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WO2019132412A1 - Acier plaqué d'alliage de zinc ayant une excellente résistance à la corrosion et un excellent lissé de surface, et son procédé de fabrication - Google Patents

Acier plaqué d'alliage de zinc ayant une excellente résistance à la corrosion et un excellent lissé de surface, et son procédé de fabrication 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
Authority
WO
WIPO (PCT)
Prior art keywords
phase
corrosion resistance
surface smoothness
alloy
plated steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/016325
Other languages
English (en)
Korean (ko)
Inventor
김흥윤
김명수
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Posco Holdings Inc
Original Assignee
Posco Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180165575A external-priority patent/KR102235255B1/ko
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority to JP2020535239A priority Critical patent/JP7060693B2/ja
Priority to US16/956,743 priority patent/US11572607B2/en
Priority to EP18895346.7A priority patent/EP3733920A4/fr
Priority to CN201880084153.5A priority patent/CN111527231B/zh
Publication of WO2019132412A1 publication Critical patent/WO2019132412A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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

La présente invention concerne un acier plaqué destiné à être utilisé pour des automobiles, des appareils électroménagers, des matériaux de construction et analogues et, plus spécifiquement, un acier plaqué d'alliage de zinc ayant une excellente résistance à la corrosion et un excellent lissé de surface, et un procédé de fabrication de celui-ci.
PCT/KR2018/016325 2017-12-26 2018-12-20 Acier plaqué d'alliage de zinc ayant une excellente résistance à la corrosion et un excellent lissé de surface, et son procédé de fabrication Ceased WO2019132412A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020535239A JP7060693B2 (ja) 2017-12-26 2018-12-20 亜鉛合金めっき鋼材及びその製造方法
US16/956,743 US11572607B2 (en) 2017-12-26 2018-12-20 Zinc alloy-plated steel having excellent corrosion resistance and surface smoothness
EP18895346.7A EP3733920A4 (fr) 2017-12-26 2018-12-20 Acier plaqué d'alliage de zinc ayant une excellente résistance à la corrosion et un excellent lissé de surface, et son procédé de fabrication
CN201880084153.5A CN111527231B (zh) 2017-12-26 2018-12-20 耐蚀性和表面平滑性优异的锌合金镀覆钢材及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0180171 2017-12-26
KR20170180171 2017-12-26
KR1020180165575A KR102235255B1 (ko) 2017-12-26 2018-12-19 내식성 및 표면 평활성이 우수한 아연합금도금강재 및 그 제조방법
KR10-2018-0165575 2018-12-19

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WO2019132412A1 true WO2019132412A1 (fr) 2019-07-04

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080004A1 (fr) * 2020-10-16 2022-04-21 日本製鉄株式会社 Feuille d'acier plaquée de zn par immersion à chaud
EP4036270A4 (fr) * 2019-09-24 2022-08-03 Posco Tôle d'acier plaquée possédant une résistance à la corrosion, une résistance au grippage, une aptitude au formage et une propriété de surface excellentes, et son procédé de fabrication
CN114901853A (zh) * 2019-12-18 2022-08-12 Posco公司 加工部耐蚀性优异的Zn-Al-Mg系热浸镀合金钢材及其制造方法
US12435405B2 (en) 2019-12-06 2025-10-07 Posco Hot-dipped galvanized steel sheet having excellent bending workability and corrosion resistance and manufacturing method therefor

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CN105483594A (zh) * 2016-01-14 2016-04-13 上海大学 一种钢材表面连续热浸镀Al–Zn–Mg–Si合金镀层的方法

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7373671B2 (ja) 2019-09-24 2023-11-02 ポスコホールディングス インコーポレーティッド 耐食性、耐かじり性、加工性及び表面品質に優れためっき鋼板、及びその製造方法
EP4036270A4 (fr) * 2019-09-24 2022-08-03 Posco Tôle d'acier plaquée possédant une résistance à la corrosion, une résistance au grippage, une aptitude au formage et une propriété de surface excellentes, et son procédé de fabrication
US12054829B2 (en) 2019-09-24 2024-08-06 Posco Plated steel sheet having excellent corrosion resistance, galling resistance, workability and surface property
JP2023500997A (ja) * 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 耐食性、耐かじり性、加工性及び表面品質に優れためっき鋼板、及びその製造方法
US12435405B2 (en) 2019-12-06 2025-10-07 Posco Hot-dipped galvanized steel sheet having excellent bending workability and corrosion resistance and manufacturing method therefor
CN114901853A (zh) * 2019-12-18 2022-08-12 Posco公司 加工部耐蚀性优异的Zn-Al-Mg系热浸镀合金钢材及其制造方法
JP2023507962A (ja) * 2019-12-18 2023-02-28 ポスコホールディングス インコーポレーティッド 加工部耐食性に優れたＺｎ－Ａｌ－Ｍｇ系溶融合金めっき鋼材及びその製造方法
CN114901853B (zh) * 2019-12-18 2024-01-02 Posco公司 加工部耐蚀性优异的Zn-Al-Mg系热浸镀合金钢材及其制造方法
JP7496876B2 (ja) 2019-12-18 2024-06-12 ポスコホールディングス インコーポレーティッド 加工部耐食性に優れたＺｎ－Ａｌ－Ｍｇ系溶融合金めっき鋼材及びその製造方法
JP7401827B2 (ja) 2020-10-16 2023-12-20 日本製鉄株式会社 溶融Ｚｎ系めっき鋼板
EP4230757A4 (fr) * 2020-10-16 2024-04-10 Nippon Steel Corporation Feuille d'acier plaquée de zn par immersion à chaud
WO2022080004A1 (fr) * 2020-10-16 2022-04-21 日本製鉄株式会社 Feuille d'acier plaquée de zn par immersion à chaud
US12247293B2 (en) 2020-10-16 2025-03-11 Nippon Steel Corporation Hot-dip Zn-based plated steel sheet
JPWO2022080004A1 (fr) * 2020-10-16 2022-04-21

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