WO2019132412A1 - Zinc alloy-plated steel having excellent corrosion resistance and surface smoothness, and manufacturing method therefor - Google Patents

Zinc alloy-plated steel having excellent corrosion resistance and surface smoothness, and manufacturing method therefor Download PDF

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Publication number
WO2019132412A1
WO2019132412A1 PCT/KR2018/016325 KR2018016325W WO2019132412A1 WO 2019132412 A1 WO2019132412 A1 WO 2019132412A1 KR 2018016325 W KR2018016325 W KR 2018016325W WO 2019132412 A1 WO2019132412 A1 WO 2019132412A1
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Prior art keywords
phase
corrosion resistance
surface smoothness
alloy
plated steel
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PCT/KR2018/016325
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French (fr)
Korean (ko)
Inventor
김흥윤
김명수
Original Assignee
주식회사 포스코
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Priority claimed from KR1020180165575A external-priority patent/KR102235255B1/en
Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to JP2020535239A priority Critical patent/JP7060693B2/en
Priority to US16/956,743 priority patent/US11572607B2/en
Priority to CN201880084153.5A priority patent/CN111527231B/en
Priority to EP18895346.7A priority patent/EP3733920A4/en
Publication of WO2019132412A1 publication Critical patent/WO2019132412A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment

Definitions

  • the present invention relates to a plated steel material used for automobiles, household appliances, building materials, and the like, and more particularly to a plated steel material excellent in corrosion resistance and surface smoothness, and a method of manufacturing the same.
  • Iron is one of the most widely used materials in the industry and has excellent physical and mechanical properties, but it is easily oxidized and degraded in physical and mechanical properties. For this reason, research has been conducted on techniques for preventing oxidation of iron for a long time.
  • One way to prevent oxidation of iron is to coat the surface of the material with a protective film of a metal that is more reactive than oxygen than iron to oxidize the protective film before the iron to form a passive state to delay the corrosion.
  • a galvanized steel sheet having a coating film formed thereon.
  • the zinc-plated steel is used for automobiles, household appliances, and architectural applications due to its simple manufacturing process and low manufacturing cost.
  • zinc is exposed to a part of iron, zinc having a higher oxidation potential dissolves first to protect the iron by a sacrificial action, and the corrosion product of zinc is formed densely to suppress the corrosion.
  • Patent Document 1 proposed by improving the corrosion resistance
  • Patent Document 2 proposed by improving the corrosion resistance of the processed portion are available.
  • the surface smoothness has an important value when exposed to the outside or when the added value is increased by the surface appearance.
  • the surface smoothness of the plated steel is deteriorated by various causes such as defects occurring in the manufacturing process or natural phenomenon of the solidification process.
  • the surface smoothness of the plated steel influences the products of the subsequent process. That is, if the surface smoothness of the plated steel is poor, unevenness can be formed in the painted or laminated product.
  • Patent Document 3 has a problem that the problem of surface smoothness due to the hairline generated by the oxidation of Mg is adjusted by the composition of the plating bath component and the oxygen concentration but the addition of components or a separate facility is required and thus the cost is increased and the process is complicated have.
  • Patent Document 4 discloses a method in which an Al intermetallic compound is formed on a plating surface to improve surface smoothness, a dross is formed due to the addition of various elements for forming an intermetallic compound, and metal sulfide acts as concavo- There is a problem of inhibiting smoothness.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 1998-226865
  • Patent Document 2 Korean Patent Laid-Open No. 10-2016-0078918
  • Patent Document 3 Korean Patent Registration No. 10-1560934
  • Patent Document 4 Korean Patent Registration No. 10-0728893
  • An aspect of the present invention is to provide an alloyed gold-plated steel material having excellent surface smoothness while securing excellent corrosion resistance by optimizing the composition and microstructure of the plating layer, and a method of manufacturing the same.
  • One embodiment of the present invention includes a base steel and a zinc alloy plating layer formed on the base steel,
  • the zinc alloy plating layer contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities,
  • the zinc alloy plating layer may be formed of Al solid phase, Zn solid phase, MgZn 2 An alloy phase, an Mg 2 Zn 11 alloy phase, and an Al-Mg-Zn phase,
  • the MgZn 2 wherein at least one of the alloy phase and the Mg 2 Zn 11 alloy phase contains 20 to 50% by area fraction,
  • the total amount of the Al solid phase and the Al-Mg-Zn phase is about 80% or less in terms of an area fraction and is excellent in corrosion resistance and surface smoothness.
  • Another aspect of the present invention provides a method of manufacturing a semiconductor device
  • the present invention also relates to a method of manufacturing a steel plate having excellent corrosion resistance and surface smoothness.
  • the sub-alloy gold-plated steel of the present invention comprises a base iron and a zinc alloy plating layer formed on the base iron.
  • the kind of the ground iron is not particularly limited, and it is sufficient that the ground iron which can be applied in the technical field to which the present invention belongs is sufficient.
  • the zinc alloy plating layer is based on zinc (Zn) and contains Mg and Al.
  • the zinc alloy plating layer preferably contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities in weight percent.
  • 0.0005 to 0.009% of at least one of Sr, Be, Ca and Li may be added.
  • the above Al serves as a corrosion barrier to stabilize the Mg component and inhibit the early corrosion in a corrosive environment when the molten metal of the plating bath is produced.
  • the Al content may vary depending on the Mg content. If the Al content is less than 10%, Mg can not be stabilized in the production of the molten bath of the plating bath, and Mg oxide is generated on the surface of the molten metal, making it difficult to use. On the other hand, if it exceeds 25%, it is not preferable because the plating temperature rises and the solubility of various facilities provided in the plating bath severely occurs.
  • Mg is less than 5%, the corrosion resistance is not sufficiently exhibited. If Mg is more than 20%, Mg oxide of the plating bath is formed in a large amount, and secondary deterioration of materials It may cause various problems such as an increase in cost, etc. Therefore, it is preferable that the Mg contains 5 to 20%.
  • it may further contain strontium (Sr), beryllium (Be), calcium (Ca), lithium (Li), and the like in addition to 0.0005 to 0.009% . If it is less than 0.0005%, it is difficult to expect a substantial Mg stabilizing effect. If it exceeds 0.009%, it may solidify at the end of plating to cause corrosion first, which may hinder corrosion resistance and increase the cost.
  • the balance includes zinc (Zn) and unavoidable impurities.
  • Zn zinc
  • unavoidable impurities unavoidable impurities.
  • the zinc alloy plating layer of the present invention may include MgZn 2 alloy phase, Mg 2 Zn 11 alloy phase, Al solid phase, Zn solid phase, Al-Zn-Mg phase, and the like.
  • the above-mentioned solid phase refers to a phase in which other components are solidified, but also includes a single phase which is not solid phase.
  • the zinc alloy plating layer of the present invention can be produced as a MgZn 2 alloy phase or an Al solid phase as a primary phase. Subsequently, the remaining MgZn 2 alloy phase, Mg 2 Zn 11 alloy phase, Al solid phase, Zn solid phase, and Al-Zn-Mg phase can be formed.
  • the crystal phase is MgZn 2 alloy phase
  • the Al solid phase, Mg 2 Zn 11 alloy phase, Zn solid phase and Al-Zn-Mg phase are generated in succession, and MgZn 2 alloy phase, Al solution phase, Mg 2 Zn 11 alloy phase, Zn solution phase and Al-Zn-Mg phase are produced.
  • the phases may be generated in a substantially non-equilibrium state.
  • the zinc alloy plating layer preferably contains 20 to 50% of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase in an area fraction, and the Al solid phase and the Al-Zn-Mg phase fraction are 80% or less desirable. It is preferable that the remainder is a Zn employment phase.
  • the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase substantially exhibit corrosion resistance. If it is less than 20%, the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase are not sufficient to ensure excellent corrosion resistance in a constant water and salt water environment. increases, but then the MgZn 2 phase alloy and Mg 2 Zn 11 alloy different light, the higher the possibility that the crack of the coating layer occur.
  • the Al process phase forms an initial corrosion barrier, and corrosion resistance is exhibited in the Al-Zn-Mg process phase, which is presumed to be formed at the end of solidification, but the effect is not significant. Therefore, it is preferable that the sum of the Al solid phase and the Al-Zn-Mg phase does not exceed 80%.
  • the corrosion resistance may be lowered due to the reduction of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase.
  • the Al solid phase and Al-Zn-Mg phase may not be produced due to compositional or non-equilibrium state solidification.
  • the method for producing the sub-alloy gold-plated steel of the present invention is prepared by preparing a base steel, providing a favorable shape of nucleation on the prepared base steel surface, immersing it in a plating bath, and then performing wiping and cooling. Each process will be described below.
  • the base steel is prepared, and the surface of the prepared base steel is given a favorable shape for nucleation.
  • a surface favorable for nucleation is imparted to the surface of the plated steel before plating.
  • solidification nuclei are formed, which are thermodynamically formed at the lowest Gibbs free energy. Gibbs free energy due to solidification is advantageous when heterogeneous nucleation is generated rather than homogeneous nucleation. The larger the area of heterogeneous nucleation sites, the more nuclei are produced and the more nuclei are produced. Thus, the number of nucleations can be adjusted by controlling the nonuniform nucleation sites.
  • the present invention it is necessary for the present invention to impart a favorable shape to nucleation on the surface of the base iron, which can be expressed by the degree of strain (Rsk). If Rsk is less than 0, the valley is dominant and if Rsk is greater than 0, the peak becomes the dominant surface.
  • the alloy gold-plated steel of the present invention is adjusted so that the surface roughness (Rsk) of the base iron is -0.2 to -1.2.
  • the Rsk (Roughness skewness) is one of the roughness parameters and is a characteristic value indicating the direction and degree of asymmetry of the profile with respect to the average line, and can be confirmed by using an apparatus for measuring roughness.
  • the mold having a surface roughness (Rsk) of -0.2 to -1.2 has a deep valley of roughness and a flat peak structure.
  • the direct molding method is to produce the above-described shape directly on the surface of the material.
  • dissolution using an acid may be mentioned.
  • Indirect molding is typically performed by applying pressure to a steel material using a rough rolling roll. The roughness of the temper rolling roll can be adjusted by grinding the peak, then grinding the peak or making the valley flat from the beginning.
  • the substrate iron is immersed in a plating bath to form a zinc alloy plating layer on the substrate iron surface.
  • the plating bath composition preferably contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities, and further contains at least one of Sr, Be, Ca and Li in an amount of 0.0005 To 0.009%.
  • the plating bath alloy composition range is not different from that described above for the alloy composition range of the zinc alloy plating layer.
  • the temperature of the plating bath varies depending on the melting point, and the melting point is a physicochemical characteristic depending on the composition of the plating bath.
  • the factors that determine the temperature of the plating bath between the substrates are various, such as ease of operation, heating cost, and plating quality. Taking these points into consideration, the temperature of the plating bath is higher than the melting point, preferably 20 to 100 ° C higher than the melting point
  • the base iron deposited in the plating bath is set in consideration of convenience of work, heat balance, and the like.
  • the plating bath temperature is preferably -10 to + 10 ° C.
  • the distortion Rsk is controlled in such a manner that the roughness of the surface of the steel sheet is given. Specifically, the roughness is applied to the roll, the steel sheet is passed through the roll, and the roughness is transferred to the steel sheet Respectively.
  • the above-mentioned distortion Rsk was controlled by changing the shapes and shapes of the valleys and peaks of the roughness when the roughness was given to the rolls.
  • the prepared test piece was immersed in a plating bath to prepare an alloyed gold-plated steel having the plating layer composition shown in Table 1. Since the temperature of the plating bath varies depending on the melting point of the plating composition, the temperature is set in the range of 480 to 570 ° C, and the immersion temperature of the steel sheet is 10 ° C higher than the plating bath temperature. After the immersion, the surface of the galvanized gold-plated steel material raised from the plating bath was gas-wiped to adjust the plating adhesion amount to 70 g / m < 3 > on one side and cooled to room temperature at an average cooling rate of 10 DEG C / s.
  • the gold-plated steel specimens were identified by energy dispersive X-ray spectroscopy (EDS) analysis and X-ray diffraction (XRD) analysis was used to determine the phase fraction. The results are also shown in Table 1.
  • the corrosion resistance is represented by the corrosion resistance index by non-dimensioning the salt spray test divided by the amount of deposition of red rust.
  • the salt spray test tank was sprayed with a salinity of 5%, a temperature of 35 ⁇ , a pH of 6.8, and a sprayed amount of salt water of 2 ml / 80 cm < 2 >
  • the surface cracks were bent 180 degrees, and the plating layer on the outer side was observed with an SEM to confirm the occurrence of cracks.
  • the depth of coagulation shrinkage was used to confirm the surface smoothness. The depth of coagulation shrinkage was measured in three dimensions and evaluated according to the following criteria.
  • the inventive example satisfying the conditions of the present invention has excellent corrosion resistance, no surface cracking, and excellent surface smoothness.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The present invention relates to a plated steel to be used for automobiles, electric home appliances, building materials and the like and, more specifically, to a zinc alloy-plated steel having excellent corrosion resistance and surface smoothness, and a method for manufacturing the same.

Description

내식성 및 표면 평활성이 우수한 아연합금도금강재 및 그 제조방법Au alloyed gold-plated steel with excellent corrosion resistance and surface smoothness and its manufacturing method
본 발명은 자동차, 가전, 건축자재 등에 사용되는 도금강재에 관한 것으로서, 보다 상세하게는 내식성 및 표면 평활성이 우수한 아연합금도금강재와 이를 제조하는 방법에 관한 것이다.The present invention relates to a plated steel material used for automobiles, household appliances, building materials, and the like, and more particularly to a plated steel material excellent in corrosion resistance and surface smoothness, and a method of manufacturing the same.
철은 산업에서 가장 많이 사용되는 소재 중 하나로, 뛰어난 물리적, 기계적인 특성을 가지고 있지만, 쉽게 산화되어 물리적, 기계적 특성이 저하되는 문제가 있다. 이 때문에 오래전부터 철의 산화를 방지하는 기술에 대한 연구가 되어 왔다. 철의 산화를 방지하는 방법 중 하나는 철보다 산소와 반응성이 높은 금속을 보호막으로 소재 표면에 코팅함으로써 보호막이 철보다 먼저 산화되어 부동태를 형성하여 부식을 지연시키는 방법으로, 대표적으로 아연 또는 아연계 피막을 형성한 아연도금강재를 제조하는 것이다.Iron is one of the most widely used materials in the industry and has excellent physical and mechanical properties, but it is easily oxidized and degraded in physical and mechanical properties. For this reason, research has been conducted on techniques for preventing oxidation of iron for a long time. One way to prevent oxidation of iron is to coat the surface of the material with a protective film of a metal that is more reactive than oxygen than iron to oxidize the protective film before the iron to form a passive state to delay the corrosion. Typically, To produce a galvanized steel sheet having a coating film formed thereon.
상기 아연도금강재, 특히 용융 아연도금강재는 제조공정이 단순하고, 저렴한 제조원가로 인해, 자동차, 가전, 건축용 등으로 많이 사용되고 있다. 아연은 철의 일부가 노출된 경우 산화전위가 더 높은 아연이 먼저 용해해서 희생방식작용으로 철을 보호하고, 아연의 부식생성물이 치밀하게 형성하여 부식을 억제하는 작용을 한다. The zinc-plated steel, especially hot-dip galvanized steel, is used for automobiles, household appliances, and architectural applications due to its simple manufacturing process and low manufacturing cost. When zinc is exposed to a part of iron, zinc having a higher oxidation potential dissolves first to protect the iron by a sacrificial action, and the corrosion product of zinc is formed densely to suppress the corrosion.
최근 부식 환경이 날로 악화되고, 자원 및 에너지 절약 차원에서 고도한 내식성 향상에 많은 노력을 기울이고 있다. 최근 들어 이러한 노력의 성과로서 Mg를 첨가하여 내식성을 대폭 향상시키는 성과를 얻고 있다. 대표적으로 아연을 기본성분으로 하는 Zn-Al 조성에 Mg을 추가한 Zn-Al-Mg 아연합금도금강재에 관한 연구가 진행되고 있다. 예를 들어, 내식성을 개선하여 제안된 특허문헌 1, 가공부 내식성을 개선하여 제안하는 특허문헌 2 등이 있다.Recently, the corrosive environment has become worse day by day, and efforts have been made to improve corrosion resistance in terms of resource and energy saving. In recent years, as a result of these efforts, Mg has been added to improve the corrosion resistance remarkably. Studies on Zn-Al-Mg alloyed gold-plated steel with Mg added to the Zn-Al composition with zinc as a basic component are being studied. For example, Patent Document 1 proposed by improving the corrosion resistance and Patent Document 2 proposed by improving the corrosion resistance of the processed portion are available.
그러나 위와 같은 아연합금도금강재의 경우에도 상시 수분 접촉이 우려되거나 염수 환경 등 열역한 환경에서는 내식성의 한계가 있어, 보다 우수한 내식성이 요구되고 있는 실정이다. However, even in the case of the above-mentioned alloyed gold-plated steel, there is a concern about constant water contact or corrosion resistance in a hot environment such as a salt water environment, and therefore, excellent corrosion resistance is required.
한편, 도금강재의 외관으로서, 표면 평활성은 외측에 노출되거나 표면외관에 의해 부가가치가 상승되는 경우에는 중요한 가치를 가진다. 도금강재는 제조과정에서 발생하는 결함 또는 응고 과정의 자연적인 현상 등 다양한 원인에 의해 표면 평활성이 열화된다. 도금강재의 표면 평활성은 후속 공정의 제품까지 영향을 미친다. 즉, 도금강재의 표면 평활성이 불량하면 도장 또는 라미네이션 제품에 요철을 형성시킬 수 있다.On the other hand, as the appearance of the plated steel, the surface smoothness has an important value when exposed to the outside or when the added value is increased by the surface appearance. The surface smoothness of the plated steel is deteriorated by various causes such as defects occurring in the manufacturing process or natural phenomenon of the solidification process. The surface smoothness of the plated steel influences the products of the subsequent process. That is, if the surface smoothness of the plated steel is poor, unevenness can be formed in the painted or laminated product.
특허문헌 3은 Mg의 산화로 생성되는 헤어라인에 의한 표면 평활성의 문제를 도금욕 성분조성과 산소 농도로 조정하지만, 별도의 성분 첨가나 별도 설비가 요구되므로 비용이 높아지고, 공정이 복잡해지는 문제가 있다. 특허문헌 4는 Al계 금속간화합물을 도금 표면에 구성되도록 하여 표면 평활성을 개선하고자 하는 것이나, 금속간화합물 형성을 위한 다양한 원소 첨가로 인한 드로스가 형성되고 금속간 화화물이 요철로 작용하여 오히려 표면 평활성을 저해하는 문제가 있다.Patent Document 3 has a problem that the problem of surface smoothness due to the hairline generated by the oxidation of Mg is adjusted by the composition of the plating bath component and the oxygen concentration but the addition of components or a separate facility is required and thus the cost is increased and the process is complicated have. Patent Document 4 discloses a method in which an Al intermetallic compound is formed on a plating surface to improve surface smoothness, a dross is formed due to the addition of various elements for forming an intermetallic compound, and metal sulfide acts as concavo- There is a problem of inhibiting smoothness.
(특허문헌 1) 일본 공개특허공보 제1998-226865호(Patent Document 1) Japanese Laid-Open Patent Publication No. 1998-226865
(특허문헌 2) 한국 공개특허공보 제10-2016-0078918호(Patent Document 2) Korean Patent Laid-Open No. 10-2016-0078918
(특허문헌 3) 한국 등록특허공보 제10-1560934호(Patent Document 3) Korean Patent Registration No. 10-1560934
(특허문헌 4) 한국 등록특허공보 제10-0728893호(Patent Document 4) Korean Patent Registration No. 10-0728893
본 발명의 일측면은 도금층의 조성 및 미세조직을 최적화하여, 우수한 내식성을 확보하는 동시에, 표면 평활성이 우수한 아연합금도금강재와 이를 제조하는 방법을 제공하고자 하는 것이다. An aspect of the present invention is to provide an alloyed gold-plated steel material having excellent surface smoothness while securing excellent corrosion resistance by optimizing the composition and microstructure of the plating layer, and a method of manufacturing the same.
본 발명의 과제는 상술한 사항에 한정되지 아니한다. 본 발명의 추가적인 과제는 명세서 전반적인 내용에 기술되어 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 명세서에 기재된 내용으로부터 본 발명의 추가적인 과제를 이해하는데 아무런 어려움이 없을 것이다.The object of the present invention is not limited to the above-mentioned matters. Additional objects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
본 발명의 일태양은 소지철 및 상기 소지철 상에 형성된 아연합금도금층을 포함하고,One embodiment of the present invention includes a base steel and a zinc alloy plating layer formed on the base steel,
상기 아연합금도금층은 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하고,Wherein the zinc alloy plating layer contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities,
상기 아연합금도금층은 Al 고용상, Zn 고용상, MgZn2 합금상, Mg2Zn11 합금상, 및 Al-Mg-Zn 공정상 중 하나 이상을 포함하고, The zinc alloy plating layer may be formed of Al solid phase, Zn solid phase, MgZn 2 An alloy phase, an Mg 2 Zn 11 alloy phase, and an Al-Mg-Zn phase,
상기 MgZn2 합금상 및 Mg2Zn11 합금상 중 하나 이상이 면적분율로 20~50% 포함하고, The MgZn 2 Wherein at least one of the alloy phase and the Mg 2 Zn 11 alloy phase contains 20 to 50% by area fraction,
상기 Al 고용상 및 Al-Mg-Zn 공정상의 합량은 면적분율로 80% 이하인 내식성 및 표면 평활성이 우수한 아연합금도금강재에 관한 것이다.The total amount of the Al solid phase and the Al-Mg-Zn phase is about 80% or less in terms of an area fraction and is excellent in corrosion resistance and surface smoothness.
본 발명의 또다른 일태양은 소지철을 준비하는 단계;Another aspect of the present invention provides a method of manufacturing a semiconductor device,
상기 준비된 소지철의 표면 왜도(Rsk)가 -0.2 ~ -1.2이 되도록 조절하는 단계;Adjusting the surface roughness (Rsk) of the prepared ferrous iron to be -0.2 to -1.2;
상기 소지철을 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하는 도금욕에 침지하여 도금하는 단계;Immersing the substrate iron in a plating bath containing 10 to 25% of Al, 5 to 20% of Mg, and the balance of Zn and unavoidable impurities in terms of% by weight;
상기 도금된 소지철을 와이핑하고 냉각하는 단계를 포함하는 내식성 및 표면 평활성이 우수한 아연합금도금강재의 제조방법에 관한 것이다.And wiping and cooling the plated tin-plated steel. The present invention also relates to a method of manufacturing a steel plate having excellent corrosion resistance and surface smoothness.
본 발명에 의하면, 우수한 내식성 및 표면 평활성을 갖는 Zn-Al-Mg계 아연합금도금강재와 이를 제조하는 방법을 제공할 수 있고, 우수한 내식성과 표면 평활성을 가지므로, 기존의 도금강재가 적용되지 못한 새로운 분야의 확대 적용이 가능하다는 장점이 있다.According to the present invention, it is possible to provide a Zn-Al-Mg-based alloyed gold-plated steel having excellent corrosion resistance and surface smoothness and a method of manufacturing the same, and has excellent corrosion resistance and surface smoothness, It has the advantage of expanding the application of new fields.
이하, 본 발명에 대해서 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 아연합금도금강재는 소지철 및 상기 소지철 상에 형성된 아연합금도금층을 포함한다. 상기 소지철의 종류는 특별히 한정하지 않으며, 본 발명이 속하는 기술분야에서 적용될 수 있는 소지철이면 충분하다. 예를 들면, 열연 강판, 냉연 강판, 선재, 강선 등이 될 수 있다. The sub-alloy gold-plated steel of the present invention comprises a base iron and a zinc alloy plating layer formed on the base iron. The kind of the ground iron is not particularly limited, and it is sufficient that the ground iron which can be applied in the technical field to which the present invention belongs is sufficient. For example, a hot-rolled steel sheet, a cold-rolled steel sheet, a wire rod, a steel wire, or the like.
상기 아연합금도금층은 아연(Zn)을 베이스로 하고, Mg과 Al을 포함한다. 상기 아연합금도금층은 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하는 것이 바람직하다. 또한, 추가적으로 Sr, Be, Ca 및 Li 중 1종 이상이 0.0005~0.009% 포함될 수 있다. 이하, 각 성분 조성범위에 대해서 상세히 설명한다.The zinc alloy plating layer is based on zinc (Zn) and contains Mg and Al. The zinc alloy plating layer preferably contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities in weight percent. In addition, 0.0005 to 0.009% of at least one of Sr, Be, Ca and Li may be added. Hereinafter, the respective component composition ranges will be described in detail.
알루미늄(Al): 10~25 중량% (이하, %)Aluminum (Al): 10 to 25% by weight (hereinafter referred to as%)
상기 Al은 도금욕의 용탕을 제조할 때, Mg 성분을 안정화하고, 부식 환경에서 초기 부식을 억제하는 부식 장벽 역할을 하는 것으로, Mg 함량에 따라 Al 함량이 달라질 수 있다. 상기 Al 함량이 10% 미만에서는 도금욕 용탕 제조시 Mg을 안정화할 수 없어, 용탕 표면에 Mg 산화물이 생성되어 사용이 곤란하게 된다. 반면, 25%를 초과하는 경우에는 도금온도 상승과 도금욕 중에 설치된 각종 설비의 용식이 심하게 발생하므로, 바람직하지 않다.The above Al serves as a corrosion barrier to stabilize the Mg component and inhibit the early corrosion in a corrosive environment when the molten metal of the plating bath is produced. The Al content may vary depending on the Mg content. If the Al content is less than 10%, Mg can not be stabilized in the production of the molten bath of the plating bath, and Mg oxide is generated on the surface of the molten metal, making it difficult to use. On the other hand, if it exceeds 25%, it is not preferable because the plating temperature rises and the solubility of various facilities provided in the plating bath severely occurs.
마그네슘(Mg): 5~20%Magnesium (Mg): 5 to 20%
상기 Mg은 내식성을 발현하는 조직을 형성하는 주성분으로 5% 미만에서는 내식성 발현이 충분하지 않고, 20%를 초과하는 경우에는 도금욕의 Mg 산화물이 다량 형성되는 문제가 있어, 2차적으로 재질 열화와 비용 상승 등의 다양한 문제를야기할 수 있으므로, 상기 Mg는 5~20%를 포함하는 것이 바람직하다.If Mg is less than 5%, the corrosion resistance is not sufficiently exhibited. If Mg is more than 20%, Mg oxide of the plating bath is formed in a large amount, and secondary deterioration of materials It may cause various problems such as an increase in cost, etc. Therefore, it is preferable that the Mg contains 5 to 20%.
한편, 상기 Al 및 Mg 이외에, Mg 성분을 더욱 안정화하기 위해서, 추가적으로 스트론튬(Sr), 베릴륨(Be), 칼슘(Ca), 리튬(Li) 등을 더 포함할 수 있으며, 0.0005~0.009%를 포함하는 것이 바람직하다. 0.0005%를 미만에서는 실질적인 Mg 안정화 효과를 기대하기 어렵고, 0.009%를 초과하는 경우에는 도금 말기에 응고되어 우선 부식이 일어나 내식성을 저해할 수 있고, 비용 상승의 문제가 있으므로 바람직하지 않다.In addition to the above Al and Mg, it may further contain strontium (Sr), beryllium (Be), calcium (Ca), lithium (Li), and the like in addition to 0.0005 to 0.009% . If it is less than 0.0005%, it is difficult to expect a substantial Mg stabilizing effect. If it exceeds 0.009%, it may solidify at the end of plating to cause corrosion first, which may hinder corrosion resistance and increase the cost.
상기 합금 조성이외에 나머지는 아연(Zn)과 불가피한 불순물을 포함한다. 상기 조성 이외에 유효한 성분의 첨가를 배제하는 것은 아니다.In addition to the alloy composition, the balance includes zinc (Zn) and unavoidable impurities. The addition of an effective component other than the above-mentioned composition is not excluded.
본 발명의 상기 아연합금도금층은 MgZn2 합금상, Mg2Zn11 합금상, Al 고용상, Zn 고용상, Al-Zn-Mg 공정상 등을 포함할 수 있다. 상기 고용상은 다른 성분이 고용된 상을 의미하지만, 고용되지 않은 단상(single phase)도 포함한다.The zinc alloy plating layer of the present invention may include MgZn 2 alloy phase, Mg 2 Zn 11 alloy phase, Al solid phase, Zn solid phase, Al-Zn-Mg phase, and the like. The above-mentioned solid phase refers to a phase in which other components are solidified, but also includes a single phase which is not solid phase.
본 발명의 아연합금도금층은 초정으로서, MgZn2 합금상 또는 Al 고용상이 생성될 수 있다. 그 후속으로 나머지 MgZn2 합금상, Mg2Zn11 합금상, Al 고용상, Zn 고용상, Al-Zn-Mg 공정상 등이 생길 수 있다. 즉, 초정이 MgZn2 합금상일 경우 후속으로 Al 고용상, Mg2Zn11 합금상, Zn 고용상 및 Al-Zn-Mg 공정상이 생성되고, 초정이 Al 고용상일 경우에는 후속으로 MgZn2 합금상, Al 고용상, Mg2Zn11 합금상, Zn 고용상 및 Al-Zn-Mg 공정상이 생성된다. 상기 상들은 실질적으로 형성되는 비평형상태에서 생성되는 것일 수 있다. The zinc alloy plating layer of the present invention can be produced as a MgZn 2 alloy phase or an Al solid phase as a primary phase. Subsequently, the remaining MgZn 2 alloy phase, Mg 2 Zn 11 alloy phase, Al solid phase, Zn solid phase, and Al-Zn-Mg phase can be formed. In other words, when the crystal phase is MgZn 2 alloy phase, the Al solid phase, Mg 2 Zn 11 alloy phase, Zn solid phase and Al-Zn-Mg phase are generated in succession, and MgZn 2 alloy phase, Al solution phase, Mg 2 Zn 11 alloy phase, Zn solution phase and Al-Zn-Mg phase are produced. The phases may be generated in a substantially non-equilibrium state.
상기 아연합금도금층은 상기 MgZn2 합금상 및 Mg2Zn11 합금상이 면적분율로 20~50%를 포함하는 것이 바람직하고, 상기 Al 고용상 및 Al-Zn-Mg 공정상이 면적분율로 80% 이하인 것이 바람직하다. 나머지는 Zn 고용상인 것이 바람직하다.The zinc alloy plating layer preferably contains 20 to 50% of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase in an area fraction, and the Al solid phase and the Al-Zn-Mg phase fraction are 80% or less desirable. It is preferable that the remainder is a Zn employment phase.
상기 MgZn2 합금상 및 Mg2Zn11 합금상은 실질적으로 내식성을 발현하는 상으로서, 20% 미만에서는 상시 수분 환경 및 염수 환경에서도 우수한 내식성을 확보하기에 충분하지 않고, 50%를 초과하는 경우에는 내식성이 증가되지만, 상기 MgZn2 합금상 및 Mg2Zn11 합금상이 경질이어서, 도금층의 크랙이 발생할 가능성이 높아진다. The MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase substantially exhibit corrosion resistance. If it is less than 20%, the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase are not sufficient to ensure excellent corrosion resistance in a constant water and salt water environment. increases, but then the MgZn 2 phase alloy and Mg 2 Zn 11 alloy different light, the higher the possibility that the crack of the coating layer occur.
한편, 상기 Al 공정상은 초기 부식장벽을 형성하며, 응고 말기에 형성되는 것으로 추정되는 Al-Zn-Mg 공정상은 내식성이 발현되지만 그 효과가 크지 않다. 따라서, 상기 Al 고용상 및 Al-Zn-Mg 공정상은 그 합계로 80%를 넘지 않는 것이 바람직하다. 상기 Al 고용상 및 Al-Zn-Mg 공정상의 합량이 80%를 초과하면, 상대적으로 MgZn2 합금상 및 Mg2Zn11 합금상의 감소로 내식성이 저하될 수 있다. 한편, 상기 Al 고용상 및 Al-Zn-Mg 공정상은 조성 또는 비평형상태 응고로 인해 생성되지 않을 수 있다.On the other hand, the Al process phase forms an initial corrosion barrier, and corrosion resistance is exhibited in the Al-Zn-Mg process phase, which is presumed to be formed at the end of solidification, but the effect is not significant. Therefore, it is preferable that the sum of the Al solid phase and the Al-Zn-Mg phase does not exceed 80%. When the total amount in the Al solid phase and the Al-Zn-Mg process exceeds 80%, the corrosion resistance may be lowered due to the reduction of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase. On the other hand, the Al solid phase and Al-Zn-Mg phase may not be produced due to compositional or non-equilibrium state solidification.
이하, 본 발명의 아연합금도금강재를 제조하는 일구현예에 대해서 상세히 설명한다. Hereinafter, one embodiment of manufacturing the sub-alloy gold-plated steel material of the present invention will be described in detail.
본 발명의 아연합금도금강재를 제조하는 방법은 소지철을 준비하고, 준비된 소지철 표면에 핵생성이 유리한 형상을 부여한 후, 도금욕에 침지하고, 와이핑 및 냉각을 행하여 제조한다. 이하, 각 과정에 대해서 설명한다.The method for producing the sub-alloy gold-plated steel of the present invention is prepared by preparing a base steel, providing a favorable shape of nucleation on the prepared base steel surface, immersing it in a plating bath, and then performing wiping and cooling. Each process will be described below.
상기 소지철을 준비하고, 준비된 소지철의 표면에 핵생성에 유리한 형상을 부여한다. 전술한 본 발명의 아연합금도금강재의 도금층을 확보하고, 평활한 표면을 확보하기 위해서는 도금을 하기 전에 소지철 표면에 핵생성에 유리한 형상을 부여한다. 액상의 합금금속이 냉각하면서 응고핵이 생성되는데, 상기 응고핵은 열역학적으로 깁스 자유 에너지가 가장 낮은 곳에서 형성된다. 응고에 따른 깁스 자유 에너지는 균일 핵생성보다 불균일 핵생성일 때 유리하며, 불균일 핵생성 자리의 면적이 클수록 핵생성이 유리하여 많은 수의 핵생성이 된다. 따라서, 불균일 핵생성 자리를 조절함으로써 핵생성의 수를 조정할 수 있다. The base steel is prepared, and the surface of the prepared base steel is given a favorable shape for nucleation. In order to secure a plated layer of the sub-alloy gold-plated steel of the present invention and to secure a smooth surface, a surface favorable for nucleation is imparted to the surface of the plated steel before plating. As the liquid metal alloy cools, solidification nuclei are formed, which are thermodynamically formed at the lowest Gibbs free energy. Gibbs free energy due to solidification is advantageous when heterogeneous nucleation is generated rather than homogeneous nucleation. The larger the area of heterogeneous nucleation sites, the more nuclei are produced and the more nuclei are produced. Thus, the number of nucleations can be adjusted by controlling the nonuniform nucleation sites.
이러한 관점에서 본 발명은 소지철의 표면에 핵생성에 유리한 형상을 부여하는 것이 필요하여, 이는 왜도(Rsk)로 나타낼 수 있다. 상기 Rsk가 0 미만이면 골(valley)이 지배적이며, Rsk가 0을 초과하면 산(peak)가 지배적인 표면이 된다. 본 발명의 아연합금도금강재는 MgZn2 합금상과 Mg2Zn11 합금상의 핵생성 수를 증가시키기 위해서, 상기 소지철의 표면 왜도(Rsk)가 -0.2 ~ -1.2가 되도록 조절한다. 상기 Rsk(Roughness skewness)는 조도 파라미터 중의 하나로서 평균선에 대한 프로파일의 비대칭성의 방향과 그 정도를 나타내는 특성값이며, 조도를 측정하는 장치를 이용하여 확인할 수 있다.From this point of view, it is necessary for the present invention to impart a favorable shape to nucleation on the surface of the base iron, which can be expressed by the degree of strain (Rsk). If Rsk is less than 0, the valley is dominant and if Rsk is greater than 0, the peak becomes the dominant surface. In order to increase the nucleation number of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase, the alloy gold-plated steel of the present invention is adjusted so that the surface roughness (Rsk) of the base iron is -0.2 to -1.2. The Rsk (Roughness skewness) is one of the roughness parameters and is a characteristic value indicating the direction and degree of asymmetry of the profile with respect to the average line, and can be confirmed by using an apparatus for measuring roughness.
상기 표면 왜도(Rsk)가 -0.2 미만이면 합금상의 핵생성이 적고 크게 형성되어 표면 요철이 심해지고, 표면 왜도(Rsk)가 -1.2를 초과하게 되면 합금상의 핵생성이 추가적으로 미세하거나 증가하지 않는다. 상기 표면 왜도(Rsk)가 -0.2 ~ -1.2로 되는 형탱는 조도의 골(valley)가 깊고, 산(peak)은 평탄한 구조이다. If the surface roughness (Rsk) is less than -0.2, nucleation of the alloy phase is small and large, so that the surface irregularities become worse. When the surface roughness Rsk exceeds -1.2, nucleation of the alloy phase is additionally fine or increased Do not. The mold having a surface roughness (Rsk) of -0.2 to -1.2 has a deep valley of roughness and a flat peak structure.
상기 표면 왜도(Rsk)를 얻기 위한 방법은 다양하며, 직접 성형법과 간접 성형법으로 구분할 수 있다. 직접 성형법은 소재 표면에 직접 상기와 같은 형태를 제작하는 것으로 것으로, 일예로 산(acid)을 이용한 용해를 들 수 있다. 간접 성형법은 대표적으로 조도가 부여된 조질압연롤을 이용하여 강재에 압력을 가해서 제작할 수 있다. 조질압연롤의 조도는 조도부여한 다음 산(peak)을 연삭하거나, 처음부터 골(valley)이 평탄하도록 할 수 있다.There are various methods for obtaining the surface roughness (Rsk), and can be classified into a direct molding method and an indirect molding method. The direct molding method is to produce the above-described shape directly on the surface of the material. For example, dissolution using an acid may be mentioned. Indirect molding is typically performed by applying pressure to a steel material using a rough rolling roll. The roughness of the temper rolling roll can be adjusted by grinding the peak, then grinding the peak or making the valley flat from the beginning.
상기 소지철은 도금욕에 침지하여 소지철 표면에 아연합금도금층을 형성한다. 상기 도금욕 조성은 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하는 것이 바람직하고, 추가적으로 Sr, Be, Ca 및 Li 중 1종 이상이 0.0005~0.009% 포함될 수 있다, 상기 도금욕 합금조성 범위는 전술한 아연합금도금층의 합금조성 범위에 대해 설명한 바와 다르지 않다.The substrate iron is immersed in a plating bath to form a zinc alloy plating layer on the substrate iron surface. The plating bath composition preferably contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities, and further contains at least one of Sr, Be, Ca and Li in an amount of 0.0005 To 0.009%. The plating bath alloy composition range is not different from that described above for the alloy composition range of the zinc alloy plating layer.
상기 도금욕의 온도는 융점에 따라 달라지며, 상기 융점은 도금욕의 조성에 의존하는 물리화학적 특성이다. 사이 도금욕의 온도를 결정하는 요소는 작업의 편리성, 가열비용 및 도금 품질 등 다양하다. 이러한 점을 종합하여 고려할 때, 상기 도금욕의 온도는 용점보다 높고, 바람직하게는 융점대비 20~100℃ 높게 한다The temperature of the plating bath varies depending on the melting point, and the melting point is a physicochemical characteristic depending on the composition of the plating bath. The factors that determine the temperature of the plating bath between the substrates are various, such as ease of operation, heating cost, and plating quality. Taking these points into consideration, the temperature of the plating bath is higher than the melting point, preferably 20 to 100 ° C higher than the melting point
한편, 도금욕에 침적되는 소지철은 작업의 편리성, 열 밸런스 등을 고려하여 설정한다. 바람직하게는 상기 도금욕 온도의 -10 ~ +10℃로 한다.On the other hand, the base iron deposited in the plating bath is set in consideration of convenience of work, heat balance, and the like. The plating bath temperature is preferably -10 to + 10 ° C.
이하, 본 발명의 실시예에 대해서 상세히 설명한다. 하기 실시예는 본 발명의 이해를 위한 것일 뿐, 본 발명의 권리범위를 해석하기 위한 것이 아니다.Hereinafter, embodiments of the present invention will be described in detail. The following examples are for the understanding of the present invention only and are not intended to be interpreted as to the scope of the present invention.
(실시예)(Example)
시험편으로 두께 0.8㎜, 폭 120㎜, 길이 200㎜의 저탄소강판(C: 0.0014wt%, Mn: 0.15wt%, P: 0.05wt%, S: 0.005wt%, Si: 0.05wt%, 잔부 Fe 및 불가피한 불순물을 포함)을 준비하고, 그 표면의 왜도(Rsk)를 표 1에 나타난 바와 같이 조절하였다. 상기 왜도(Rsk)는 강판 표면의 조도를 부여하는 방식으로 조절하였으며, 구체적으로 롤(roll)에 조도를 부여하고 강판을 상기 롤(roll)에 통과시켜, 강판에 조도가 전사되는 방식을 적용하였다. 상기 왜도(Rsk)는 롤에 조도를 부여할 때, 조도의 골(valley)과 산(peak)의 모양과 형태를 변경하여 조절하였다.(C: 0.0014wt%, Mn: 0.15wt%, P: 0.05wt%, S: 0.005wt%, Si: 0.05wt%, the remainder Fe and the like) having a thickness of 0.8 mm, a width of 120 mm and a length of 200 mm (Including inevitable impurities) were prepared, and the surface roughness (Rsk) thereof was adjusted as shown in Table 1. The distortion Rsk is controlled in such a manner that the roughness of the surface of the steel sheet is given. Specifically, the roughness is applied to the roll, the steel sheet is passed through the roll, and the roughness is transferred to the steel sheet Respectively. The above-mentioned distortion Rsk was controlled by changing the shapes and shapes of the valleys and peaks of the roughness when the roughness was given to the rolls.
준비된 시험편을 도금욕에 침지하여, 표 1의 도금층 조성을 갖는 아연합금도금강재를 제조하였다. 이때 도금욕 온도는 도금 조성의 융점에 따라 달라지므로, 480~570℃의 범위로 설정하였고, 강판의 침지온도는 상기도금욕 온도보다 10℃ 높게 하였다. 상기 침지 후, 도금욕으로부터 올라온 아연합금도금강재 표면을 가스 와이핑하여 도금부착량을 편면 70g/㎥로 조절하고, 상온까지 평균냉각속도 10℃/s로 냉각하여 아연합금도금강재를 제조하였다.The prepared test piece was immersed in a plating bath to prepare an alloyed gold-plated steel having the plating layer composition shown in Table 1. Since the temperature of the plating bath varies depending on the melting point of the plating composition, the temperature is set in the range of 480 to 570 ° C, and the immersion temperature of the steel sheet is 10 ° C higher than the plating bath temperature. After the immersion, the surface of the galvanized gold-plated steel material raised from the plating bath was gas-wiped to adjust the plating adhesion amount to 70 g / m < 3 > on one side and cooled to room temperature at an average cooling rate of 10 DEG C / s.
이렇게 제조된 아연합금도금강재 시편들을 EDS(energy dispersive x-ray spectroscopy) 분석을 통해서 상을 동정하고, XRD(X-ray diffraction) 분석을 통하여 상분율을 측정하였다. 그 결과를 표 1에 함께 나타내었다. The gold-plated steel specimens were identified by energy dispersive X-ray spectroscopy (EDS) analysis and X-ray diffraction (XRD) analysis was used to determine the phase fraction. The results are also shown in Table 1.
상기 시편에 대해서, 내식성, 표면 크랙여부 및 응고 수축 깊이를 측정하여 그 결과를 하기 표 2에 나타내었다. The specimens were measured for corrosion resistance, surface cracking, and coagulation shrinkage depth, and the results are shown in Table 2 below.
상기 내식성은 염수분무시험을 적청발생시간을 부착량으로 나누어 무차원화하여 내식성 지수로 표시하였다. 상기 염수분무시험 조적은 염도 5%, 온도 35℃, pH 6.8, 염수 분무량 2㎖/80㎠·1Hr로 분무하였다. The corrosion resistance is represented by the corrosion resistance index by non-dimensioning the salt spray test divided by the amount of deposition of red rust. The salt spray test tank was sprayed with a salinity of 5%, a temperature of 35 캜, a pH of 6.8, and a sprayed amount of salt water of 2 ml / 80 cm < 2 >
상기 표면 크랙은 180° 굴곡하여 외측의 도금층을 SEM으로 관찰하여 크랙 발생여부를 확인하였다. 한편, 응고 수축 깊이는 표면 평활성을 확인하기 위한 것으로서, 응고수축에 따른 깊이를 3차원 형상을 측정하고 다음 기준으로 평가하였다.The surface cracks were bent 180 degrees, and the plating layer on the outer side was observed with an SEM to confirm the occurrence of cracks. On the other hand, the depth of coagulation shrinkage was used to confirm the surface smoothness. The depth of coagulation shrinkage was measured in three dimensions and evaluated according to the following criteria.
○: 응고수축깊이 0~2㎛ 미만, ?: Coagulation shrinkage depth of less than 0 to 2 占 퐉,
△: 응고수축깊이 2~4㎛ 미만, ?: Coagulation shrinkage depth of less than 2 to 4 占 퐉,
×: 응고수축깊이 4㎛ 이상X: coagulation shrinkage depth 4 탆 or more
구분division 소지철 왜도(Rsk)Possession of iron (Rsk) 도금층 조성(중량%)Plating layer composition (% by weight) 도금층 상분율(면적%)Platelet phase fraction (area%)
AlAl MgMg Sr, Be, Ca, Li 총량Total amount of Sr, Be, Ca, Li MgZn2 MgZn 2 Mg2Zn11 Mg 2 Zn 11 Al 고용상Al Employment Award Al-Zn-Mg 공정상In the Al-Zn-Mg process Zn 고용상Zn employment phase
비교예 1Comparative Example 1 0.160.16 1414 77 1212 44 1616 3535 3333
비교예 2Comparative Example 2 0.280.28 1.51.5 1.51.5 55 22 33 7878 1212
발명예 1Inventory 1 -0.01-0.01 1414 77 1414 66 1818 2828 3434
발명예 2Inventory 2 -0.85-0.85 1010 55 1919 1515 1212 77 4747
발명예 3Inventory 3 -0.85-0.85 1414 77 2222 1313 1818 88 3939
발명예 4Honorable 4 -0.85-0.85 1414 77 0.00050.0005 2323 1414 1515 66 4242
발명예 5Inventory 5 -0.85-0.85 1414 77 0.00900.0090 2121 1515 1616 88 4040
비교예 3Comparative Example 3 -0.85-0.85 1414 77 0.02000.0200 2222 1212 1616 88 4242
발명예 6Inventory 6 -0.85-0.85 1515 1010 2626 1717 2020 66 3131
발명예 7Honorable 7 -0.85-0.85 2525 66 2020 1313 2525 44 3838
발명예 8Honors 8 -0.85-0.85 2525 2020 3737 1212 1515 44 3232
비교예 4Comparative Example 4 -0.38-0.38 3030 2222 4848 1414 1919 88 1111
발명예 9Proposition 9 -1.20-1.20 1414 77 2222 1616 1818 55 3939
비교예 5Comparative Example 5 -1.50-1.50 1414 77 1111 88 1818 2828 3535
구분division MgZn2 + Mg2Zn11 MgZn 2 + Mg 2 Zn 11 내식지수Corrosion resistance index 표면크랙Surface crack 응고수축깊이Coagulation shrinkage depth
비교예 1Comparative Example 1 1616 3232 미발생Not occurring ××
비교예 2Comparative Example 2 77 1919 미발생Not occurring ××
발명예 1Inventory 1 2020 4040 미발생Not occurring ○○
발명예 2Inventory 2 3434 5555 미발생Not occurring ○○
발명예 3Inventory 3 3535 4848 미발생Not occurring ○○
발명예 4Honorable 4 3737 4949 미발생Not occurring ○○
발명예 5Inventory 5 3636 4848 미발생Not occurring ○○
비교예 3Comparative Example 3 3333 2828 미발생Not occurring △△
발명예 6Inventory 6 4343 4444 미발생Not occurring ○○
발명예 7Honorable 7 3333 4646 미발생Not occurring ○○
발명예 8Honors 8 4949 5454 미발생Not occurring ○○
비교예 4Comparative Example 4 6262 5252 발생Occur ××
발명예 9Proposition 9 3838 5050 미발생Not occurring ○○
비교예 5Comparative Example 5 1919 3434 미발생Not occurring ××
상기 표 2의 결과에서 알 수 있듯이, 본 발명의 조건을 충족하는 발명예의 경우에는 우수한 내식성을 갖는 동시에, 표면 크랙 발생이 없고, 표면 평활성이 우수한 것을 알 수 있다. As can be seen from the results of Table 2, the inventive example satisfying the conditions of the present invention has excellent corrosion resistance, no surface cracking, and excellent surface smoothness.
그러나 비교예 1, 2 및 5의 경우에는 본 발명의 도금층 조성은 충족하지만, 소지강판의 표면 왜도가 충족되지 못한 것이다. 결국, 본 발명에서 요구하는 도금층 조직을 확보하지 못하여, 내식성 및 표면 평활성이 열위한 것을 알 수 있다. 한편, 비교예 3 및 4의 경우에는 소지강판의 조건은 충족하지만, 도금 조성이 벗어난 경우로서, 내식성이 열위할 뿐만 아니라, 표면 크랙이 발생하거나, 표면 평활성이 열위한 것을 알 수 있다.However, in the case of Comparative Examples 1, 2 and 5, the coating layer composition of the present invention was satisfied, but the surface distortion of the base steel sheet was not satisfied. As a result, it can be seen that the plating layer structure required in the present invention can not be secured, and the corrosion resistance and the surface smoothness are heated. On the other hand, in the case of Comparative Examples 3 and 4, it was found that the conditions of the base steel sheet were satisfied, but the plating composition was out of order to cause not only the corrosion resistance but also the surface cracking or surface smoothness.

Claims (5)

  1. 소지철 및 상기 소지철 상에 형성된 아연합금도금층을 포함하고,And a zinc alloy plating layer formed on the base iron,
    상기 아연합금도금층은 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하고,Wherein the zinc alloy plating layer contains 10 to 25% of Al, 5 to 20% of Al, and the balance of Zn and unavoidable impurities,
    상기 아연합금도금층은 Al 고용상, Zn 고용상, MgZn2 합금상, Mg2Zn11 합금상, 및 Al-Mg-Zn 공정상 중 하나 이상을 포함하고, Wherein the zinc alloy plating layer comprises at least one of an Al solid phase, a Zn solid phase, a MgZn 2 alloy phase, a Mg 2 Zn 11 alloy phase, and an Al-Mg-Zn phase,
    상기 MgZn2 합금상 및 Mg2Zn11 합금상 중 하나 이상이 면적분율로 20~50% 포함하고, At least one of the MgZn 2 alloy phase and the Mg 2 Zn 11 alloy phase contains 20 to 50% by area fraction,
    상기 Al 고용상 및 Al-Mg-Zn 공정상의 합량은 면적분율로 80% 이하인 내식성 및 표면 평활성이 우수한 아연합금도금강재.The total amount of the Al solid phase and the Al-Mg-Zn phase is 80% or less in terms of an area fraction, and is excellent in corrosion resistance and surface smoothness.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 아연합금도금층은 추가적으로 Sr, Be, Ca 및 Li 중 1종 이상을 0.0005~0.009% 포함하는 내식성 및 표면 평활성이 우수한 아연합금도금강재.Wherein the zinc alloy plating layer further comprises 0.0005 to 0.009% of at least one of Sr, Be, Ca and Li, and is excellent in corrosion resistance and surface smoothness.
  3. 소지철을 준비하는 단계;Preparing a base iron;
    상기 준비된 소지철의 표면 왜도(Rsk)가 -0.2 ~ -1.2이 되도록 조절하는 단계;Adjusting the surface roughness (Rsk) of the prepared ferrous iron to be -0.2 to -1.2;
    상기 소지철을 중량%로, Al: 10~25%, Mg: 5~20%, 나머지는 Zn 및 불가피한 불순물을 포함하는 도금욕에 침지하여 도금하는 단계;Immersing the substrate iron in a plating bath containing 10 to 25% of Al, 5 to 20% of Mg, and the balance of Zn and unavoidable impurities in terms of% by weight;
    상기 도금된 소지철을 와이핑하고 냉각하는 단계A step of wiping and cooling the plated undoped iron
    를 포함하는 내식성 및 표면 평활성이 우수한 아연합금도금강재의 제조방법.And the surface smoothness of the steel sheet.
  4. 청구항 3에 있어서,The method of claim 3,
    상기 도금욕은 추가적으로 Sr, Be, Ca 및 Li 중 1종 이상을 0.0005~0.009% 포함하는 내식성 및 표면 평활성이 우수한 아연합금도금강재의 제조방법.Wherein the plating bath further comprises 0.0005 to 0.009% of at least one of Sr, Be, Ca and Li, and further has excellent corrosion resistance and surface smoothness.
  5. 청구항 3에 있어서,The method of claim 3,
    상기 도금욕의 온도는 융점 보다 20~100℃ 높은 내식성 및 표면 평활성이 우수한 아연합금도금강재의 제조방법.Wherein the temperature of the plating bath is 20 to 100 占 폚 higher than the melting point in corrosion resistance and surface smoothness.
PCT/KR2018/016325 2017-12-26 2018-12-20 Zinc alloy-plated steel having excellent corrosion resistance and surface smoothness, and manufacturing method therefor WO2019132412A1 (en)

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JP2020535239A JP7060693B2 (en) 2017-12-26 2018-12-20 Zinc alloy plated steel and its manufacturing method
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EP4036270A4 (en) * 2019-09-24 2022-08-03 Posco Plated steel sheet having excellent corrosion resistance, galling resistance, workability and surface property and method for manufacturing same
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EP4036270A4 (en) * 2019-09-24 2022-08-03 Posco Plated steel sheet having excellent corrosion resistance, galling resistance, workability and surface property and method for manufacturing same
JP2023500997A (en) * 2019-09-24 2023-01-17 ポスコホールディングス インコーポレーティッド Galvanized steel sheet with excellent corrosion resistance, galling resistance, workability and surface quality, and its manufacturing method
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CN114901853B (en) * 2019-12-18 2024-01-02 Posco公司 Zn-Al-Mg-based hot dip alloy steel product excellent in corrosion resistance of working part and method for producing same
WO2022080004A1 (en) * 2020-10-16 2022-04-21 日本製鉄株式会社 Hot-dip zn plated steel sheet
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