction rate) of 20% or more. More preferred is 50% or more. If processing is performed at such a processing rate, the dislocations introduced thereby become precipitation nuclei during the aging treatment, leading to refinement of the precipitates and shortening the time required for precipitation, thereby improving conductivity. Reduction of harmful solid solution elements can be realized early.
  • the aging treatment is performed by depositing a metal or a compound of copper and an additive element, or a precipitate such as a compound of the additive elements to increase the strength of the copper alloy and, at the same time, a solid solution element (Cr, It is effective to improve conductivity by reducing Ti and the like.
  • a solid solution element Cr, It is effective to improve conductivity by reducing Ti and the like.
  • the treatment temperature is less than 150 ° C, it takes a long time for the diffusion of the precipitated elements, which reduces productivity.
  • the treatment temperature exceeds 750 ° C, the precipitates become too coarse and not only can not be strengthened by precipitation hardening, but also have low ductility, bending workability, impact resistance and fatigue properties. I will give you. For this reason, it is desirable to perform the aging treatment in a temperature range of 150 to 750 ° C. Desirable aging temperature is 200-650 ° C, more preferably 250-550 ° C.
  • the aging treatment time is less than 30 seconds, the desired precipitation amount cannot be secured even if the aging treatment temperature is set high. Therefore, it is desirable to perform an aging treatment in the temperature range of 150 to 750 ° C for 30 seconds or more.
  • This treatment time is preferably 5 minutes or more, and more preferably 10 minutes or more. Most desirable is 15 minutes or more. There is no upper limit on the processing time, but it is desirable that it be 72 hours or less from the viewpoint of processing costs.
  • the aging treatment temperature is high, the treatment time can be shortened.
  • the aging treatment is preferably performed in a reducing atmosphere, an inert gas atmosphere, or a vacuum of 20 Pa or less in order to prevent the generation of scale due to surface oxidation. Excellent mating properties are also ensured by processing in such an atmosphere.
  • the processing may be performed after the solution treatment, or the solution treatment may be performed after the processing. Also good. Moreover, you may repeat these as needed. If it is repeated, the desired amount of precipitation can be obtained in a shorter time than with a single treatment (force and aging treatment), and a compound of metal or copper and an additive element, or a compound of additive elements. The precipitates such as can be deposited more finely.
  • conditions other than the above production conditions for example, conditions such as melting and forging are not particularly limited, but may be carried out as follows, for example.
  • the dissolution is preferably performed in a non-acidic or reducing atmosphere. This is also a force that causes so-called hydrogen disease, in which water vapor is generated and blisters are generated in the subsequent process when the amount of dissolved oxygen in the molten copper increases.
  • solid solution elements that easily oxidize such as Ti, Cr, Zr, Mg, Li, Ca and rare earth elements, Al, Si, etc. If this remains in the final product, ductility, bending workability and fatigue properties are significantly reduced.
  • continuous forging is preferred in terms of productivity and solidification rate, but other methods such as an ingot method may be used as long as the method satisfies the above conditions.
  • the filling temperature is 1250 ° C or higher. More preferred is 1350 ° C or higher. At this temperature, Cr, Ti, Zr, etc. can be sufficiently dissolved, inclusions such as metal oxides, metal carbides, metal nitrides, etc., compounds of metal or copper and additive elements, or the same additive elements. This is because a precipitate such as a chemical compound is not generated.
  • a method using a graphite mold usually performed with a copper alloy is recommended from the viewpoint of lubricity.
  • a refractory that does not easily react with the main alloying elements such as Ti, Cr, Zr, etc., for example, zirconia may be used.
  • a copper alloy having the chemical composition shown in Table 1 was vacuum-melted in a high-frequency melting furnace, and was poured into a zirconia mold to a depth of 20 mm to obtain a flake. For rare earth elements, single elements or misch metals were added.
  • the obtained piece was cooled by spray cooling from 900 ° C, which was the temperature immediately after fabrication (the temperature immediately after removal from the mold).
  • the temperature change of the vertical shape at a given location was measured by a thermocouple embedded in the vertical shape, and the surface temperature after the piece exited the vertical shape was measured with a contact thermometer.
  • the solidification start point was obtained by thermal analysis during continuous cooling at a predetermined rate after preparing 0.2 g of molten metal for each component.
  • a rolled material having a thickness of 15 mm, a width of 150 mm, and a length of 200 mm was produced from the obtained piece by cutting and cutting.
  • inventive examples 1 to 9 and comparative examples 10 to 12 were subjected to the solution treatment and Z or hot rolling under the conditions shown in Table 2, and the comparative examples 13 to 20 were subjected to solution heat treatment and heat treatment.
  • No hot rolling was performed.
  • These rolled materials are rolled at a reduction rate of 73 to 94% at room temperature (first rolling) to form a 0.8 mm thick plate, and subjected to aging treatment (first aging) under specified conditions.
  • aging treatment first aging
  • ⁇ Total number of precipitates and inclusions> A cross section perpendicular to the rolling surface of each specimen and parallel to the rolling direction is mirror-polished, etched with a corrosive liquid in which ammonia and hydrogen peroxide solution are mixed at a volume ratio of 9: 1, and then optical microscope is used. A 1 mm x 1 mm field of view was observed with a microscope at a magnification of 100 times. After that, the value obtained by measuring the major axis of the precipitates and inclusions (the length of the straight line in the grain that is the longest in the grain without touching the grain boundary in the middle) is defined as the grain size.
  • 10) is defined as the total number of all precipitates and inclusions according to the particle size of each sample.
  • a No. 13B tensile test piece specified in JIS Z 2201 was sampled from 0 ° and 90 ° with respect to the rolling direction, and subjected to a tensile test at room temperature (25 ° C) to obtain a tensile strength (TS).
  • TS tensile strength
  • EL fracture ductility
  • a specimen having a width of 10 mm and a length of 10 mm is taken from the direction of 0 ° and 90 ° with respect to the rolling direction, and a cross section perpendicular to the rolling surface and parallel to the rolling direction is mirror-polished, A square pyramid diamond indenter was pushed into the test piece with a load of 50 g, and the Vickers hardness defined by the ratio between the load and the surface area of the indentation was measured. Furthermore, after heating this at a predetermined temperature for 2 hours and cooling to room temperature, the Vickers hardness was measured again, and the heating temperature at which the hardness was 50% of the hardness before heating was defined as the heat resistant temperature. [0084] Bending workability>
  • the chemical composition, production conditions, crystal structure of the copper base matrix, and the total number of precipitates and inclusions are within the range specified by the present invention.
  • high values were obtained for conductivity, strength, workability (ductility, bendability), and heat resistance temperature.
  • the anisotropy of their characteristics is very small, and has excellent features!
  • Comparative Examples 10 to 20 are defined by the present invention in terms of chemical composition, production conditions, the total number of precipitates and inclusions, the average crystal grain size of the copper base matrix, and the difference in aspect ratio. Since it was out of the range, the characteristics were inferior to those of the examples of the present invention, and their anisotropy was strong.
  • a Cu alloy having the chemical composition shown in Table 4 was vacuum-melted in a high-frequency melting furnace and placed in a pig iron mold to obtain a piece having a thickness of 150 mm x width 170 mm x length 500 mm.
  • Rare earth elements were added in the form of individual elements or misch metal.
  • the temperature history during cooling after pouring was measured with a thermocouple embedded in the bottom of the saddle, and the cooling curve at the center of the alloy lump was estimated in combination with heat transfer calculations.
  • the average cooling rate up to 900 ° C after the start of solidification was 2 ⁇ 0.3 ° C / s.
  • the hot metal portion of the obtained piece is cut off and hot forged to give a thickness of 50mm x width of 200mm
  • An alloy lump with an X length of 1200 mm was prepared. These were heated to 950 ° C and then hot rolled to a thickness of 10 mm. Note that the rolling end temperature was about 750 to 400 ° C., and cooling was performed in water after the end of rolling. Some were heat-treated by solution heat treatment and surface grinding to produce a rolled material with a thickness of 9 mm. These rolled materials were rolled at room temperature (first rolling) to form a plate with a thickness of 0.6 mm, and a second solution treatment was performed at 800 ° C for 30 seconds.
  • REM rare earth element
  • Rminj of ⁇ time J means minutes and rhj means hours.
  • Example 2130 of the present invention the tensile strength, ductility and bending workability were all good. Since the value of the good way B is equal to or more than that of the bad way (below it in terms of the value of B), only the bad way is shown in Table 6. .
  • Example 38 of the present invention the melting furnace power is the pouring power to the holding furnace by pouring, and then charcoal is added in the same manner to prevent acidification, An 80 ⁇ 250 mm cross-section piece was obtained by intermittent drawing using a mold. The average drawing speed was 50 mm / min.
  • Example 39 of the present invention In the drawing method of Example 39 of the present invention, after pouring into the tundish, the acid is prevented with charcoal. The molten metal was poured continuously through the layer covered with.
  • a water-cooled copper type made of copper alloy was used and continuously drawn at an average speed of 70 mm to obtain a piece having a cross-sectional force of 100 mm ⁇ 400 mm.
  • the average cooling rates up to 900 ° C after the start of solidification are 2.8 ⁇ 0.3 ° C / s, 2.5 ⁇ 0.3 ° C / s and 2.4 ⁇ 0.2 ° C / s, respectively. s.
  • the cooling rate at the center of the slab during solidification and cooling during continuous fabrication was calculated by the combined use of the temperature history measured on the surface after exiting the saddle and the heat transfer calculation.
  • the cooling rate at the time of darvil fabrication was the same as in Example 1 by using both temperature measurement and heat transfer calculation with thermocouple embedded in the vertical side
  • time J fminj means minutes and fhj means hours.
  • Rminj for “hour” means minutes and “hour” means hours.
  • the balance of tensile strength, formability and electrical conductivity is excellent. However, it is excellent in high-temperature strength, and further, performance required for safety tool materials, that is, thermal conductivity. It is possible to provide a copper alloy excellent in wear resistance and spark resistance, and a method for producing the same.
  • FIG. 1 is a diagram showing the relationship between electrical conductivity and thermal conductivity.
  • FIG. 2 is a schematic diagram showing a forging method by the Darville method.

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Abstract

L'invention a pour objet un alliage de cuivre sans béryllium satisfaisant en ce qui concerne différentes performances. L'alliage de cuivre a une composition chimique donnée, le reste étant constitué de cuivre et d'impuretés. Dans l'alliage de cuivre, la structure cristalline a un rapport d'allongement inférieur ou égal à 5 et le nombre total des précipités et inclusions ayant un diamètre des particules supérieur ou égal à 1 µm satisfait à la relation (1) suivante. Cet alliage de cuivre est obtenu en faisant fondre, en coulant et en refroidissant à la suite de cela la pièce coulée à une vitesse supérieure ou égale à 1°C/s au moins dans la plage des températures allant de la température de la pièce coulée juste après la coulée à 900°C et en soumettant la pièce coulée à un traitement thermique en solution et/ou à un laminage à chaud. logN ≤ 0,4742 + 17,629 × exp(-0,1133 × X) (1) Dans la relation (1), N est le nombre total des précipités et inclusions par unité de surface (mm2) et X est le diamètre des particules des précipités et inclusions (µm).
PCT/JP2006/307658 2005-04-12 2006-04-11 Alliage de cuivre et procédé servant à produire celui-ci WO2006109801A1 (fr)

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CN104928523A (zh) * 2015-07-10 2015-09-23 苏州科茂电子材料科技有限公司 一种通信电缆用铜合金导线材料及其制备方法
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US10056166B2 (en) 2010-08-24 2018-08-21 Jx Nippon Mining & Metals Corporation Copper-cobalt-silicon alloy for electrode material
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CN103498068A (zh) * 2013-10-13 2014-01-08 王增琪 一种高强度稀土掺杂铜合金的制备方法
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CN105018821A (zh) * 2015-08-05 2015-11-04 启东市佳宝金属制品有限公司 高碳合金
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