US20220145434A1 - Kiniz alloy having homogeneous microstructure - Google Patents

Kiniz alloy having homogeneous microstructure Download PDF

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US20220145434A1
US20220145434A1 US17/434,398 US202017434398A US2022145434A1 US 20220145434 A1 US20220145434 A1 US 20220145434A1 US 202017434398 A US202017434398 A US 202017434398A US 2022145434 A1 US2022145434 A1 US 2022145434A1
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alloy
kiniz
iron
copper
zirconium
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Pyeong Yeol Park
Jin Ho Kim
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Kiswire Ltd
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Kiswire Ltd
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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
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D46/00—Controlling, supervising, not restricted to casting covered by a single main group, e.g. for safety reasons
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • 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

Definitions

  • the present disclosure relates to a KINIZ alloy having a homogeneous microstructure, and more particularly, to a KINIZ alloy having a homogeneous microstructure which is obtained by adding small amounts of elements such as nickel (Ni), zirconium (Zr), or manganese (Mn) to an alloy including copper (Cu) and iron (Fe).
  • Cu—Fe alloys containing copper (Cu) and iron (Fe) are used in various industrial fields.
  • a Cu—Fe alloy may be produced through a casting process by melting copper (Cu) and iron (Fe) and then cooling the molten metals.
  • Cu—Fe alloys of the related art have the following problems.
  • FIG. 1 shows a Cu—Fe phase diagram.
  • a Cu—Fe alloy containing copper (Cu) and iron (Fe) is cast, since the enthalpy of mixing copper (Cu) with iron (Fe) is high, a metastable region in which the liquid phase of the Cu—Fe alloy is separated into two phases is present just below the solidus at which the Cu—Fe alloy starts to solidify into a dendritic microstructure.
  • the liquid phase of the molten Cu—Fe alloy is separated into two phases, and thus, a heterogeneous microstructure in which the two elements are separately present is formed.
  • a Cu—Fe alloy which has undergone phase separation has a heterogeneous microstructure in which iron (Fe) 20 and copper (Cu) 10 are separately present in the form of Fe droplets within a Cu matrix.
  • Such Cu—Fe alloys as the Cu—Fe alloy shown in FIG. 2 which has undergone phase separation are difficult to process because of non-uniform deformation. Also, a Cu—Fe alloy which has undergone phase separation has a problem in that the Cu—Fe alloy has relatively low conductivity in a local region in which iron (Fe) having relatively low conductivity is separately present, and has relatively low strength in a local region in which copper (Cu) having relatively low strength is separately present.
  • the present disclosure is provided to solve the above problems, and particularly relates to a KINIZ alloy having a homogeneous microstructure which is produced by adding small amounts of elements such as nickel (Ni), zirconium (Zr), or manganese (Mn) to an alloy including copper (Cu) and iron (Fe).
  • a KINIZ alloy having a homogeneous microstructure includes: copper (Cu) and iron (Fe) in a total amount of 75 wt % to 95 wt %; and nickel (Ni) in an amount of 1 wt % to 20 wt %, zirconium (Zr) in an amount of 0.1 wt % to 5.0 wt %, and a balance of inevitable impurities.
  • the KINIZ alloy having a homogeneous microstructure may include copper (Cu) in an amount of 20 wt % to 80 wt %, iron (Fe) in an amount of 20 wt % to 80 wt %, nickel (Ni) in an amount of 2.0 wt % to 5.0 wt %, and zirconium (Zr) in an amount of 0.3 wt % to 1.0 wt %.
  • the zirconium (Zr) may react with oxygen and form ZrO 2 , and the ZrO 2 may function as nuclei for nucleation of dendrites during a casting process of the KINIZ alloy.
  • a KINIZ alloy having a homogeneous microstructure includes: copper (Cu) and iron (Fe) in a total amount of 75 wt % to 95 wt %; and manganese (Mn) in an amount of 2.0 wt % to 5.0 wt %, zirconium (Zr) in an amount of 0.3 wt % to 1.0 wt %, and a balance (excluding 0%) of inevitable impurities.
  • the KINIZ alloy having a homogeneous microstructure may have a weight ratio of iron (Fe) to copper (Cu) and iron (Fe) within a range of 70% or more.
  • the KINIZ alloy having a mechanical switch may further include nickel (Ni) in an amount of 2.0 wt % to 5.0 wt %.
  • molten metals may be cooled at a rate of 5.3 ⁇ 10 4 ° C./sec or less.
  • KINIZ alloys are produced by adding small amounts of elements, such as nickel (Ni), zirconium (Zr), or manganese (Mn), to alloys including copper (Cu) and iron (Fe), and thus the KINIZ alloys may have a homogeneous microstructure without phase separation.
  • elements such as nickel (Ni), zirconium (Zr), or manganese (Mn)
  • Cu copper
  • Fe iron
  • FIG. 1 is a view illustrating a Cu—Fe phase diagram having a metastable region.
  • FIG. 2 is a view illustrating a cross-section of a Cu—Fe alloy which includes copper (Cu) and iron (Fe) and underwent phase separation.
  • FIG. 3 is a view illustrating the variation of a metastable region in a Cu—Fe phase diagram for different contents of nickel (Ni) according to an embodiment of the present disclosure.
  • FIGS. 4 and 5 are views illustrating the occurrence of phase separation in examples of the present disclosure and comparative examples.
  • FIG. 6 is a view illustrating the conductivity of a KINIZ alloy with respect to the content of nickel (Ni) according to an embodiment of the present disclosure.
  • FIG. 7 is a view illustrating the variation of a metastable region in a Cu—Fe phase diagram for different contents of manganese (Mn) according to an embodiment of the present disclosure.
  • FIG. 8 is a view illustrating the conductivity of a KINIZ alloy with respect to the content of manganese (Mn) according to an embodiment of the present disclosure.
  • FIG. 9 is a view illustrating a region in which microstructural phase separation was observed with respect to the cooling rate of molten metals according to an embodiment of the present disclosure.
  • FIG. 10 is a view illustrating a cross-section of a KINIZ alloy having a homogeneous microstructure according to an embodiment of the present disclosure.
  • the present disclosure relates to a KINIZ alloy having a homogeneous microstructure, and more particularly, to a KINIZ alloy having a homogeneous microstructure which is produced by adding small amounts of elements such as nickel (Ni), zirconium (Zr), or manganese (Mn) to an alloy including copper (Cu) and iron (Fe).
  • Ni nickel
  • Zr zirconium
  • Mn manganese
  • Cu copper
  • Fe iron
  • a KINIZ alloy having a homogeneous microstructure includes copper (Cu), iron (Fe), nickel (Ni), zirconium (Zr), and the balance of inevitable impurities.
  • the sum of the contents of copper (Cu) 110 and iron (Fe) 120 may be within the range of 75 wt % to 95 wt %, and the weight ratio of copper (Cu) 110 and iron (Fe) 120 may be varied according to the intended use of the alloy.
  • the content of copper (Cu) 110 may be within the range of 20 wt % to 80 wt %, and the content of iron (Fe) 120 may be within the range of 20 wt % to 80 wt %. More preferably, the content of copper (Cu) 110 may be within the range of 40 wt % to 60 wt %, and the content of iron (Fe) 120 may be within the range of 30 wt % to 50 wt %. In these ranges, the sum of the contents of copper (Cu) 110 and iron (Fe) 120 may be within the range of 75 wt % to 95 w %. However, the weight percentages of copper (Cu) 110 and iron (Fe) 120 are not limited thereto and may be varied as necessary.
  • the KINIZ alloy having a homogeneous microstructure of the embodiment of the present disclosure may include nickel (Ni) and zirconium (Zr) to solve the problem.
  • FIG. 3 shows a Cu—Fe phase diagram for different contents of nickel (Ni). Referring to FIG. 3 , it may be understood that a metastable region descends as the content of nickel (Ni) increases.
  • the metastable region descends, and thus the gap between the solidus and the metastable region increases, such that when the molten KINIZ alloy is cooled and solidified, molten metals may be prevented from being cooled across the metastable region.
  • the molten KINIZ alloy is cooled and solidified not across the metastable region, it is possible to prevent the liquid phase of the KINIZ alloy from separating into two phases, and thus the KINIZ alloy may be produced without phase separation to have a homogeneous microstructure.
  • the content of nickel (Ni) may be within the range of 1 wt % to 20 wt %, and more preferably within the range of 2 wt % to 5 wt %. As the content of nickel (Ni) increases, the metastable region descends, but the conductivity of the KINIZ alloy decreases. (Since the conductivity of copper (Cu) is higher than the conductivity of nickel (Ni), the conductivity of the KINIZ alloy decreases as the content of nickel (Ni) increases.)
  • the content of nickel (Ni) is preferably 20 wt % or less, and it is preferable that the content of nickel (Ni) be 5 wt % or less in terms of efficient prevention of a decrease in conductivity.
  • the content of nickel (Ni) is 1 wt % or less, the effect of lowering the metastable region is insufficient, and thus it is preferable that the content of nickel (Ni) be 1 wt % or more.
  • the content of nickel (Ni) is within the range of 2 wt % to 5 wt %.
  • FIGS. 4 and 5 are views showing the occurrence of phase separation according to the content of nickel (Ni). Referring to FIGS. 4 and 5 , when the content of nickel (Ni) is 2 wt % or less, phase separation may occur, and when the content of nickel (Ni) is greater than 2 wt %, phase separation does not occur. Therefore, it is preferable that the content of nickel (Ni) be greater than 2 wt %.
  • the KINIZ alloy having a homogeneous microstructure utilizes the merit of copper (Cu), that is, electrical conductivity, and it is preferable that the electrical conductivity of the KINIZ alloy be 40% IACS or higher for utilizing electrical conductivity.
  • Cu copper
  • Ni nickel
  • the resistivity of the KINIZ alloy may increase, and thus the electrical conductivity of the KINIZ alloy may decrease.
  • the content of nickel (Ni) when the content of nickel (Ni) is greater than 5 wt %, the conductivity of the KINIZ alloy decreases to 40% IACS, and as the content of nickel (Ni) becomes greater than 5 wt %, the conductivity of the KINIZ alloy decreases steeply. Therefore, it is preferable that the content of nickel (Ni) be less than 5 wt %.
  • nickel (Ni) is added to the KINIZ alloy having a homogeneous microstructure within the range of the minimum amount (2 wt %) for suppressing phase separation to an amount (5 wt %) not causing a significant decrease in conductivity.
  • the KINIZ alloy having a homogeneous microstructure according to the embodiment of the present disclosure may include zirconium (Zr) for the effect of rapid solidification of a dendritic structure.
  • zirconium (Zr) included in the KINIZ alloy may react with oxygen and form ZrO 2 , and the ZrO 2 may function as nucleation nuclei forming dendrites when the KINIZ alloy is cast.
  • Zirconium (Zr) functioning as described above has an effect of quickening the solidification of a dendritic structure, and thus, it is possible to solidify the molten KINIZ alloy before phase separation occurs in the liquid phase of the molten KINIZ alloy.
  • nickel (Ni) prevents phase separation by descending the metastable region, and along with this, zirconium (Zr) quickens the solidification of a dendritic structure, thereby preventing the KINIZ alloy from solidifying across the metastable region from a molten state.
  • the content of zirconium (Zr) may be from 0.1 wt % to 5 wt %, and more preferably from 0.3 wt % to 1.0 wt %.
  • the content of zirconium (Zr) is preferably 5 wt % or less, and it is preferable that the content of zirconium (Zr) be 1 wt % or less in terms of efficient prevention of a decrease in conductivity.
  • the content of zirconium (Zr) is 0.1 wt % or less, the effect of quickening the solidification of a dendritic structure is insufficient, and thus it is preferable that the content of zirconium (Zr) be 0.1 wt % or more.
  • the content of zirconium (Zr) is preferably 0.3 wt % to 1.0 wt %.
  • the content of zirconium (Zr) may be varied depending on the metastable region lowered by nickel (Ni), but when the solidification of a dendritic structure occurs slows due to a low zirconium (Zr) content, there is a risk that molten metals solidify across the metastable region.
  • the content of zirconium (Zr) is less than 0.3 wt %, the effect of suppressing phase separation may not be obtained because of insufficient formation of the ZrO 2 . Therefore, to prevent this, the content of zirconium (Zr) is preferably 0.3 wt % or more.
  • the content of zirconium (Zr) is 1.0 wt % or less.
  • the content of zirconium (Zr) is greater than 1.0 wt %, the size of ZrO 2 increases, and thus, ZrO 2 may act as an inclusion rather than acting as nucleation nuclei and may thus have an adverse effect on conductivity. Therefore, it is preferable that the content of zirconium (Zr) be 1.0 wt % or less.
  • the KINIZ alloy having a homogeneous microstructure of the embodiment of the present disclosure may include carbon (C) in addition to copper (Cu), iron (Fe), nickel (Ni), and zirconium (Zr), and in this case, the content of carbon (C) may be 0.02 wt % or less (excluding 0%).
  • the KINIZ alloy having a homogeneous microstructure may include the balance of inevitable impurities in addition to copper (Cu), iron (Fe), nickel (Ni), and zirconium (Zr), and the inevitable impurities may include various elements required for the KINIZ alloy.
  • the inevitable impurities may include chromium (Cr), magnesium (Mg), aluminum (Al), silicon (Si), or the like.
  • a KINIZ alloy having a homogeneous microstructure includes copper (Cu), iron (Fe), nickel (Ni), zirconium (Zr), and the balance of inevitable impurities.
  • the sum of the contents of copper (Cu) 110 and iron (Fe) 120 may be within the range of 75 wt % to 95 wt %, and the weight ratio of copper (Cu) 110 and iron (Fe) 110 may be varied according to the intended use of the KINIZ alloy.
  • the content of copper (Cu) 110 may be within the range of 20 wt % to 80 wt %, and the content of iron (Fe) 120 may be within the range of 20 wt % to 80 wt %. More preferably, the content of copper (Cu) 110 may be within the range of 40 wt % to 60 wt % %, and the content of iron (Fe) 120 may be within the range of 30 wt % to 50 wt %. In these ranges, the sum of the contents of copper (Cu) 110 and iron (Fe) 120 may be within the range of 75 wt % to 95 w %. However, the weight percentages of copper (Cu) 110 and iron (Fe) 120 are not limited thereto and may be varied as necessary.
  • the KINIZ alloy having a homogeneous microstructure may include manganese (Mn) and zirconium (Zr) to solve the problem.
  • FIG. 7 shows a Cu—Fe phase diagram for different contents of manganese (Mn). Referring to FIG. 7 , as the content of manganese (Mn) increases, the metastable region descends.
  • the metastable region descends, and thus the gap between the solidus and the metastable region increases, such that when the molten KINIZ alloy is cooled and solidified, the molten KINIZ alloy may be prevented from being cooled across the metastable region.
  • the molten KINIZ alloy is cooled and solidified not across the metastable region, it is possible to prevent the liquid phase of the KINIZ alloy from separating into two phases, and thus the KINIZ alloy may be produced without phase separation to have a homogeneous microstructure.
  • the ratio of the weight of iron (Fe) to the sum of the weights of copper (Cu) and iron (Fe) is preferably 70% or more.
  • the metastable region descends as the content of manganese (Mn) increases.
  • the ratio of the weight of iron (Fe) to the sum of the weights of copper (Cu) and iron (Fe) is preferably set to be 70% or more.
  • the content of manganese (Mn) may be from 2 wt % to 5 wt %. As the content of manganese (Mn) increases, the metastable region descends, but the conductivity of the KINIZ alloy decreases. (Since the conductivity of copper (Cu) is higher than the conductivity of manganese (Mn), the conductivity of the KINIZ alloy decreases as the content of manganese (Mn) increases.)
  • the content of manganese (Mn) when the content of manganese (Mn) is 2 wt % or less, the effect of lowering the metastable region is insufficient, and thus it is preferable that the content of manganese (Mn) is 2 wt % or more.
  • the content of manganese (Mn) becomes greater than 5 wt %, the conductivity (% IACS) of the KINIZ alloy rapidly decreases. Therefore, it is preferable that the content of manganese (Mn) be less than 5 wt % for the prevention of a decrease in conductivity (% IACS).
  • the KINIZ alloy having a homogeneous microstructure of the other embodiment of the present disclosure may include zirconium (Zr) for the effect of rapid solidification of a dendritic structure.
  • Zirconium (Zr) may be included within the range of 0.3 wt % to 1.0 wt %, and descriptions of the reason for adding zirconium (Zr) and the weight content of zirconium (Zr) are not provided here because the same descriptions are given in the above description of the KINIZ alloy including nickel (Ni).
  • the KINIZ alloy having a homogeneous microstructure according to the other embodiment of the present disclosure may further include nickel (Ni).
  • nickel (Ni) When nickel (Ni) is included, the metastable region may be lowered as described above, and to this end, nickel (Ni) may be included in a range of 2.0 wt % to 5.0 wt %. Descriptions of the reason for adding nickel (Ni) and the weight content of nickel (Ni) are not provided here because the same descriptions are given in the above description of the KINIZ alloy including nickel (Ni).
  • the KINIZ alloy having a homogeneous microstructure according to the other embodiment of the present disclosure may include carbon (C) in addition to copper (Cu), iron (Fe), manganese (Mn), and zirconium (Zr), and in this case, the content of carbon (C) may be 0.02 wt % or less (excluding 0%).
  • the KINIZ alloy having a homogeneous microstructure of the other embodiment of the present disclosure may include the balance of inevitable impurities in addition to copper (Cu), iron (Fe), manganese (Mn), and zirconium (Zr), and the inevitable impurities may include various elements required for the KINIZ alloy.
  • the inevitable impurities may include chromium (Cr), magnesium (Mg), aluminum (Al), silicon (Si), or the like.
  • a KINIZ alloy having a homogeneous microstructure may be cast while melting elements included in the KINIZ alloy and cooling the elements.
  • the cooling rate of molten metals is preferably 5.3 ⁇ 10 4 ° C./sec or less.
  • the metastable region is lowered by using nickel (Ni) and manganese (Mn) and the solidification of the KINIZ alloy is quickened by using zirconium (Zr) as described above, the solidification of the KINIZ alloy may occur across the metastable region when the solidification rate of the KINIZ alloy is excessively high.
  • the cooling rate of molten metals decreases below 5.3 ⁇ 10 4 ° C./sec.
  • the region in which phase separation is observed decreases.
  • the cooling rate is high, molten metals may solidify across the metastable region and thus undergo phase separation.
  • the cooling rate decreases below 5.3 ⁇ 10 4 ° C./sec, the phase separation region gradually decreases. Therefore, when the KINIZ alloy of the embodiment of the present disclosure is cast, it is preferable that the cooling rate of molten metals be 5.3 ⁇ 10 4 ° C./sec or less.
  • the KINIZ alloys having a homogeneous microstructure according to the above-described embodiments of the present disclosure may have the following effects.
  • the KINIZ alloys of the embodiments of the present disclosure are produced by adding small amounts of elements such as nickel (Ni), zirconium (Zr), or manganese (Mn), the KINIZ alloys may have a homogeneous microstructure without phase separation.
  • the metastable region may be lowered by the addition of nickel (Ni) and manganese (Mn), and the dendritic solidification may be quickened by the addition of zirconium (Zr).
  • Ni nickel
  • Mn manganese
  • Zr zirconium
  • FIG. 2 is a view illustrating a cross-section of a conventional Cu—Fe alloy which includes copper (Cu) and iron (Fe) and underwent phase separation
  • FIG. 10 is a view illustrating a cross-section of a KINIZ alloy having a homogeneous microstructure according to an embodiment of the present disclosure.
  • the KINIZ alloy of the embodiment of the present disclosure is produced by adding small amounts of elements such as nickel (Ni), zirconium (Zr), or manganese (Mn), the KINIZ alloy does not has a heterogeneous microstructure in which iron (Fe) 20 and copper (Cu) 10 are separately present in the form of Fe droplets in a Cu matrix, but has a homogeneous microstructure in which Fe dendrites 120 are uniformly distributed in copper (Cu) 110 .

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PCT/KR2020/004335 WO2020251145A1 (ko) 2019-06-11 2020-03-30 균질한 미세조직을 가지는 키니즈 합금

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