US20090038439A1 - Process for producing steel for high-carbon steel wire material with excellent drawability and fatique characteristics - Google Patents

Process for producing steel for high-carbon steel wire material with excellent drawability and fatique characteristics Download PDF

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US20090038439A1
US20090038439A1 US12/162,550 US16255007A US2009038439A1 US 20090038439 A1 US20090038439 A1 US 20090038439A1 US 16255007 A US16255007 A US 16255007A US 2009038439 A1 US2009038439 A1 US 2009038439A1
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steel
less
raw materials
molten
converter
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Sei Kimura
Tsuyoshi Mimura
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Kobe Steel Ltd
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Kobe Steel Ltd
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Assigned to KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) reassignment KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIMURA, SEI, MIMURA, TSUYOSHI
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle
    • 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
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/072—Treatment with gases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for manufacturing a steel material for obtaining a high-carbon steel wire rod with excellent drawability and fatigue property, and more particularly to a method suitable for manufacturing a steel for a steel wire rod in which the amount of nonmetallic inclusions having high hardness and very low ductility is reduced and the drawability and fatigue property are improved.
  • inclusions that are hard and have a very low ductility, such as alumina (Al 2 O 3 ) or spinel (Al 2 O 3 .MgO) are contained in a steel for tire cords or a steel for springs
  • the inclusions cause a loss of drawability in the process of drawing into an ultrafine steel wire and become the starting points for fatigue fracture at the product stage. Therefore, it is important to reduce the content of inclusions to a minimum or increase the ductility thereof by softening, thereby rendering them harmless, in the process of manufacturing the steel wire rod.
  • Patent Documents 1, 2 disclose a method for reducing the amount of impurities by using Si and Mn as deoxidizing agents for a steel melt and regulating the concentration of Al.
  • Patent References 3, 4 suggest a technology relating to the reduction in the amount of impurities by regulating the concentration of Al 2 O 3 present in a refractory container that accommodates the steel melt.
  • a technology for reducing the amount of impurities in steels by refining the steel melt by using a CaO—SiO 2 flux with a low concentration of Al 2 O 3 has also been suggested (for example, Patent Documents 5, 6).
  • Patent Document 1 Japanese Patent Application Laid-open No. 50-081907, Claims, etc.
  • Patent Document 2 Japanese Patent Application Laid-open No. 50-11618, Claims, etc.
  • Patent Document 3 Japanese Patent Application Laid-open No. 2003-245758, Claims, etc.
  • Patent Document 4 Japanese Patent Application Laid-open No. 2004-211148, Claims, etc.
  • Patent Document 5 Japanese Patent Application Laid-open No. 4-110413, Claims, etc.
  • Patent Document 6 Japanese Patent Application Laid-open No. 9-059744, Claims, etc.
  • the present invention was made in view of above circumstances, it is an object of the present invention to provide a suitable method for manufacturing a steel material for obtaining a steel wire rod that has improved drawability and fatigue property and in which the amount of hard nonmetallic inclusions is reduced by adequately controlling the conditions in secondary refining and manufacturing conditions in a converter.
  • converter blowing is performed by taking molten iron, cold iron, and steel scrap as main raw materials to be charged into a converter, the ratio of these components based on all the main raw materials being such that molten iron takes 96 to 100% (means wt.
  • a flow rate of gas for stirring molten steel during secondary refining after completion of the converter blowing is set to 0.0005 Nm 3 /min (N means “normal” and represents a volume at 298 K and 10 5 Pa; same hereinbelow) or more to 0.004 Nm 3 /min or less per 1 t of molten steel, and then a flow rate of Ar used to purge the inside of a tundish in continuous casting is set to 0.04 Nm 3 /min or more to 0.10 Nm 3 /min or less per 1 t of molten steel within the tundish.
  • the steel for a steel wire rod that is an object of the method in accordance with the present invention preferably has a chemical composition comprising C, 0.4 to 1.3%, Si: 0.1 to 2.5%, Mn: 0.2 to 1.0%, and Al: 0.003% or less with Fe and unavoidable impurities as the balance.
  • the steel for a steel wire rod that is an object of the method in accordance with the present invention also can contain as another element at least one element selected from the group consisting of (a) Ni: 0.05 to 1%, Cu: 0.05 to 1%, and Cr: 0.05 to 1.5% and at least one element selected from the group consisting of (b) Li: 0.02 to 20 ppm, Mg: 0.02 to 20 ppm, Ce: 3 to 100 ppm, and La: 3 to 100 ppm, and the properties of the steel wire rod can thus be further modified according to the type of the contained components.
  • FIG. 1 is a graph illustrating the relationship between the molten iron ratio in the main raw materials and the number of wire breakages per 10 t of steel.
  • FIG. 2 is a graph illustrating the relationship between the cold iron ratio in the main raw materials and the number of wire breakages per 10 t of steel.
  • FIG. 3 is a graph illustrating the relationship between the steel scrap ratio in the main raw materials and the number of wire breakages per 10 t of steel.
  • FIG. 4 is a graph illustrating the relationship between the flow rate of purge Ar in a tundish and the number of wire breakages per 10 t of steel.
  • molten iron is subjected to dephosphorization treatment prior to charging into a converter. Therefore, the temperature of the molten iron charged into the converter is low and a thermal margin necessary for charging the steel scrap is small.
  • the low thermal margin can be compensated by excess oxidation of C contained in the molten iron, but in the manufacture of steel for tire cords or steel for springs that are adversely affected by hard inclusions such as alumina every effort has to be made to avoid the excess oxidation of C.
  • the excess oxidation of C increases the concentration of dissolved oxygen in molten steel at the completion of converter blowing and increases the amount of FeSi alloy used in deoxidation of molten steel.
  • a small amount of Al is unavoidably contained in the FeSi alloy and, as a result, the amount of alumina-based inclusions in the molten steel is increased.
  • the inventors examines the relationship between the molten iron ratio, cold iron ratio, and steel scrap ratio in the main raw materials (the ratio of each raw material when the sum total of the molten iron, cold iron, and steel scrap is taken as 100%) that will be charged into a converter and the number of wire breakages during drawing of 10 t of steel wire rods.
  • the relationship between the molten iron ratio in the main raw materials and the number of wire breakages is shown in FIG. 1
  • the relationship between the cold iron ratio in the main raw materials and the number of wire breakages is shown in FIG. 2
  • the relationship between the steel scrap ratio in the main raw materials and the number of wire breakages is shown in FIG. 3 (the meaning of the number of wire breakages is explained in the below-described embodiments).
  • the molten iron ratio is preferably 98% or more, even more preferably 100%.
  • the preferred range of the cold iron ratio is 2% or less.
  • the average P concentration in the raw materials charged into a converter has to be 0.02% or less.
  • Dephosphorization during converter blowing proceeds simultaneously with decarburization, but because in high-carbon steels such as steels for tire cords and steels for springs, decarburization has to be suppressed, dephosphorization cannot be expected to proceed during converter blowing.
  • concentration of P in the steel wire rod exceeds 0.02%, the segregation of P causes more frequent occurrence of wire breakage and decrease in fatigue strength. Accordingly the concentration of P in the entire raw material has to be decreased to 0.02% or less before the converter blowing. It is preferred that this concentration be 0.015% or less.
  • the stirring gas flow rate (sometimes referred to hereinbelow simply as “gas flow rate”) during stirring of slag and molten steel also has to be adequately controlled during secondary refining (for example, ladle refining) after completion of converter blowing.
  • Molten steel after completion of converter blowing is deoxidized with Si or Mn, but in this process Al 2 O 3 is generated by a very small amount of Al contained in the alloy (deoxidizing agent) such as FeSi, FeMn, and SiMn, and harmful inclusions remain in the product. Accordingly, Al 2 O 3 has to be removed during secondary refining.
  • the gas flow rate is preferably 0.0006 Nm 3 /min or more, more preferably 0.0007 Nm 3 /min or more.
  • the gas flow rate has to be 0.004 Nm 3 /min or less, preferably 0.0035 Nm 3 /min or less, more preferably 0.003 Nm 3 /min or less.
  • the molten steel subjected to secondary refining is cast in a continuous casting machine.
  • the molten steel is transferred and temporarily accommodated in a container called “tundish”. If air remains in the space inside the tundish, then molten steel is oxidized by oxygen present in the air, thereby generating inclusions and increasing the breaking frequency of wire when a steel wire rod is produced. Accordingly, the inside of the tundish has to be purged during casting with Ar gas.
  • FIG. 4 shows the relationship between the purge Ar flow rate in the tundish (flow rate per 1 t of molten steel inside the tundish) and the number of wire breakages (per 1 t of molten steel).
  • the results clearly indicate that when the purge Ar flow rate is less than 0.04 Nm 3 /min, the oxidation of molten steel by oxygen contained in the air becomes significant and the number of wire breakages increases. Accordingly, the purge Ar flow rate has to be 0.04 Nm 3 /min or more. However, if the purge Ar flow rate per 1 t of molten steel exceeds 0.10 Nm 3 /min, the aforementioned effect tends to be saturated.
  • the steel material high-carbon steel
  • Al the amount of Al from amongst the steel components is limited as described hereinbelow, no special limitation is placed on other components and, as shown hereinabove, they are contained in the same amounts as in generally used steel for springs or steel materials for drawing such as steel cords. More specifically, the steel contains C, 0.4 to 1.3%, Si: 0.1 to 2.5%, Mn: 0.2 to 1.0%, and Al: 0.003% or less (excluding 0%). Reasons for setting such preferred ranges of components are described below.
  • C is an element useful for increasing the strength and is preferably contained at 0.4% or more to demonstrate this effect. Even more preferred content is 0.5% or more. However, if the content of C becomes too high, the steel is embrittled and loses its drawability. Therefore, it is preferred that the content of carbon be suppressed to 1.3% or less (more preferably, 1.2% or less).
  • Si is an element demonstrating a deoxidizing function.
  • the content of silicon be 0.1% or more, even more preferably 0.2% or more.
  • the content of Si is preferably suppressed to 2.5% or less (more preferably 2.3% or less).
  • Mn is an element that demonstrates a deoxidizing function, similarly to Si, and also has a function for controlling inclusion property. For this functions to be demonstrated effectively, it is preferred that the content of Mn be 0.2% or more (more preferably 0.3% or more). On the other hand, if the amount of Mn is too high, the steel is embrittled and loses its drawability. Therefore, it is preferred that the content of manganese be suppressed to 1.0% or less (more preferably, 0.9% or less).
  • the content of aluminum is preferably suppressed to a minimum. From this standpoint, it is preferred that the content of aluminum be suppressed to 0.003% or less (more preferably 0.002% or less).
  • the basic components of the steel material that is the object of the present invention are described above, the balance being iron and unavoidable impurities.
  • impurities the admixture of elements carried by raw materials, source materials, and production equipment can be allowed. Furthermore, properties can be further effectively improved by introducing the following elements.
  • Ni is an element making no significant contribution to the increase in strength of steel wire, but demonstrating an effect of increasing the toughness of drawn wire material.
  • the content of nickel be 0.01% or more, more preferably 0.02% or more.
  • the content of nickel be 1% or less (more preferably 0.9% or less).
  • Cu is an element making contribution to strengthening of steel wire due to precipitation hardening function thereof.
  • the contents of copper is preferably 0.01% or more, more preferably 0.02% or more.
  • the content of copper is preferably 1% or less (more preferably, 0.9% or less).
  • Cr increases a work hardening ratio during wire drawing and easily ensures a high strength even at a comparatively low processing ratio.
  • Cr also acts to increase the corrosion resistance of steel.
  • the content of Cr be 0.05% or more, more preferably 0.1% or more.
  • the content of Cr is preferably 1.5% or less, more preferably 1.4% or less.
  • the content be 0.02 ppm or more (more preferably 0.03 ppm or more), in the case of Mg the content be 0.02 ppm or more (more preferably 0.03 ppm or more), in the case of Ce the content be 3 ppm or more (more preferably 5 ppm or more), and in the case of La the content be 3 ppm or more (more preferably 5 ppm or more).
  • the amount of Li and Na may be restricted to 20 ppm or less (more preferably 10 ppm or less) each.
  • the amount of Ce and La may be restricted to 100 ppm or less (more preferably 80 ppm or less) each.
  • the steel material obtained by the manufacturing method in accordance with the present invention is thereafter hot rolled to obtain a steel wire rod.
  • the cross section diameter of the wire rod is 3 to 10 mm.
  • This steel wire rod is suitable as a workpiece for ultrafine high-strength steel wire such as a tire cord or a piano wire that is required to have high drawability, for example, in a cold drawing process. Further, the steel wire rod is also suitable as a workpiece for springs or wires that require good fatigue property.
  • Ar was used as a stirring gas for molten steel during ladle refining, and the flow rate of argon was changed within a range of 0.0002 to 0.0080 Nm 3 /min/t per 1 t of molten steel.
  • the gas stirring time was 15 min or more in all the cases.
  • a piece of 1000 g was cut from the obtained steel wire rod and used for inclusion extraction by acid dissolution and composition analysis of inclusions. Methods for the inclusion extraction and composition analysis (quantities) of inclusions are described below.
  • a beaker was prepared containing an acid solution in which pure water, nitric acid (concentration 60%), and sulfuric acid (concentration 96%) were mixed at a volume ratio of 5:25:1, respectively, and the steel wire rod (1000 g) was placed into the beaker.
  • the beaker was heated, and the wire rod was completely dissolved, while maintaining the solution temperature at 90 to 95° C.
  • filtration with a 10 ⁇ m filter was performed.
  • An EPMA Electron Probe Microanalyzer, manufactured by Japan Electron Optics Laboratory Co., Ltd. (JXA-8000 Series) was used for quantitative determination of inclusions, and quantitative analysis was conducted by characteristic X-ray energy dispersion spectroscopy under the conditions of accelerating voltage 20 kV and probe current 0.01 ⁇ A.
  • Elements that were the objects of the quantitative analysis included Al, Mn, Si, Mg, Ca, Ti, Zr, and O.
  • the method for quantitative determination included the steps of measuring X-ray intensity of a substance of already known concentration of these elements, plotting the relationship between the X-ray intensity and element concentration in advance as a calibration curve, and finding the concentration at which each element is present from the X-ray intensity of the inclusions that are the observation objects by using the calibration curve.
  • each element was assumed to be present in the form of Al 2 O 3 , MnO, SiO 2 , MgO, CaO, TiO 2 , ZrO 2 , the concentration at which the Al 2 O 3 , MnO, SiO 2 , MgO, CaO, TiO 2 , ZrO 2 were present in the inclusions was calculated based on the concentration of each element found by the above-described quantitative analysis, inclusions containing 80% or more of Al 2 O 3 were taken as alumina-based inclusions, and the long diameter and number thereof were measured.
  • An oxidation surface film on the steel wire rod with a diameter of 5.5 mm was removed with hydrochloric acid and then dry drawing was conducted to a diameter of 1.2 mm with a continuous drawing machine (model CD-610 ⁇ 7+BD610 manufactured by Showa Machine Works, Ltd.).
  • the diameter of drawing dies used in the drawing process was 4.8, 4.2, 3.7, 3.26, 2.85, 2.5, 2.2, 1.93, 1.69, 1.48, 1.3 (units: mm for all the dies).
  • the drawing speed in the die with a diameter of 1.2 mm was 400 m/min.
  • the wire rod surface was coated with zinc phosphate prior to drawing, and the drawing was preformed by using a lubricant based on sodium stearate.
  • the wire rod that was drawn to a diameter of 1.2 mm was heated to 1230 K, and subjected to patenting in a lead bath at 830 K to obtain a fine pearlitic structure, followed by plating with brass (film thickness: about 1.5 um) containing Cu and Zn at a 7:3 ratio (mass ratio). Finally, the wire rod was drawn to the diameter of 0.2 mm with a wet-type drawing machine (Type KPZIII/25-SPZ250, manufactured by Koch, Ernst & Co., Ltd.). In the dipping bath employed for wire drawing, a solution containing 75% water and prepared by mixing a natural fatty acid, an amino acid, and a surfactant was used.
  • the diameter of the dies used in the drawing process was 1.176, 0.959, 0.880, 0.806, 0.741, 0.680, 0.625, 0.574, 0.527, 0.484, 0.444, 0.408, 0.374, 0.343, 0.313, 0.287, 0.260, 0.237, and 0.216 (units: mm for all the dies).
  • the drawing speed at a diameter of 0.2 mm was 500 m/min.
  • Fatigue property in the case of applying the steel wire rod with a diameter of 8.0 mm that was obtained in the above-described manner to a spring was evaluated according to the following items.
  • a steel wire rod with a diameter of 8.0 mm was subjected sequentially to oil tempering, stress-relief annealing, shot peening, and secondary stress-relief annealing. Then, a fatigue test was performed under the following conditions by using a Nakamura-type rotating-bending fatigue machine and the fatigue property was evaluated by finding a wire breakage ratio.
  • Test piece length 650 mm
  • Wire breakage ratio (number of broken test pieces)/(total number of test pieces) ⁇ 100(%)
  • the concentration of P in the raw materials for a converter exceeded 0.02%. Therefore, excellent fatigue property could not be ensured.
  • the mixing ratio of raw materials, P concentration, and purge Ar flow rate in the tundish were within the ranges stipulated by the present invention, but the flow rate of the stirring gas for the molten steel in secondary refining was outside the range stipulated by the present invention. As a result, the fatigue property was degraded.
  • the mixing ratio of raw materials, P concentration, and flow rate of the stirring gas for the molten steel in secondary refining were within the ranges stipulated by the present invention, but the purge Ar flow rate in the tundish was outside the range stipulated by the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
US12/162,550 2006-03-30 2007-03-26 Process for producing steel for high-carbon steel wire material with excellent drawability and fatique characteristics Abandoned US20090038439A1 (en)

Applications Claiming Priority (3)

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JP2006095555 2006-03-30
JP2006-095555 2006-03-30
PCT/JP2007/056199 WO2007114100A1 (ja) 2006-03-30 2007-03-26 伸線性と疲労特性に優れた高炭素鋼線材用鋼の製造方法

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KR (1) KR101022068B1 (ko)
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