US20130042949A1 - Method of manufacturing soft-dilute-copper-alloy-material - Google Patents

Method of manufacturing soft-dilute-copper-alloy-material Download PDF

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Publication number
US20130042949A1
US20130042949A1 US13/571,781 US201213571781A US2013042949A1 US 20130042949 A1 US20130042949 A1 US 20130042949A1 US 201213571781 A US201213571781 A US 201213571781A US 2013042949 A1 US2013042949 A1 US 2013042949A1
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Prior art keywords
copper
soft
dilute
wire
less
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US13/571,781
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Inventor
Hideyuki Sagawa
Seigi Aoyama
Hiromitsu Kuroda
Toru Sumi
Keisuke Fujito
Ryohei Okada
Shinichi Masui
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Proterial Ltd
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Hitachi Cable Ltd
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Assigned to HITACHI CABLE, LTD. reassignment HITACHI CABLE, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AOYAMA, SEIGI, FUJITO, KEISUKE, KURODA, HIROMITSU, MASUI, SHINICHI, OKADA, RYOHEI, SAGAWA, HIDEYUKI, SUMI, TORU
Publication of US20130042949A1 publication Critical patent/US20130042949A1/en
Assigned to HITACHI METALS, LTD. reassignment HITACHI METALS, LTD. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: HITACHI CABLE, LTD.
Abandoned legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • 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
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Definitions

  • the invention relates to a method of manufacturing a high conductive soft-dilute-copper-alloy material having high tensile strength and high elongation percentage even though it is a soft material.
  • copper Although it is generically called “copper”, it is broadly classified into hard copper and soft copper depending on a molecular arrangement thereof. In addition, copper of the type having desired properties is used depending on the intended use.
  • a hard copper wire is often used for a lead wire for electronic component.
  • a rigid hard copper wire is unsuitable as a cable used in, e.g., electronic devices, etc., such as medical equipment, industrial robot or notebook computer since it is used in an environment in which a combined external force of extreme bending, torsion and tension, etc., is repeatedly applied, and thus, a soft copper wire is used instead.
  • a conductor used for such an application is required to have conflicting characteristics, which are good conductivity (high conductivity), good tensile strength, elongation percentage, bending characteristics and small hardness, and accordingly, a copper material maintaining conductivity, tensile strength and an elongation percentage has been developed to date.
  • the invention according to JP-A-2002-363668 relates to a flexible cable conductor having good tensile strength, elongation percentage and conductivity, and particularly, a flexible cable conductor is described in which a wire rod is formed of a copper alloy made of oxygen-free copper with a purity of not less than 99.99 mass containing indium with a purity of not less than 99.99 mass % at a concentration range of 0.05 to 0.70 mass % and P with a purity of not less than 99.9 mass % at a concentration range of 0.0001 to 0.003 mass %.
  • JP-A-61-224443 proposes a conductor which is used for a wire bonding and has small hardness as a raw material in addition to good tensile strength and elongation percentage, wherein the conductor achieves all of high tensile strength, high elongation percentage and softness by adjusting the amount of impurity in high purity copper of not less than 99.999 mass %.
  • JP-A-2002-363668 only relates to a hard copper wire containing a large amount of In as an additional element, and a soft copper wire excellent in tensile strength and elongation percentage is not examined. In addition, conductivity is low due to the large amount of In as an additional element.
  • JP-A-9-256084 which is the invention related to a soft copper wire, conductivity is low due to the large amount of additional elements in the same manner as the invention according to JP-A-2002-363668.
  • oxygen-free copper OFC
  • a highly conductive copper material such as oxygen-free copper (OFC), etc.
  • OFC oxygen-free copper
  • a method of manufacturing a soft-dilute-copper-alloy material comprises:
  • a plastic working of a soft-dilute-copper-alloy comprising an additional element selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn and Cr, and a balance consisting of copper and inevitable impurity; and
  • annealing treatment is continuously performed by passing a material through a tubular furnace at a temperature of 250° C. to 800° C. for 0.6 seconds to 10.0 seconds, or is performed by an electric annealer at an applied voltage of 21V to 35V and at a velocity of 100 m/min to 600 m/min or is performed by batch processing at a temperature of 150° C. to 700° C. for not more than 3 hours, and the soft-dilute-copper-alloy contains 2 to 12 mass ppm of sulfur, more than 2 mass ppm and not more than 30 mass ppm of oxygen and 4 to 55 mass ppm of Ti as the additional element.
  • the soft-dilute-copper-alloy material of the invention is formed of a soft copper material which satisfies a conductivity of 98% LACS (International Annealed Copper Standard, conductivity is defined as 100% when resistivity is 1.7241 ⁇ 10 ⁇ 8 ⁇ m), 100% IACS, or further, 102% IACS.
  • the soft-dilute-copper-alloy material is preferably formed of a material having a softening temperature of not more than 148° C.
  • a working ratio of a wire rod is 90% (e.g., processing from an 8 mm diameter wire into a 2.6 mm diameter wire) by using a SCR continuous casting and rolling machine which allows stable production in a wide range of manufacturing with less generation of surface flaws.
  • the oxygen concentration in the material be increased to more than 2 mass ppm, followed by the addition of Ti. It is considered that, as a result, TIS, titanium oxide (TiO 2 ) or Ti—O—S particles are initially formed in molten copper.
  • the hot rolling temperature be set to 880 to 550° C. which is lower than 950 to 600° C. of the typical manufacturing conditions of copper so that dislocation is introduced into copper for easy precipitation of S.
  • S is precipitated on the dislocation or is precipitated using titanium oxide (TiO 2 ) as a nucleus, and for example, particles of Ti—O—S, etc., are formed in the same manner as in the molten copper.
  • element(s) selected from the group consisting of Ti, Mg, Zr, Nb, Ca, V, Ni, Mn, and Cr is chosen as an additional element is that these elements are active elements being prone to bind to other elements, especially to sulfur (S), and thus can trap S, which allows a copper base material (matrix) to be highly purified and hardness of the material to be reduced. In addition, an effect of realizing higher conductivity is obtained by trapping S.
  • One or two or more additional elements are contained.
  • other elements and impurities which do not adversely affect the properties of an alloy may be contained in the alloy.
  • the total content of one or two or more of Ti, Ca, V, Ni, Mn, and Cr as an additional element is 4 to 55 mass ppm, more preferably 10 to 20 mass ppm.
  • the content of Mg is 2 to 30 mass ppm, more preferably 5 to 10 mass ppm, and the content of Nb is 8 to 100 mass ppm, more preferably 20 to 40 mass ppm.
  • the favorable oxygen content is more than 2 mass ppm and not more than 30 mass ppm, more preferably 5 to 15 mass ppm, and more than 2 up to 400 mass ppm of oxygen can be contained within a range providing the properties of the alloy, depending on the added amount of the additional element and the sulfur content.
  • the sulfur content is 3 to 12 mass ppm, and more preferably, 3 to 8 mass ppm.
  • a soft-dilute-copper-alloy material in which pure copper with inevitable impurities contains 3 to 12 mass ppm of sulfur, more than 2 mass ppm and not more than 30 mass ppm of oxygen and 4 to 55 mass ppm of Ti is used to manufacture a wire rod (a roughly drawn wire).
  • So-called low-oxygen copper (LOC) is used in the present embodiment since more than 2 mass ppm and not more than 30 mass ppm of oxygen is contained.
  • a wire rod is formed of a soft-dilute-copper-alloy material containing pure copper with inevitable impurities, 2 to 12 mass ppm of sulfur, more than 2 mass ppm and not more than 30 mass ppm of oxygen and 4 to 37 mass ppm of Ti.
  • a wire rod is formed of a soft-dilute-copper-alloy material containing pure copper with inevitable impurities, 3 to 12 mass ppm of sulfur, more than 2 mass ppm and not more than 30 mass ppm of oxygen and 4 to 25 mass ppm of Ti.
  • Sulfur is generally introduced into copper at the time of manufacturing electrolytic copper in the industrial production of pure copper and it is thus difficult to adjust sulfur to be not more than 3 mass ppm.
  • the upper limit of the sulfur concentration in general-purpose electrolytic copper is 12 mass ppm.
  • Oxygen is preferably controlled to be more than 2 mass ppm since the softening temperature is less likely to decrease when the amount of oxygen is low, as described above. On the other hand, since surface flaws are likely to be generated during the hot process when the amount of oxygen is too large, it is preferably adjusted to not more than 30 mass ppm.
  • dispersed particles are small in size and a large number of dispersed particles are distributed. It is because the dispersed particle functions as a precipitation site of sulfur and it is thus required to be small in size and large in number.
  • sulfur and titanium form a compound or an aggregate in the form of TiO, TiO 2 , TiS or Ti—O—S, and the remainders of S and Ti are present in the form of solid solution.
  • TiO with a size of not more than 200 nm
  • TiO 2 with a size of not more than 1000 nm
  • TiS with a size of not more than 200 nm
  • Ti—O—S with a size of not more than 300 nm is distributed in the crystal grain.
  • the “crystal grain” means a crystalline structure of copper.
  • a wire rod is manufactured by the SCR (Southwire Continuous Rod System) continuous casting and rolling method where a working ratio for processing an ingot rod is 90% (30 mm in diameter) to 99.8% (5 mm in diameter). As an example, a method of manufacturing an 8 mm diameter wire rod at a working ratio of 99.3% is employed.
  • the molten copper temperature in a melting furnace be not less than 1100° C. and not more than 1320° C.
  • the molten copper temperature is determined to be not more than 1320° C. since there is a tendency that a blow hole is increased, a flaw is generated and a particle size is enlarged when the temperature of the copper is high.
  • the molten copper temperature is determined to be not less than 1100° C. since otherwise copper is likely to solidify and the manufacturing is not stable, the casting temperature is desirably as low as possible.
  • the hot rolling temperature is desirably not more than 880° C. at the initial roll and not less than 550° C. at the final roll.
  • the subject of the invention is to crystallize sulfur in the molten copper and to precipitate the sulfur during the hot rolling, and accordingly, the molten copper temperature and the hot rolling temperature should be as described in (a) and (b) in order to further decrease a solid solubility limit as an activation energy thereof.
  • the typical hot rolling temperature is not more than 950° C. at the initial roll and not less than 600° C. at the final roll, however, in order to further decrease the solid solubility limit, it is desirable to set to not more than 880° C. at the initial roll and not less than 550° C. at the final roll.
  • a soft-dilute-copper-alloy wire or sheet material such that a wire rod with a diameter of 8 mm has a conductivity of not less than 98% IACS, not less than 100% IACS, or more preferably not less than 102% IACS and that a wire rod after the cold wire drawing process (e.g., 2.6 mm in diameter) has a softening temperature from 130° C. to 148° C.
  • the softening temperature is not more than 148° C. in light of the industrial value thereof.
  • the softening temperature in case of not adding Ti is 160 to 165° C. Since the softening temperature of high purity copper (6N) is 127 to 130° C., the threshold limit value is determined to be 130° C. based on the obtained data. This slight difference is caused by inevitable impurities which are not present in high purity copper (6N).
  • the conductivity of oxygen-free copper is about 101.7% IACS and that of high purity copper (6N) is 102.8% IACS, and therefore, it is desirable to have a conductivity as close to high purity copper (6N) as possible.
  • the method should be such that, after melting the copper, casting is carried out in a ladle controlled to be a reduced-state, i.e., under reductive gas (CO) atmosphere while controlling concentrations of sulfur, Ti and oxygen, which are constituent elements of a dilute alloy, to stably manufacture a wire rod to be rolled.
  • a ladle controlled to be a reduced-state i.e., under reductive gas (CO) atmosphere while controlling concentrations of sulfur, Ti and oxygen, which are constituent elements of a dilute alloy, to stably manufacture a wire rod to be rolled.
  • the soft-dilute-copper-alloy material manufactured by the manufacturing method of the invention allows a practical soft-dilute-copper-alloy material excellent in conductivity, softening temperature and surface quality to be obtained and can be used as a molten solder plating material (wire, plate, foil), an enameled wire, soft pure copper, high conductivity copper and a soft copper wire and it is possible to reduce energy at the time of annealing, and high productivity is thereby obtained.
  • a plating layer may be formed on a surface thereof.
  • a plating layer consisting mainly of, e.g., tin, nickel, silver, zinc or palladium is applicable, or, so-called Pb-free plating may be used therefor.
  • a coaxial cable in which plural wires formed of the soft-dilute-copper-alloy material manufactured by the manufacturing method of the invention are twisted to form a central conductor, an insulation cover is formed on an outer periphery of the central conductor, an outer conductor formed of copper or copper alloy is arranged on an outer periphery of the insulation cover and a jacket layer is provided on an outer periphery of the outer conductor.
  • a composite cable in which plural coaxial cables are arranged in a shield layer and a sheath is provided on an outer periphery of the shield layer.
  • the soft-dilute-copper-alloy material manufactured by the manufacturing method of the invention is suitable for a wide range of applications such as a copper sheet used for a heatsink, a gauge copper strip used for a lead frame and copper foil used for a circuit board, etc.
  • the intended use of the soft-dilute-copper-alloy material of the invention includes use as, e.g., a wiring material for consumer solar cell, a motor enameled wire, a soft copper material for high-temperature application used at 200° C. to 700° C., a power cable conductor, a signal line conductor, a molten solder plating material which does not require annealing, a conductor for FPC wiring, a copper material excellent in thermal conductivity and a substitute material for high purity copper, and meets such a wide range of needs.
  • the shape is not specifically limited, and a conductor having a circular cross section, a rod-shaped conductor or a rectangular conductor may be used.
  • a wire rod is made by the SCR continuous casting and rolling method and a soft material is made by the hot rolling
  • a twin-roll continuous casting and rolling method or a Properzi continuous casting and rolling method may be used for the manufacturing.
  • a working ratio during plastic working before heat treatment for annealing is not less than 50% in order to obtain a desired crystalline structure.
  • the working ratio here is defined as follows.
  • a soft-dilute-copper-alloy is cold-drawn in multiple steps at a working ratio of not less than 50% for each time, and annealing treatment is performed after each step.
  • the soft-dilute-copper-alloy material obtained by the manufacturing method of the invention has a crystalline structure in which the average crystal grain size from the surface toward the inner side up to a depth of 20% of a wire diameter or a sheet thickness is not more than 20 ⁇ M.
  • annealing method using a plastic-worked material to obtain a desired crystalline structure continuous annealing by passing a material through a tubular furnace at a temperature of 250° C. to 550° C. for 0.6 seconds to 5.0 seconds is applicable to a line-shaped material having a diameter of less than 1 mm.
  • the reason therefor is that, when the temperature is lower than 250° C. or the annealing time is shorter than 0.6 seconds, the worked structure is still present in the material and the value of the elongation percentage is small. On the other hand, when the temperature is more than 550° C.
  • a desired crystalline structure or elongation percentage may not be obtained due to coarsened crystal grains or an excessively softened conductor may be deformed by tension at the time of winding up.
  • continuous annealing by passing a material through a tubular furnace at a temperature of 300° C. to 800° C. for 1.0 second to 10.0 seconds is applicable to a line-shaped material having a diameter of not less than 1 mm.
  • batch annealing at a temperature of 150° C. to 550° C. for not more than 3 hours is applicable to a line-shaped material having a diameter of less than 1 mm.
  • the batch annealing is characterized in that use of a large capacity annealing furnace allows a large amount of material to be annealed for each annealing process and it is effective to anneal a thin conductor of which volume per unit length is small.
  • the reason for selecting such annealing conditions is that, when the temperature is lower than 150° C., softening is not enough and the value of the elongation percentage is low in the same manner as described above.
  • the temperature is more than 550° C. or the annealing time is longer than 3 hours, a desired crystalline structure may not be obtained due to coarsened crystal grains, or elongation percentage may be small or defects such as adhesion between wires may be likely to occur.
  • batch annealing at a temperature of 170° C. to 700° C. for not more than 3 hours is applicable to a line-shaped material having a diameter of not less than 1 mm.
  • the lower limit of the annealing time is desirably not less than 0.5 hours in order to obtain a desired crystalline structure and to soften the material.
  • annealing using an electric annealer allows softening at a high processing speed and it is thus possible to contribute to high efficiency production, i.e., cost reduction.
  • the reason for selecting such annealing conditions is that, when the applied voltage is less than 20V or the velocity is greater than 600 m/min, softening is not enough and the value of the elongation percentage is low.
  • the applied voltage is more than 30V or the velocity is less than 300 m/min, a desired crystalline structure may not be obtained due to coarsened crystal grains, or elongation percentage may be small or the conductor may be deformed or broken due to excessive thermal energy.
  • continuous treatment using an electric annealer at an applied voltage of 25V to 35V and at a velocity of 100 m/min to 500 m/min is applicable to a line-shaped material having a diameter of not less than 1 mm.
  • these annealings be performed in an inert gas such as nitrogen gas or argon gas in order to prevent oxidation of the copper alloy material.
  • the soft-dilute-copper-alloy material in the invention has a crystalline structure in which the average size of crystal grains included in a surface layer is not more than 20 ⁇ m at least from the surface of a wire or a sheet toward the inner side of the copper conductor up to a depth of 20% of a wire diameter or a sheet thickness and the average crystal grain size of the inner side is larger than that in the surface layer.
  • One embodiment of the invention can offer a method of manufacturing a high conductive soft-dilute-copper-alloy material that has high tensile strength and high elongation percentage even though it is a soft copper material, wherein the manufacturing steps are simple and low-cost.
  • FIG. 1 is graph showing a relation between an annealing temperature and elongation percentage of Example Material 1 and Comparative Material 1;
  • FIG. 2 is a photograph showing a radial cross section structure of Example Material 1 at an annealing temperature of 500° C.;
  • FIG. 3 is a photograph showing a radial cross section structure of Example Material 1 at an annealing temperature of 700° C.;
  • FIG. 4 is a photograph showing a radial cross section structure of Comparative Material 1;
  • FIG. 5 is a schematic view showing a bending fatigue test
  • FIG. 6 is a graph as a result of measuring a bending life, showing a relation between surface bending strain and the number of bending cycle of Example Material 2 and Comparative Material 2;
  • FIG. 7 is a photograph showing a cross section structure across-the-width of Example Material 2;
  • FIG. 8 is a photograph showing a cross section structure across-the-width of a sample Comparative Material 2;
  • FIG. 9 is a graph as a result of measuring a bending life, showing a relation between surface bending strain and the number of bending cycle of Example Material 3 and Comparative Material 3;
  • FIG. 10 is a photograph showing a cross section structure across-the-width of Example Material 3;
  • FIG. 11 is a photograph showing a cross section structure across-the-width of Comparative Material 3;
  • FIG. 12 is a schematic view showing a method of measuring an average crystal grain size in a surface layer of a sample
  • FIG. 13 is a graph showing a relation between tensile strength and an elongation percentage of Example Material 4 and Comparative Material 4;
  • FIG. 14 is a graph showing a relation between an elongation percentage and hardness of Example Material 4 and Comparative Material 4;
  • FIG. 15 is a graph showing a relation between tensile strength and hardness of Example Material 4 and Comparative Material 4;
  • FIGS. 16A and 16B are photographs showing a cross section structure across-the-width of Example Material 4.
  • FIG. 17 is a photograph showing a cross section structure across-the-width of Comparative Material 4.
  • FIG. 18 is a schematic view showing a method of measuring an average crystal grain size in a surface layer.
  • 8 mm diameter copper wires (wire rods, a working ratio of 99.3%) containing low-oxygen copper (oxygen concentration of 7 mass ppm to 8 mass ppm and sulfur concentration of 5 mass ppm) and 13 mass ppm of Ti were made as experimental materials.
  • the 8 mm diameter copper wires have been hot rolled by SCR continuous casting and rolling.
  • Copper molten metal which was melted in a shaft furnace was poured into a ladle under a reductive gas atmosphere, the molten copper poured into the ladle was introduced into a casting pot under the same reductive gas atmosphere, and Ti was added in the casting pot, and subsequently, an ingot rod was made in a casting mold formed between a casting wheel and an endless belt by sending the resulting molten copper through a nozzle.
  • the 8 mm diameter copper wire was made by hot rolling the ingot rod. Then, each experimental material was cold-drawn. A 2.6 mm diameter copper wire (copper bonding wire, a working ratio of 89.4%) was thereby made.
  • Comparative Material 1 using an oxygen-free copper wire and Example Material 1 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti were used as samples and were annealed at different annealing temperatures for 1 hour, and the results of examining Vickers hardness (Hv) thereof are shown in Table 1.
  • Table 1 shows that Vickers hardness (Hv) of Comparative Material 1 is at the equivalent level to that of Example Material 1 at the annealing temperature of 400° C., as well as at the annealing temperature of 600° C. This shows that the soft-dilute-copper-alloy wire of the invention has sufficient softening characteristics and is especially excellent in softening characteristics at the annealing temperature of more than 400° C. even in comparison to an oxygen-free copper wire.
  • Comparative Material 1 using an oxygen-free copper wire and Example Material 1 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti were annealed at different annealing temperatures for 1 hour, and the result of examining variation in a 0.2% proof stress value thereof are shown in Table 2.
  • the samples having a diameter of 2.6 mm were used.
  • Table 2 shows that the 0.2% proof stress value of Comparative Material 1 and that of Example Material 1 are at the equivalent level at the annealing temperature of 400° C., and are nearly the same at the annealing temperature of 600° C.
  • FIG. 1 is a graph showing variation in elongation (%) of Comparative Material 1 using a 2.6 mm diameter oxygen-free copper wire and Example Material 1 using a 2.6 mm diameter soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti which were annealed at different annealing temperatures for 1 hour.
  • a circle point indicates Example Material 1 and a square point indicates Comparative Material 1.
  • FIG. 1 shows that Example Material 1 exhibits better elongation characteristics than Comparative Material 1 at an annealing temperature of more than 100° C. in a wide range of around 130° C. to 900° C.
  • FIG. 2 is a photograph showing a cross section of a copper wire of Example Material 1 at an annealing temperature of 500° C. As shown in FIG. 2 , a fine crystalline structure is formed on the entire cross section of the copper alloy wire and it appears that the fine crystalline structure contributes to the elongation characteristics. On the other hand, secondary recrystallization has proceeded in the cross section structure of Comparative Material 1 at the annealing temperature of 500° C., and crystal grains in the cross section structure were coarsened as compared to the crystalline structure of FIG. 2 . It is considered that this decreases the elongation characteristics.
  • FIG. 3 is a photograph showing a cross section of the copper wire of Example Material 1 at an annealing temperature of 700° C. It is found that the crystal aain size in the surface layer on the cross section of the copper alloy wire is extremely smaller than the crystal grain size of the inner side. Although secondary recrystallization has proceeded in the crystalline structure of the inner side, a fine crystal grain layer remains as the outer layer. It is considered that the high elongation characteristics are maintained since the fine crystal layer remains as the surface layer even though the crystalline structure of the inner side grows to be large.
  • FIG. 4 is a photograph showing across section structure in Comparative Material 1.
  • Comparative Material 1 it is considered that the elongation characteristics in a high temperature range of not less than 600° C. are lower than those of Example Material 1 since crystal grains having a substantially equal size all around are uniformly aligned from the surface to the middle portion and secondary recrystallization has proceeded in the entire cross section structure.
  • Example Material 1 exhibits better elongation characteristics than Comparative Material 1, handling properties are excellent at the time of manufacturing a stranded wire using this conductor, bending resistance characteristics are excellent and it is advantageous in that it is easy to lay a cable due to flexibility.
  • a long bending life is required for the soft-dilute-copper-alloy material of the invention. Accordingly, the bending life was measured on Comparative Material 2 using an oxygen-free copper wire and on Example Material 2 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti.
  • the samples used here are a 0.26 mm diameter wire rod annealed at the annealing temperature of 400° C. for 1 hour.
  • Comparative Material 2 has the same element composition as that of Comparative Material and also Example Material 2 has the same element composition as that of Example Material 1.
  • FIG. 5 shows a method of measuring the bending life, and a bending fatigue test was conducted by this method.
  • the bending fatigue test is a test in which a load is applied to a sample to impart tension and compression strain to the surface thereof by cyclic bending.
  • the sample is placed between bending jigs (which are referred to as “ring” in the drawing) as shown in (A) and is bent by a 90° rotation of the jigs as shown in (B) while the load is still applied.
  • a compressive strain is applied to a surface of the wire rod in contact with the bending jig and a tensile strain is applied to an opposite surface. After that, it returns to a state (A) again.
  • the sample is bent by a 90° rotation in a direction opposite to the direction shown in (B). Also in this case, a compressive strain is applied to the surface of the wire rod in contact with the bending jig and a tensile strain is applied to the opposite surface, and it becomes a state (C). Then, it returns to the initial state (A) from (C).
  • One bending fatigue cycle consisting of (A)-(B)-(A)-(C)-(A) requires 4 seconds.
  • the surface bending strain can be derived by the following formula.
  • FIG. 6 is a graph showing a relation between surface bending strain and the number of bending cycle when the bending life is measured on Comparative Material 2 using an oxygen-free copper wire and Example Material 2 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti which were annealed at 400° C. for 1 hour.
  • the number of bending cycles at the surface bending strain of 0.45% was slightly more than 4000 cycles in Example Material 2 of the invention while that of Comparative Material 2 is slightly less than 2000 cycles, which shows that the bending life of Example Material 2 is twice longer than Comparative Material 2.
  • FIG. 7 is a photograph of a cross section structure showing a crystalline structure across-the-width of Example Material 2
  • FIG. 8 is a photograph of a cross section structure showing a crystalline structure across-the-width of Comparative Material 2.
  • Example Material 2 is a 0.26 mm diameter wire rod which has the same element composition as that of Comparative Material 1 and the highest soft material conductivity and is made through annealing treatment at an annealing temperature of 400° C. for 1 hour.
  • Comparative Material 2 is a 0.26 mm diameter wire rod formed of oxygen-free copper (OFC) and is made through annealing treatment at an annealing temperature of 400° C. for 1 hour.
  • OFC oxygen-free copper
  • Example Material 2 The conductivity of Example Material 2 and Comparative Material 2 is shown in Table 3.
  • Example Material 2 As shown in Table 3, when passing an electric current through Example Material 2, electron flow is less disturbed as compared to Comparative Material 2, hence, electrical resistance decreases. Therefore, the conductivity (% IACS) of Example Material 2 is greater than that of Comparative Material 2.
  • Example Material 2 has a difference in the size of crystal grain between the surface layer and the inner side and a crystal grain size of the inner side is extremely larger than that in the surface layer.
  • Example Material 2 S in copper of a conductor which is processed to have a diameter of, e.g., 2.6 mm or 0.26 mm is trapped in the form of Ti—S or Ti—O—S.
  • oxygen (O) included in copper is present in the form of Ti 3 O y , e.g., TiO 2 , and is precipitated in a crystal grain or at crystal grain boundary.
  • Example Material 2 recrystallization is likely to proceed when copper is annealed to recrystallize the crystalline structure, and thus, the crystal grains of the inner side grow to be large. Accordingly, when passing an electric current through Example Material 2, electron flow is less disturbed as compared to Comparative Material 2, hence, electrical resistance decreases. Therefore, the conductivity (%IACS) of Example Material 2 is greater than that of Comparative Material 2.
  • Example Material 2 As a result, a product using Example Material 2 is soft and can have an improved conductivity and improved bending characteristics.
  • a conventional conductor requires high temperature annealing treatment in order to recrystallize the crystalline structure to have a size equivalent to that in Example Material 2.
  • S is re-dissolved when the annealing temperature is too high.
  • the conventional conductor is softened when recrystallized and the bending characteristics decreases.
  • Example Material 2 while crystal grains of the inner side become large and the material becomes soft since it can be recrystallized without twining at the time of annealing, the bending characteristics do not decrease since fine crystals remain in the surface layer.
  • FIG. 9 is a graph showing a relation between surface bending strain and the number of bending cycle, indicating the results of the bending life measured on Comparative Material 3 using an oxygen-free copper wire and Example Material 3 using a soft-dilute-copper-alloy wire containing low-oxygen copper and Ti which were annealed at 600° C. for 1 hour.
  • the samples used here are a 0.26 mm diameter wire rod annealed at the annealing temperature of 600° C. for 1 hour.
  • Comparative Material 3 has the same element composition as that of Comparative Material 1 and also Example Material 3 has the same element composition as that of Example Material 1.
  • the bending life was measured under the same conditions as the measuring method shown in FIG. 5 .
  • Example Materials 2 and 3 exhibit a greater 0.2% proof stress value than Comparative Materials 2 and 3 under any annealing conditions.
  • FIG. 10 is a photograph of a cross section structure showing a crystalline structure across-the-width of Example Material 3
  • FIG. 11 is a photograph of a cross section structure showing a crystalline structure across-the-width of Comparative Material 3.
  • FIGS. 10 and 11 it is found that crystal grains having an equal size all around are uniformly aligned from the surface to the middle portion in the crystalline structure of Comparative Material 3.
  • the size of crystal grain in the crystalline structure of Example Material 3 is uneven as a whole, and it is notable here that a crystal grain size in a thin layer formed on the sample near a surface thereof in a cross-sectional direction is extremely smaller than that of inner side.
  • Example Material 3 which is not formed in Comparative Material 3, contributes to improve bending characteristics of Example Material 3.
  • FIG. 12 shows a method of measuring an average crystal grain size in the surface layer.
  • a crystal grain size was measured within 1 mm in length from a surface of a widthwise cross section of a 0.26 mm diameter wire rod up to a depth of 50 ⁇ m at intervals of 10 ⁇ m in a depth direction as shown in FIG. 12 , and an average of the actual measured values was defined as an average crystal grain size in the surface layer.
  • the average crystal grain size in the surface layer of Comparative Material 3 was 50 ⁇ m, and is largely different from that of Example Material 3 which was 10 ⁇ m. It is believed that a fine average crystal grain size in the surface layer suppresses development of cracks caused by the bending fatigue test, which extends the bending fatigue life. That is, cracks are developed along a crystal grain boundary when the crystal grain size is large. However, the development of cracks is suppressed when the crystal grain size is small since a developing direction of cracks is changed, and it is considered that this is the reason why a large difference in the bending characteristics is caused between Comparative Material 3 and Example Material 3 as described above.
  • the crystal grain size in the surface layers of Example Material 1 and Comparative Material 1 each having a diameter of 2.6 mm was measured within 10 mm in length from the surface of a widthwise cross section of a 2.6 mm diameter wire rod up to a depth of 50 ⁇ m in a depth direction.
  • the average crystal grain size in the surface layer of Comparative Material 1 was 100 ⁇ m and that of Example Material 1 was 20 ⁇ m.
  • the upper limit of the average crystal grain size in the surface layer is preferably not more than 20 ⁇ m, and considering a limit value for production, the average crystal grain size is supposed to be not less than 5 ⁇ m.
  • the procedure to make a 2.6 mm diameter copper wire is the same as that in Example Material 1 of the soft-dilute-copper-alloy material. Then, the copper wire was drawn to have a diameter of 0.9 mm, was once annealed by an electric annealer and was drawn again to have a diameter of 0.05 mm. A working ratio for processing from 2.6 mm to 0.9 mm in diameter is 88.0%.
  • the 0.05 mm diameter material was continuously annealed by an electric annealer at an applied voltage of 21V to 33V and at a take-up speed of 500 m/min, thereby preparing a material as Example Material 4.
  • oxygen-free copper (OFC with a purity of not less than 99.99%) having a diameter of 0.05 mm which was made under the same thermomechanical treatment conditions was prepared as a material as Comparative Material 4.
  • the wire drawing working ratio for processing from 0.9 mm to 0.05 mm diameter is 99.7%.
  • the soft-dilute-copper-alloy material drawn from 0.9 mm to 0.05 mm in diameter in the same manner as described above was annealed by running in a tubular furnace at 400° C. to 600° C. for 0.8 to 4.8 seconds, thereby preparing a material as Example Material 4.
  • oxygen-free copper (OFC with a purity of not less than 99.99%) having a diameter of 0.05 mm which was made under the same thermomechanical treatment conditions was prepared as a material as Comparative Material 4.
  • FIG. 13 shows a relation between tensile strength and elongation percentage of Example Material 4 and Comparative Material 4 which are measured after a wire rod of Comparative Material 1 using an oxygen-free copper wire and a wire rod of Example Material 1 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti are drawn from 0.9 mm (annealed material) to 0.05 mm in diameter and are annealed by an electric annealer (voltage: 21 to 33V, take-up speed: 500 m/min).
  • Example Material 4 is 15 MPa or more greater than that of Comparative Material 4 when compared at substantially the same elongation percentage. Since it is possible to increase tensile strength without decreasing elongation percentage even in comparison to oxygen-free copper, occurrence of wire breakage due to application of stress can be more reduced in, e.g., the soft-dilute-copper-alloy wire of Example Material 4 than in a conductor using oxygen-free copper.
  • FIG. 14 shows a relation between cross-sectional hardness (Hv) and a mechanical characteristic (elongation percentage) which are measured on a wire rod of Comparative Material 4 using an oxygen-free copper wire and a wire rod of Example Material 4 using a soft-dilute-copper-alloy wire containing low-oxygen copper and 13 mass ppm of Ti after drawing from 0.9 mm (annealed material) to 0.05 mm in diameter and annealing by running in a tubular furnace (temperature: 300° C. to 600° C., annealing time: 0.8 to 4.8 seconds).
  • a horizontal section of the 0.05 mm diameter wire embedded in a resin was polished and Vickers hardness at the center portion of the wire was measured.
  • Tensile strength and an elongation percentage were measured and evaluated by conducting a tensile test on the 0.05 mm diameter wire under the conditions of a gage length of 100 mm and a tension rate of 20 mm/min.
  • the maximum tensile stress at which the material is fractured is defined as tensile strength
  • the maximum deformation volume (strain) at which the material is fractured is defined as an elongation percentage.
  • Example Material 4 is about 10 Hv smaller than that of Comparative Material 4 when compared at substantially the same elongation percentage. Since it is possible to reduce the hardness without decreasing the elongation percentage even in comparison to oxygen-free copper, damage to a pad at the time of bonding can be more reduced in, e.g., the soft-dilute-copper-alloy wire of Example Material 4 than in a bonding wire using oxygen-free copper.
  • Example Material 4 The data under the conditions in which the hardness of Example Material 4 is substantially equal to that of Comparative Material 4 is extracted from the evaluation results shown in FIG. 13 , and comparison of the results is shown in Table 4.
  • the data of Example Material 4 is mechanical characteristics and hardness when the wire rod of Example Material 1 was drawn from 0.9 mm (annealed material) to 0.05 mm in diameter and was annealed by running in a tubular furnace at 400° C. for 1.2 seconds.
  • Comparative Material 4 is mechanical characteristics and hardness when the wire rod of Comparative Material 1 was drawn from 0.9 mm (annealed material) to 0.05 mm in diameter and was annealed by running in a tubular furnace at 600° C. for 2.4 seconds.
  • Example Material 4 As shown in Table 4, the elongation percentage of Example Material 4 is 7% or more higher than Comparative Material 4 even though Example Material 4 and Comparative Material 4 are materials having the same hardness. Therefore, when Example Material 4 is used as, e.g., a bonding wire, it is possible to greatly contribute to improvement in connection reliability and handling properties at the time of wire bonding. In addition, since the tensile strength is higher than that of the bonding wire using oxygen-free copper even though the hardness is the same, it is possible to greatly contribute to strength reliability of a connecting portion (a ball neck portion).
  • connection reliability of the wire bonding portion is resistance to stress generated by a difference in thermal expansion between a copper wire and a resin material after performing wire bonding and then resin molding.
  • the handling properties are resistance to stress at the time of feeding a wire from a wire spool to the bonding portion, and also being not susceptible to permanent set of winding.
  • FIG. 15 is a graph showing a relation between hardness (Hv) and tensile strength. As shown in FIG. 15 , it is understood that the hardness of Example Material 4 is about 10 Hv smaller than that of Comparative Material 4 when compared at substantially the same tensile strength. Since it is possible to reduce the hardness without decreasing the tensile strength, damage to a pad at the time of bonding can be reduced when the soft-dilute-copper-alloy material of Example Material 4 is used for, e.g., a bonding wire.
  • Example Material 4 The data under the conditions in which the tensile strength of Example Material 4 is substantially equal to that of Comparative Material 4 is extracted and comparison of the results is shown in Table 5.
  • the data of Example Material 4 is mechanical characteristics and hardness when the wire rod of Example Material 1 was drawn from 0.9 mm (annealed material) to 0.05 mm in diameter and was annealed by running in a tubular furnace at 500° C. for 4.8 seconds.
  • the data of Comparative Material 4 is mechanical characteristics and hardness the wire rod of Comparative Material 1 was drawn from 0.9 mm (annealed material) to 0.05 mm in diameter and was annealed by running in a tubular furnace at 600° C. for 2.4 seconds.
  • Example Material 4 As shown in Table 5, the elongation percentage of Example Material 4 is 5% higher than Comparative Material 4 even though Example Material 4 and Comparative Material 4 are materials having the same tensile strength. Therefore, when Example Material 4 is used as, e.g., a bonding wire, it is possible to greatly contribute to improvement in connection reliability and handling properties at the time of wire bonding. In addition, since the hardness of Example Material 4 is sufficiently smaller than that of Comparative Material 4 even though the tensile strength is the same, damage to a pad at the time of bonding can be reduced.
  • connection reliability and the handling properties of the wire bonding portion are the same as described above.
  • the invention can provide a conductor having a tensile strength of not less than 270 MPa and elongation of not less than 7% when considering that the tensile strength is important, and can provide a conductor having a tensile strength of not less than 210 MPa up to 270 MPa, an elongation percentage of not less than 15% and a hardness of not more than 65 Hv when considering that small hardness is additionally important.
  • FIGS. 16A and 16B are photographs showing a cross section structure across-the-width of Example Material 4 and FIG. 17 is a photograph showing a cross section structure across-the-width of Comparative Material 14. The photographs of FIGS. 16A and 16B are taken at different positions.
  • Example Material 4 which is not formed in Comparative Material 4 contributes to having softening characteristics of Example Material 4 and achieving both of tensile strength and elongation characteristics.
  • FIG. 18 is a schematic view showing a method of measuring an average crystal grain size in the surface layer.
  • a crystal grain size was measured within 0.25 mm in length from a surface of a widthwise cross section of a 0.05 mm diameter wire up to a depth of 10 ⁇ m at intervals of 5 ⁇ m in a depth direction as shown in FIG. 18 . Then, an average of the measured values (actual measured values) was derived and was defined as an average crystal grain size.
  • the average crystal grain size in the surface layer of Comparative Material 4 was 22 ⁇ m, and is different from that of Example Material 4 which was 7 ⁇ m in FIG. 16A and 15 ⁇ m in FIG. 16B .
  • One of the reasons why high tensile strength and elongation percentage were obtained is believed that the average crystal grain size in the surface layer is fine. Note that, cracks are developed along a crystal grain boundary when the crystal grain size is large. However, the development of cracks is suppressed when the crystal grain size is small since a developing direction of cracks is changed. It is considered that this is the reason why fatigue characteristics of Example Material 4 are better than those of Comparative Material 4.
  • the fatigue characteristics mean the number of stress application cycles or time until the material is fractured when receiving stress repeatedly.
  • the average crystal grain size in the surface layer is preferably not more than 15 ⁇ m.
  • Tables 6 to 8 show working ratios and heat treatment conditions of the 0.05 mm diameter soft-dilute-copper-alloy material, presence of fine crystals in the surface layer which contributes to improvement in tensile strength, an elongation percentage and bending characteristics as described above, and evaluation results of elongation percentage or hardness.
  • the procedure to make a 0.9 mm diameter copper wire is the same as that in Example Material 1 of the soft-dilute-copper-alloy material.
  • the wire with a final diameter was annealed by running in a tubular furnace, and Table 6 shows the evaluations of the average crystal grain size in the surface layer and the elongation percentage with respect to the temperature and the annealing time.
  • Table 7 shows the evaluations of the average crystal grain size in the surface layer and the cross sectional hardness of the conductor with respect to the applied voltage and the velocity.
  • the elongation percentage was evaluated by conducting a tensile test, and then, not less than 15% of elongation percentage was regarded as “passed the test ( ⁇ )”, 10 to less than 15% was regarded as “insufficient ( ⁇ )” and below 10% was regarded as “unsuitable (X)”.
  • Vickers hardness test was conducted on the horizontal section of the material embedded in a resin, and then, not more than 80 Hv was regarded as “passed the test ( ⁇ )” and more than 80 Hv was regarded as “unsuitable (X)”.
  • Table 8 shows the evaluations of the average crystal grain size in the surface layer and the elongation with respect to the temperature and the annealing time.
  • the working ratios of the samples used for evaluations in Tables 8 were adjusted by annealing the wire still having a non-final diameter for several times during the processing of an annealed material from a 0.9 mm diameter to 0.25 mm as a final diameter of each sample.
  • the average crystal grain size in the surface layer was measured by the same method as in Tables 6 and 7.
  • the value of the elongation percentage was evaluated by conducting a tensile test, and then, not less than 18% of elongation percentage was regarded as “passed the test ( ⁇ )”, 13 to less than 18% was regarded as “insufficient ( ⁇ )” and below 13% was regarded as “unsuitable (X)”.
  • the heat treatment temperature is less than 250° C. or more than 550° C. or when the heat treatment time is not more than 0.5 seconds or more than 5.0 seconds, it is not possible to obtain a fine crystal grain size and a high elongation percentage. This is because a worked structure is still present due to insufficient recrystallization in the case of the temperature of less than 250° C. or the treatment time of not more than 0.5 seconds, and on the other hand, crystals are coarsened due to excessive heat and also an elongation percentage decreases in the case of the temperature of more than 550° C. or the treatment time of more than 5.0 seconds.
  • a soft-dilute-copper-alloy material of the invention it is desirable that continuous annealing be performed by passing a material through a tubular furnace under the annealing conditions of a temperature of 250° C. to 550° C. for 0.6 seconds to 5.0 seconds when the working ratio is not less than 50% and the wire diameter is less than 1.0 mm.
  • Tables 9 to 11 show working ratios and heat treatment conditions of the material, presence of fine crystals in the surface layer which contributes to improvement in tensile strength, an elongation percentage and bending characteristics and evaluation results of elongation percentage or hardness.
  • the procedure to make a 2.6 mm diameter copper wire is the same as that in Experimental Example of the soft-dilute-copper-alloy material.
  • the wire with a final diameter was annealed by running in an tubular furnace, and Table 9 shows the evaluations of the average crystal grain size in the surface layer and the elongation percentage with respect to the temperature and the annealing time.
  • Table 10 shows the evaluations of the average crystal grain size in the surface layer and the cross sectional hardness of the conductor with respect to the applied voltage and the velocity.
  • Table 11 shows the evaluations of the average crystal grain size in the surface layer and the cross sectional hardness of the conductor with respect to the temperature and heat holding time.
  • the elongation percentage was evaluated by conducting a tensile test, and then, not less than 18% of elongation percentage was regarded as “passed the test ( ⁇ )”, 13 to less than 18% was regarded as “insufficient ( ⁇ )” and below 13% was regarded as “unsuitable (X)”.
  • Vickers hardness test was conducted on the horizontal section of the material embedded in a resin, and then, not more than 80 Hv was regarded as “passed the test ( ⁇ )” and more than 80 Hv was regarded as “unsuitable (X)”.
  • the heat treatment temperature is less than 300° C. or more than 820° C. or when the heat treatment time is not more than 0.5 seconds or more than 10.0 seconds
  • a worked structure is still present due to insufficient recrystallization in the case of the temperature of less than 300° C. or the treatment time of not more than 0.5 seconds
  • crystals are coarsened due to excessive heat and also an elongation percentage decreases in the case of the temperature of more than 820° C. or the treatment time of more than 10.0 seconds.
  • the working ratio be not less than 50% and the annealing be performed by a tubular furnace under the annealing treatment conditions of a temperature of 250° C. to 800° C. for 0.6 seconds to 10.0 seconds after the compression.
  • annealing by a tubular furnace under the annealing treatment conditions of a temperature of 250° C. to 550° C. for 0.6 seconds to 5.0 seconds is more desirable
  • annealing by an electric annealer under the annealing treatment conditions of an applied voltage of 21V to 33V and a velocity of 300 m/min to 600 m/min is more desirable as an another aspect
  • batch annealing under the annealing treatment conditions of a temperature of 150° C. to 550° C. for not more than 3 hours is more desirable as a still another aspect.
  • annealing by a tubular furnace under the annealing treatment conditions of a temperature of 300° C. to 800° C. for 1.0 second to 10.0 seconds is more desirable, and in addition, annealing by an electric annealer under the annealing treatment conditions of an applied voltage of 25V to 35V and a velocity of 100 m/min to 500 m/min is more desirable as an another aspect, and also, batch annealing under the annealing treatment conditions of a temperature of 170° C. to 700° C. for not more than 3 hours is more desirable as a still another aspect.
  • a crystalline structure in which an average crystal grain size at least from the surface up to a depth of 20% of a wire diameter is not more than 15 ⁇ m can be obtained by plastic working of a soft-dilute-copper-alloy containing Ti, etc., and a balance consisting of copper and inevitable impurity and then by adjusting the working ratio prior to the annealing treatment to be not less than 50%, high conductivity is provided and also it is possible to achieve both of high tensile strength and elongation percentage even though it is a soft material, hence, it is possible to improve connection reliability of the product.
  • the soft-dilute-copper-alloy material obtained by the manufacturing method of the present embodiment does not require high purification of copper (not less than 99.999 mass %) and can realize high conductivity by a cheap SCR continuous casting and rolling method, productivity is high and it is possible to reduce the cost.
  • a copper bonding wire formed of the soft-dilute-copper-alloy material obtained by the manufacturing method of the present embodiment is applicable as a substitute for an Al bonding wire having a diameter of about 0.3 mm for vehicle power module. Therefore, even though current density is increased by downsizing of the module in accordance with reduction of wire diameter due to high thermal conductivity of a material or an increase in heat dissipation due to improvement in thermal conductivity, a decrease in connection reliability caused thereby can be avoided.

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JP5747970B2 (ja) 2013-10-10 2015-07-15 三菱マテリアル株式会社 ボンディングワイヤ用銅素線
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