WO2012096238A1 - Procédé de coulée continue pour le cuivre ou un alliage de cuivre - Google Patents

Procédé de coulée continue pour le cuivre ou un alliage de cuivre Download PDF

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Publication number
WO2012096238A1
WO2012096238A1 PCT/JP2012/050212 JP2012050212W WO2012096238A1 WO 2012096238 A1 WO2012096238 A1 WO 2012096238A1 JP 2012050212 W JP2012050212 W JP 2012050212W WO 2012096238 A1 WO2012096238 A1 WO 2012096238A1
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Prior art keywords
copper
conductivity
casting
cast
wheel
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PCT/JP2012/050212
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English (en)
Japanese (ja)
Inventor
司 高澤
吉田　浩一
俊郎 阿部
修司 富松
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古河電気工業株式会社
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Priority to JP2012552715A priority Critical patent/JP5863675B2/ja
Publication of WO2012096238A1 publication Critical patent/WO2012096238A1/fr

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    • 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
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0602—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a casting wheel and belt, e.g. Properzi-process

Definitions

  • the present invention relates to a method for producing a copper alloy wire used as a copper wire or an automobile wire harness, a robot cable, and other signal wires.
  • the present invention relates to a belt and a copper or copper alloy suitable for such wire use.
  • the present invention relates to a continuous casting method using a wheel method.
  • an alloy used as a mold is required to have high temperature strength and high thermal conductivity.
  • Cast ring materials currently used in the belt and wheel method are mainly Cu—Cr—Zr alloys and Cu—Ag alloys of high conductivity (EC) (80 to 95% IACS) copper alloy.
  • EC high conductivity
  • a material with high conductivity has good thermal conductivity, excellent ingot cooling capability, and high production capability (see Patent Document 1).
  • pure copper alloys having a conductivity of 60% IACS or higher were cast using an iron casting ring.
  • the iron cast ring has a conductivity of 17% IACS, and its heat transfer coefficient is smaller than that of the copper cast ring, so the cooling capacity is weak and it is difficult to increase the casting speed. Moreover, cracking occurred on the ring surface due to the brittleness of iron, and long-term casting work could not be performed.
  • a mold release material is applied to the inner surface of the casting ring to prevent seizure.
  • this mold release material has a large thermal resistance, if the thickness varies, solidification becomes uneven and ingot defects occur. Will occur.
  • Patent Document 2 a material having a conductivity of 80% IACS or less for the casting ring.
  • Patent Document 3 a material having a low conductivity of 20 to 50% IACS for the mold conductivity is used in order to reduce the amount of heat removal and raise the ingot temperature.
  • an alloy having poor heat conduction is difficult to be cooled, so that solidification is delayed and solidification cracking and shrinkage are likely to occur.
  • the productivity is significantly reduced.
  • alloys with poor thermal conductivity are susceptible to cooling conditions.
  • the heat conduction of the cast alloy referred to here indicates that in a state immediately after solidification.
  • a precipitation type alloy it means heat conduction in a solid solution state.
  • An object of the present invention is to provide a continuous casting method of copper or copper alloy which is excellent in ingot quality and has a high cooling capacity and excellent productivity.
  • the inventors of the present invention created cast rings with various electrical conductivities, and conducted intensive studies on the conditions for achieving both ingot and rough drawn wire surfaces, internal quality, and productivity. Found rate casting ring.
  • the present invention has been completed based on this finding. That is, the present invention provides the following solutions.
  • d Depth of rough line surface defect (mm)
  • r radius of rough drawing wire (mm)
  • the conductivity satisfying the following formula (II-1) with respect to the conductivity a1 (% IACS) of the cast copper or copper alloy as a casting ring The continuous casting method according to (1), wherein a material having a rate b (% IACS) is used.
  • a1 Conductivity of cast copper or copper alloy (% IACS)
  • b Conductivity of cast ring (% IACS)
  • the following formula (for the conductivity a2 (% IACS) of the copper alloy to be cast as a cast ring The continuous casting method according to (1) or (2), wherein a material having a conductivity b (% IACS) that satisfies II-2) is used.
  • the molten metal in the tundish is poured from a pouring nozzle into a belt and wheel casting machine constituted by a belt and a wheel that is rotated by a turn roll, and is cooled and solidified to form an ingot.
  • the continuous casting method according to (2) wherein a casting ring having the above is used.
  • the molten metal in the tundish is poured from the pouring nozzle into a belt and wheel casting machine constituted by a belt and a wheel that is rotated by a turn roll, and is cooled and solidified to form an ingot.
  • a casting method for continuously pulling out the ingot from the mold, and having a conductivity of the relationship of the above formula (II-2) with respect to a copper alloy to be cast as a casting ring constituting the wheel The continuous casting method according to (3), wherein a ring is used.
  • the continuous casting method of the present invention it is possible to cast an ingot having excellent ingot surface and internal quality, and by using this ingot, high quality copper or copper alloy that can be drawn to an ultrafine wire.
  • the productivity of rough drawing can be increased.
  • FIG. 1 is a schematic explanatory view showing a process of manufacturing a wire in one embodiment of a continuous casting method according to the belt and wheel method of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a preferred embodiment of a belt and wheel casting machine used in the continuous casting method of the present invention.
  • FIG. 3 is an enlarged sectional view taken along line III-III of the casting machine shown in FIG.
  • FIG. 4 is a graph showing the relationship between the conductivity of the alloy to be cast and the conductivity of the casting ring.
  • FIG. 5 is an explanatory diagram schematically showing heat removal when the conductivity of the cast ring is high.
  • FIG. 6 is an explanatory diagram schematically showing heat removal when the conductivity of the casting ring is low.
  • FIG. 7 is an explanatory view schematically showing heat removal when the conductivity of the cast ring is within the scope of the present invention.
  • FIG. 1 is an explanatory view showing an example of the entire process of obtaining an ingot obtained by the continuous casting method of the present invention and further using this ingot.
  • molten copper is obtained in a reducing atmosphere using a shaft furnace 1 to obtain molten copper, and the molten copper is obtained. Copper is continuously led into the tundish 3 through the basket 2.
  • the molten metal 5 in the tundish 3 is poured from a pouring nozzle (spout) 4 into a belt & wheel casting machine 8 constituted by a belt 6 and a wheel 7 which are rotated by a turn roll, cooled and solidified, and ingot.
  • the ingot 9 is continuously drawn out from the mold.
  • the wheel 7 comprises a cast ring and a wheel body.
  • the continuous ingot 10 (two-way roll method or three-way roll method) is rolled to a predetermined wire diameter, and roughing is performed.
  • the wire 11 is used.
  • the rough drawn wire 11 is wound as it is, or further rolled by a wire drawing machine 12 shown in FIG. 1 to be drawn on a pallet 14 as a wire drawing material 13.
  • the installation of the wire drawing mill 12 is arbitrary.
  • FIG. 2 shows a longitudinal sectional view of a preferred embodiment of the belt and wheel casting machine used in the belt and wheel method according to the present invention.
  • FIG. 3 is an enlarged cross-sectional view taken along line III-III in FIG.
  • the belt-and-wheel casting machine of the moving mold type has a wheel body 21, a casting belt 22 having a cooling action that is movable by a drive roll 24, and a casting ring 23 provided on the outer periphery of the wheel body 21.
  • the belt 22 is made of carbon steel or stainless steel. Carbon steel or stainless steel is applied to the wheel body 21. A material having a specific conductivity described later is applied to the casting ring 23.
  • a molten metal (a molten metal of copper or copper alloy, hereinafter simply referred to as a molten metal) 26 is poured from a pouring nozzle 25 to a casting ring 23 on the outer periphery of the wheel 21.
  • the poured molten metal 26 is cooled in a rotating casting ring and gradually solidifies to form an ingot 27.
  • FIG. 2 schematically shows the molten metal solidifying and forming an ingot.
  • the casting speed is preferably 6 to 15 m / min (100 to 250 mm / second, or 10 to 50 ton / hour) which is put into practical use in normal operation, and the ingot cross-sectional area is preferably 1930 mm 2 to 6450 mm. 2 .
  • the depth of the surface defect of the copper or copper alloy rough wire produced by the belt and wheel method satisfies the following formula (I). d ⁇ r ⁇ 0.1 (I) d: Depth of rough line surface defect (mm) r: radius of rough drawing wire (mm)
  • the radius r of the rough drawing line is not particularly limited, but is usually 2 to 12 mm.
  • the measurement method of d was calculated from the correlation between the output of the eddy current flaw detector and the depth of the dummy defect by scanning the rough line with an eddy current flaw detector. If d is too large, disconnection is likely to occur in the wire drawing process, and a lot of skin must be removed in order to remove the defective portion, resulting in a significant reduction in productivity. A method for producing such copper or copper alloy rough drawn wire will be described below.
  • [Casting ring] (conductivity) 5 to 7 are schematic diagrams showing the relationship between the conductivity of the casting ring and the heat removal from the ingot.
  • FIG. 5 shows the case where the conductivity of the casting ring is high
  • FIG. 6 shows the case where the conductivity is low
  • FIG. 7 shows the case where it is within the scope of the present invention.
  • the larger the arrow the higher the heat removal rate.
  • the casting speed is overwhelmingly faster than the known DC casting and horizontal horizontal continuous casting methods, so the solid-liquid coexistence region is long in the casting direction.
  • the thickness of the solidified shell tends to vary at the final solidified site.
  • the cast ring with high conductivity immediately after the molten metal comes into contact with the ring is strongly cooled because it has good heat conduction, so that an air gap due to solidification shrinkage immediately occurs, cooling is inhibited, cooling becomes uneven, It was found that the thickness of the solidified shell was not constant. In particular, an alloy with poor thermal conductivity is more likely to have a temperature distribution within the solidified shell than copper or copper alloy with good thermal conductivity, resulting in uneven thickness of the solidified shell and local stress concentration due to solidification shrinkage and thermal shrinkage. And solidification cracks occur on the ingot surface.
  • the inventors investigated the relationship between the conductivity of the copper or copper alloy to be treated and the conductivity of the cast ring in order to study the cooling conditions for realizing the growth of the solidified shell under stable conditions.
  • the conductivity (% IACS) of the cast ring is as follows depending on whether the product obtained by casting is pure copper or copper alloy. It has become clear that it is preferable to set the value within the range of the formula (II-1) or the following formula (II-2). This relationship is shown in FIG.
  • a1 Conductivity of cast copper or copper alloy (% IACS)
  • b Conductivity of cast ring (% IACS) 0.25 ⁇ a2 + 15 ⁇ b ⁇ 0.25 ⁇ a2 + 35 (II-2)
  • a2 Conductivity of cast copper alloy (% IACS)
  • b Conductivity of cast ring (% IACS) That is, in a preferred embodiment of the present invention, the use of a copper alloy cast ring having a specific conductivity can extremely effectively suppress the formation of an air gap immediately after pouring.
  • the inhibition of heat transfer due to the air gap in the initial stage of solidification can be alleviated and stable cooling can be performed, and as a result, a uniform and stable solidified shell having no fragile portions can be formed.
  • a sufficient cooling rate can be obtained by suppressing the air gap and cooling with a cast ring having a conductivity of a certain value or more, and the occurrence of shrinkage can also be prevented.
  • the nucleation frequency is increased by increasing the supercooling, and the ingot structure near the ingot surface can be refined. With these effects, the surface quality of the ingot can be improved, and cracking of the ingot surface can be suppressed.
  • the surface defect of the rough drawn wire can be suppressed by improving the ingot quality, and the yield can be improved as well as the quality of the rough drawn wire is improved.
  • the heat transfer between the ingot and the casting ring can be changed depending on the amount of release material applied to the ring surface, it is difficult to finely control and is not suitable for stable operation, and is controlled by the conductivity of the casting ring. However, simple and stable casting is possible.
  • the conductivity means a value measured by the measurement method employed in the examples unless otherwise specified. In particular, when producing an alloy having low heat conductivity and low conductivity, the effect of the method of the present invention is remarkable because the cooling condition greatly affects the quality.
  • the alloy materials constituting the cast ring include Cu—Cr—Zr—Al alloy, Cu—Cr alloy, Cu—Be alloy, phosphor bronze, Corson alloy, Cu—Zn alloy, Cu Copper alloys such as —Ni—Sn alloys are preferred.
  • the preferable thing of a typical component composition about each copper alloy is described below.
  • Example 1 As shown in Tables 1-9, cast rings with an ingot cross-sectional area of 3220 mm 2 each having a conductivity of 15-80% IACS were used. The component composition of the alloy material constituting the cast ring is described together with the following examples and comparative examples.
  • TPC Ag-containing tough pitch copper
  • Table 2 0.15% Sn-containing tough pitch copper
  • Table 3 0.7% Sn-containing tough pitch copper
  • Table 4 Cu-0.3% Cr-0.3% Sn
  • Table 5 Cu-0.5% Cr alloy
  • Table 6 Cu-1.5% Ni-1.0% Sn
  • Table 7 Cu-2.5% Ni-0.6% Si Corson alloy
  • Table 8) Cu-1.0%
  • a copper or copper alloy rough drawn wire of Fe-0.3% P was produced by the SCR method and drawn to ⁇ 0.1 mm.
  • Tables 1 to 9 show the quality of the product based on the detection results of the eddy current flaw detector during rough wire drawing, the amount of porosity when observing the longitudinal section of the ingot, and the presence or absence of wire breakage when the wire is drawn with rough wire The result of having performed is shown.
  • the conductivity of the cast ring was determined by measuring the polished surface of the cast ring using AutoSigma 3000 (trade name) manufactured by GE Inspection Technologies.
  • the detection results of the eddy current flaw detector shown in Tables 1 to 9 are detected per ton, where “s” is a minute defect that satisfies the above formula (I) and “l” is a large defect that does not satisfy the above formula (I). The number of each was counted. The deepest (maximum defect depth) of the detected and measured surface defects was defined as the surface defect depth d (mm).
  • the center porosity was obtained by collecting a 1 m length of the ingot, observing the longitudinal section of the center, and measuring the total length of the porosity with a width of 0.5 mm or more.
  • the amount of peel and disconnection is judged as “ ⁇ (impossible” when the ⁇ 8 mm rough drawing wire 5000 kg is peeled with 0 to 0.2 mm thickness on one side and drawn to ⁇ 0.1 mm as shown. ) ”, Those that were not disconnected were evaluated as“ ⁇ (possible) ”.
  • “ ⁇ (excellent)” indicates that the skin peel on one side was 0 mm, and the wire was cut off on one side if the peel on one side was 0 mm.
  • Table 10 shows the lower and upper limits of the conductivity of each copper or copper alloy and the mold conductivity determined by the following formula (II).
  • the conductivity of the copper or copper alloy cast here refers to the conductivity in a solid solution state.
  • the formula (II) is a combination of the formula (II-1) and the formula (II-2), and has the same meaning.
  • a cast ring whose conductivity does not exceed the upper limit is preferable because it prevents the occurrence of fine cracks on the ingot surface and deterioration of the surface quality as described above.
  • an alloy whose cast alloy has a conductivity higher than 60% IACS can avoid disconnection due to skin peeling unless the conductivity of the cast ring is too low.
  • the alloy of 60% IACS or less is broken even with a 0.2 mm peel on one side, and it can be seen that the present invention is particularly effective for an alloy having a cast alloy conductivity of 60% IACS or less.
  • Example-2 It is an Example when changing a casting speed.
  • Various casting rings (molds) with a Cu-2.5% Ni-0.6% Si Corson alloy with an ingot cross-sectional area of 3220 mm 2 and electrical conductivity shown in Table 11 were used, and the casting speed was changed, Otherwise, the casting was performed in the same manner as in Example 1.
  • the pass / fail judgment of the implementation result is “ ⁇ (possible)” for those that did not break when the 5,000-kg rough drawing wire of ⁇ 8 mm was drawn 0.1 mm on one side, and “ ⁇ (impossible)” for those that did not break. evaluated. The results are shown in Table 11.
  • the formation of the air gap can be suppressed, so that it can be cooled strongly rather than the casting ring with high conductivity in the initial stage of solidification, and moreover than the iron casting ring. Due to the high conductivity, the overall cooling capacity could be higher than that of the high conductivity ring. In experiments using casting rings with various electrical conductivity, the casting speed could be increased up to 1.2 times from the current level in the region satisfying formula (II) (that is, formula (II-1) and formula (II-2)). .
  • Example 3 Various copper or copper alloys were cast, rolled, and drawn in the same manner as in Example 1 using cast rings having different electrical conductivities.
  • the crystal grain size ( ⁇ m) of the ingot was measured by the intersection method in the direction perpendicular to the crystal grain growth direction at a location 2 mm from the ingot surface.
  • the evaluation was performed in the same manner as in Example 1.
  • the upper limit value of the casting ring formula (II) (that is, formulas (II-1) and (II-2)) is 60% IACS, and the lower limit value is 16% IACS. The obtained results are shown in Table 12.
  • the supercooling near the mold is increased, the nucleation frequency is increased, and the vicinity of the ingot surface is increased. It has become clear that the ingot structure can be refined and the ingot surface quality can be improved. As a result, surface defects could be reduced, and wire could be drawn without disconnection even with a smaller amount of skin peeling.
  • Table 13 shows the components of the cast ring of each conductivity used.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
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Abstract

[Problème] Fournir un procédé de coulée continue pour le cuivre ou un alliage de cuivre présentant une qualité supérieure de lingot, une capacité élevée de refroidissement, et une productivité supérieure. [Solution] La présente invention concerne un procédé de coulée continue pour le cuivre ou un alliage de cuivre, caractérisé en ce que la profondeur (d) (mm) pour les défauts de surface dans des fils-machine de cuivre ou d'alliage de cuivre fabriqués par le procédé à courroie et roue satisfait l'équation (I). d ≤ r × 0,1 (I) d : profondeur (mm) des défauts de surface dans le fil-machine r : rayon (mm) du fil-machine
PCT/JP2012/050212 2011-01-11 2012-01-06 Procédé de coulée continue pour le cuivre ou un alliage de cuivre WO2012096238A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021203127A1 (de) 2020-03-30 2021-09-30 Ngk Insulators, Ltd. Beryllium/Kupfer-Legierungsring und Verfahren zu seiner Herstellung
CN115044846A (zh) * 2022-06-23 2022-09-13 中国科学院宁波材料技术与工程研究所 CuCrSn合金及其变形热处理方法

Citations (5)

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JP2007237260A (ja) * 2006-03-09 2007-09-20 Furukawa Electric Co Ltd:The 皮剥き性に優れた無酸素銅及び無酸素銅合金の荒引線材
JP2008266764A (ja) * 2006-06-01 2008-11-06 Furukawa Electric Co Ltd:The 銅合金線材の製造方法および銅合金線材
JP2009226419A (ja) * 2008-03-19 2009-10-08 Furukawa Electric Co Ltd:The 銅または銅合金線材の製造方法および銅または銅合金線材
JP2010188362A (ja) * 2009-02-16 2010-09-02 Mitsubishi Materials Corp Ｃｕ−Ｍｇ系荒引線の製造方法及びＣｕ−Ｍｇ系荒引線の製造装置
WO2011004888A1 (fr) * 2009-07-10 2011-01-13 古河電気工業株式会社 Procédé pour coulée continue de bronze ou d’alliage de bronze et cylindre de coulée associé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007237260A (ja) * 2006-03-09 2007-09-20 Furukawa Electric Co Ltd:The 皮剥き性に優れた無酸素銅及び無酸素銅合金の荒引線材
JP2008266764A (ja) * 2006-06-01 2008-11-06 Furukawa Electric Co Ltd:The 銅合金線材の製造方法および銅合金線材
JP2009226419A (ja) * 2008-03-19 2009-10-08 Furukawa Electric Co Ltd:The 銅または銅合金線材の製造方法および銅または銅合金線材
JP2010188362A (ja) * 2009-02-16 2010-09-02 Mitsubishi Materials Corp Ｃｕ−Ｍｇ系荒引線の製造方法及びＣｕ−Ｍｇ系荒引線の製造装置
WO2011004888A1 (fr) * 2009-07-10 2011-01-13 古河電気工業株式会社 Procédé pour coulée continue de bronze ou d’alliage de bronze et cylindre de coulée associé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021203127A1 (de) 2020-03-30 2021-09-30 Ngk Insulators, Ltd. Beryllium/Kupfer-Legierungsring und Verfahren zu seiner Herstellung
US11746404B2 (en) 2020-03-30 2023-09-05 Ngk Insulators, Ltd. Beryllium copper alloy ring and method for producing same
CN115044846A (zh) * 2022-06-23 2022-09-13 中国科学院宁波材料技术与工程研究所 CuCrSn合金及其变形热处理方法

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JP5863675B2 (ja) 2016-02-17
TWI556888B (zh) 2016-11-11
TW201233465A (en) 2012-08-16

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