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WO2015099455A1 - Tôle d'acier plaquée par du zinc fondu présentant une excellente résistance aux fissures dues à un bromure métallique liquide - Google Patents

Tôle d'acier plaquée par du zinc fondu présentant une excellente résistance aux fissures dues à un bromure métallique liquide Download PDF

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Publication number
WO2015099455A1
WO2015099455A1 PCT/KR2014/012824 KR2014012824W WO2015099455A1 WO 2015099455 A1 WO2015099455 A1 WO 2015099455A1 KR 2014012824 W KR2014012824 W KR 2014012824W WO 2015099455 A1 WO2015099455 A1 WO 2015099455A1
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Prior art keywords
steel sheet
alloy layer
layer
hot
dip galvanized
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Korean (ko)
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WO2015099455A8 (fr
Inventor
이주연
진광근
전선호
김종상
김명수
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Posco Holdings Inc
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Posco Co Ltd
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Priority to US15/108,263 priority Critical patent/US20160319415A1/en
Priority to JP2016543078A priority patent/JP6317453B2/ja
Priority to EP14875617.4A priority patent/EP3088557B1/fr
Priority to CN201480071104.XA priority patent/CN105849304A/zh
Publication of WO2015099455A1 publication Critical patent/WO2015099455A1/fr
Publication of WO2015099455A8 publication Critical patent/WO2015099455A8/fr
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    • 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
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    • C22C18/00—Alloys based on zinc
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • 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
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    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
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    • 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
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material

Definitions

  • the present invention relates to a hot-dip galvanized steel sheet excellent in crack resistance due to liquid metal embrittlement.
  • the steel sheet for use as automotive parts need to secure high strength, ductility and corrosion resistance.
  • Patent Document 1 is a representative technology for this.
  • the technology is 0.15 to 0.30 wt% of carbon (C), 0.01 to 0.03 wt% of silicon (Si), 15 to 25 wt% of manganese (Mn), 1.2 to 3.0 wt% of aluminum (Al), and 0.020 wt% of phosphorus (P).
  • sulfur (S) 0.001 to 0.002% by weight
  • balance iron (Fe) and other unavoidable impurities and the TWIP (Twin Induced Plasticity) type ultra high strength steel sheet, characterized in that the steel microstructure consists of austenite phase.
  • TWIP Twin Induced Plasticity
  • hot-dip galvanized steel sheet is excellent in corrosion resistance and widely used in building materials, structures, home appliances and automobile bodies.
  • Hot-dip galvanized steel sheet which is used most recently can be divided into hot-dip galvanized steel sheet (hereinafter referred to as 'GI steel sheet') and alloyed hot-dip galvanized steel sheet (hereinafter referred to as 'GA steel sheet').
  • GI steel sheet is a steel plate in which molten zinc is plated on a steel plate, and is easily used for automobile body due to its easy plating and excellent corrosion resistance.
  • a GI steel sheet is a steel plate which formed the plating layer by immersing in the zinc plating bath which added 0.16-0.25 weight% of Al.
  • the plating layer is mostly composed of zinc, but the alloying inhibitor layer capable of suppressing alloying of iron and zinc is present at a thickness of 1 ⁇ m or less at the base iron and the zinc plated layer interface, so that the adhesion between the base iron and the plating layer is reduced. great.
  • the alloying inhibiting layer is usually made of Fe 2 Al 5-x Zn x .
  • the alloying inhibiting layer formed on the GI steel sheet generates liquid zinc while melting by welding heat.
  • the welded portion rises to about 1500 ° C. or more within about 1 second, whereby the base iron and the plating layer are melted and welded.
  • the temperature of the plating layer is raised to 600 ⁇ 800 °C in the welding heat affected (HAZ) portion, whereby Fe is diffused in the plating layer, a portion of the plating layer is alloyed with Fe-Zn alloy layer, the rest is liquid It becomes zinc.
  • liquid zinc penetrates into the grain boundary of the surface of the body, and when the tensile stress is operated on the HAZ, cracks having a size of about 10 to 100 ⁇ m are generated, causing brittle fracture. This is called liquid metal embrittlement (hereinafter referred to as 'LME').
  • 'LME' liquid metal embrittlement
  • the metal has a higher resistance value than other steel grades, resulting in a higher temperature, and the grain boundary due to the high coefficient of thermal expansion is expanded.
  • thermal stress may occur because it has a higher coefficient of thermal expansion than other steel grades such as ferritic steel sheets, which may cause liquid metal embrittlement because the thermal stress is applied to the weld part without external tensile stress. This is very high.
  • FIG. 1 is a photograph observing the GI TWIP steel generated LME crack in the weld. As shown in FIG. 1, when the LME crack is generated, it causes breakage of the steel sheet, and thus it is difficult to be used as an automotive part.
  • Patent Document 1 Korean Unexamined Patent Publication No. 2007-0018416
  • the present invention is to provide a hot-dip galvanized steel sheet excellent in crack resistance due to liquid metal embrittlement.
  • One embodiment of the present invention is a steel sheet having a microstructure having a fraction of austenite of 90 area% or more; And a hot dip galvanized layer formed on the base steel sheet, wherein the hot dip galvanized layer comprises: a Fe—Zn alloy layer; And a Zn layer formed on the Fe—Zn alloy layer, wherein the Fe—Zn alloy layer is hot-dip galvanized steel sheet having excellent crack resistance due to liquid metal embrittlement having a thickness of [(3.4 ⁇ t) / 6] ⁇ m or more.
  • the present invention it is possible to provide a hot-dip galvanized steel sheet in which the plating layer peeling phenomenon easily occurring under ordinary automotive welding and molding conditions is not only prevented, but also the occurrence of cracks due to embrittlement of liquid metal is suppressed.
  • FIG. 2 (a) is a schematic diagram showing a cross section of a conventional GI TWIP steel
  • Figure 2 (b) is a schematic diagram showing a cross section of a hot-dip galvanized steel sheet according to an embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a welded part of Inventive Example 1 according to an embodiment of the present invention.
  • Figure 4 is a cross-sectional photograph of the welded portion of Comparative Example 1 outside the scope of the present invention.
  • the inventors of the present invention while researching a method for effectively suppressing the occurrence of cracks due to liquid metal embrittlement in the manufacturing of the aforementioned GI TIWP steel, the surface oxide and Fe-Al or Fe-Al-Zn to suppress the diffusion of Fe
  • the present invention has been completed under the knowledge that formation of an alloy layer can be suppressed and formation of a Fe-Zn alloy layer having a sufficient thickness can prevent crack generation by LME.
  • FIG. 2 is merely a representation of one embodiment of the present invention in order to explain the present invention, and does not limit the scope of the present invention.
  • the existing conventional GI TWIP steel is a Fe-Al or Fe-Al-Zn alloy layer (2) on the base steel sheet (1), the Fe-Al or Fe-Al-Zn alloy It can be seen that the Zn layer 3 is formed on the layer 2, and that a surface oxide 4 such as MnO is present between the base steel sheet 1 and the Zn layer 3. .
  • the Fe-Al or Fe-Al-Zn alloy layer 2 generates liquid zinc during spot welding, causing LME cracks.
  • the hot-dip galvanized layer 20 is formed on the holding steel sheet 10 and the holding steel sheet, and at this time, the molten zinc plated steel sheet
  • the galvanized layer 20 has a structure in which the Fe—Zn alloy layer 21 and the Zn layer 22 are sequentially formed to secure not only the plating adhesion but also the crack generation resistance due to excellent LME.
  • the hot dip galvanized layer 20 of the present invention formed on the base steel sheet 10 preferably has a structure in which the Fe—Zn alloy layer 21 and the Zn layer 22 are sequentially formed.
  • the base steel sheet 100 to be applied to the present invention targets TWIP steel which is severely cracked by LME as mentioned above. Accordingly, the present invention has a microstructure having an austenitic fraction of 90 area% or more. It is preferable.
  • the base steel sheet used in the hot-dip galvanized steel sheet of the present invention is a weight% as an embodiment, C: 0.10 ⁇ 0.30%, Mn: 10 ⁇ 30 %, Si: 0.01 to 0.03%, Ti: 0.05 to 0.2%, Mn: 10 to 30%, Al: 0.5 to 3.0%, Ni: 0.001 to 10%, Cr: 0.001 to 10%, N: 0.001 to 0.05% , P: 0.020% or less, S: 0.001% to 0.005%, residual Fe, and other unavoidable impurities.
  • the Fe-Zn alloy layer 21 is formed to a sufficient thickness.
  • the Fe—Zn alloy layer 21 is effective in suppressing the occurrence of cracks by LME by reducing the formation of liquid zinc.
  • the thickness of the said Fe-Zn alloy layer is [(3.4xt) / 6] micrometer or more.
  • the thickness of the Fe—Zn alloy layer is less than [(3.4 ⁇ t) / 6] ⁇ m, the effect of suppressing crack generation by LME cannot be sufficiently obtained.
  • t mentioned above means the thickness of the hot dip galvanized layer.
  • the thicker the Fe-Zn alloy layer the thicker the preferred effect, so that the upper limit of the Fe-Zn alloy layer thickness is not particularly limited.
  • the Fe-Zn alloy layer 21 preferably contains 3 to 15% by weight of Fe.
  • the Fe content in the Fe-Zn alloy layer is less than 3% by weight, the LME is the same as the existing GI steel sheet. There may be a disadvantage in that cracks are generated, and if it exceeds 15% by weight may cause a problem that workability is lowered.
  • the Fe-Zn alloy layer 21 does not react with Fe and Zn remains as a Zn layer.
  • the formation of the Fe—Al or Fe—Al—Zn alloy layer 23 formed under the hot dip galvanized layer 30, that is, between the base steel sheet 10 and the Fe—Zn alloy layer 21 is performed. It is desirable to suppress as much as possible.
  • the Fe-Al or Fe-Al-Zn alloy layer 23 forms liquid zinc during welding, causing cracks by LME, so that the Fe-Al or Fe-Al-Zn alloy layer 23 is formed as thin as possible in the present invention.
  • the component content of the Fe-Al and Fe-Al-Zn alloy layer is not particularly limited, but as an example, the Fe-Al alloy layer may be Fe 2 Al 5 , the Fe-Al The Zn alloy layer may be Fe 2 Al 5 Znx.
  • the alloy layer 23 preferably contains less than 0.3% by weight of Al, when the Al content contained in the alloy layer 23 exceeds 0.3% by weight Fe diffusion is suppressed to a sufficient thickness It may be difficult to secure the Fe—Zn alloy layer.
  • the Fe-Ni alloy layer 30 is further included directly below the surface of the base steel sheet.
  • the Fe-Ni alloy layer 30 suppresses surface oxides such as MnO formed by concentrating oxidative elements such as Mn on the surface of the Fe-Ni alloy layer 30, such as conventional GI TWIP steels. It ensures the excellent plating adhesion by being present.
  • the Fe-Ni alloy layer may be formed by a Ni coating layer having an adhesion amount of 300 ⁇ 1000mg / m 2 , the thickness can be different under the influence of the manufacturing conditions.
  • the thickness of the Fe-Ni alloy layer may have a range of 0.05 ⁇ 5 ⁇ m.
  • the Fe—Ni alloy layer is formed to be less than 0.05 ⁇ m, the zinc wettability may deteriorate, resulting in unplating or plating adhesion.
  • the thickness of the Fe-Ni alloy layer exceeds 5 ⁇ m may cause a problem that the amount of Fe diffused from the base steel plate to the plating layer is reduced, there is a disadvantage that the manufacturing cost increases rapidly.
  • the base steel sheet and the hot-dip galvanized layer 1 selected from the group consisting of Fe-X alloy layer, Fe-Al-X alloy layer, Fe-Al-Zn-X alloy layer and Fe-Zn-X alloy layer. More than one species may be further included.
  • the alloy layer it is possible to secure not only plating adhesion but also crack generation resistance due to excellent LME.
  • X mentioned above may be one of Ni and Cr, for example, as a material capable of having a cation in the electroplating solution.
  • the hot-dip galvanized steel sheet of the present invention provided as described above can not only secure crack resistance by excellent LME, but also can secure a good level of plating adhesion, which is usually required for hot-dip galvanized steel sheet.
  • the hot-dip galvanized steel sheet of the present invention can be produced by a variety of methods, preferably after forming the Ni coating layer on the steel plate, 700 ⁇ 900 in a reducing atmosphere furnace H 2 -N 2 mixed gas is charged After heating to °C, the heated steel sheet can be cooled using, and then immersed in a hot dip galvanizing bath of 440 ⁇ 460 °C containing Al of 0.13% by weight or less, the technique If the person skilled in the art other than the conditions can be easily controlled without additional repetitive experiments can be produced hot-dip galvanized steel sheet proposed by the present invention.
  • a base steel sheet having a microstructure having a fraction of austenite of 90 area% or more is prepared.
  • the steel sheet is a TWIP steel, and has a high austenite fraction.
  • the steel sheet includes a large amount of oxidizing elements Mn, Al, and Ni, it is necessary to clean the surface of the steel sheet in advance. For example, in order to remove foreign substances, oxide films, etc. on the surface, it is preferable to perform a pickling or washing process. If the pickling or washing process is not performed, the coating layer or the plating layer may be uneven, and the appearance and adhesion of the plating may deteriorate.
  • the Ni coating layer is formed on the base steel sheet prepared as above.
  • the Ni coating layer may be formed by electroplating, thereby forming a coating layer having a uniform thickness.
  • the Ni coating layer is preferably having an adhesion amount of 300 ⁇ 1000mg / m 2, when the adhesion amount of the Ni coating layer is less than 300mg / m 2 Fe-Ni alloy layer of sufficient thickness is not formed, the surface concentration of Mn It may not be sufficiently inhibited and the zinc wettability may also deteriorate, resulting in unplating or deterioration of plating adhesion.
  • the steel sheet on which the Ni coating layer is formed is heated to 700 to 900 ° C. in a reducing atmosphere in which the H 2 -N 2 mixed gas is charged.
  • Ni of the Ni coating layer may be penetrated into the base steel sheet to form a Fe—Ni alloy layer.
  • the heating temperature is less than 700 ° C there is a problem that the steel sheet structure does not transform into austenite phase after cold rolling, and when the temperature exceeds 900 ° C, the possibility of deformation and breakage in the steel sheet increases.
  • the fraction of the H 2 -N 2 mixed gas used for forming the reducing atmosphere may be used as commonly used in the art, the present invention specifically refers to the fraction of the H 2 -N 2 mixed gas. I never do that.
  • the holding steel sheet is preferably maintained for 20 seconds or more in the heating temperature range.
  • the holding time is less than 20 seconds, a Fe-Ni alloy layer having a sufficient thickness is not formed, thereby sufficiently increasing the surface concentration of Mn. It may not be suppressed.
  • the heated steel sheet is cooled to a cooling rate of 5 ° C / s or more to 400 ⁇ 500 ° C. If the cooling rate is less than 5 ° C / s it is difficult to secure austenite of more than 90 area%.
  • the plating bath inlet temperature of the cooled steel sheet is controlled to have a range of (hot dip galvanizing bath -40 °C) ⁇ (hot dip galvanizing bath +10 °C).
  • the plating bath inlet temperature is lower than (hot dip galvanizing bath -40 °C)
  • Fe contained in the steel sheet is less eluted to suppress the formation of Fe-Zn alloy phase, and exceeds (hot dip galvanizing bath +10 °C)
  • the holding plate is cooled when the cooling stop temperature is higher than the plating bath inlet temperature, and when the cooling stop temperature is the same as the plating bath inlet temperature When the cooling stop temperature is lower than the plating bath inlet temperature, the holding steel sheet may be heated.
  • the plated steel sheet controlled to the plating bath inlet temperature range is immersed in a hot dip galvanizing bath at 440 to 460 ° C. containing 0.13% by weight or less of Al to apply a plating solution to the surface of the plated steel sheet.
  • a hot dip galvanizing bath at 440 to 460 ° C. containing 0.13% by weight or less of Al to apply a plating solution to the surface of the plated steel sheet.
  • the Al content of the hot-dip galvanizing bath exceeds 0.13% by weight, diffusion of Fe may be suppressed and it may be difficult to secure a Fe—Zn alloy layer having a sufficient thickness.
  • the temperature of the hot dip galvanizing bath is less than 440 °C, it is difficult to secure the fluidity of the plating solution and plating may not be performed smoothly, if the temperature exceeds 460 °C, problems such as volatilization of the plating solution occurs.
  • the base steel plate coated with the plating liquid is slowly cooled at a cooling rate of 4 to 20 ° C./s to form a hot dip galvanized layer. If the slow cooling rate is less than 4 °C / s uncoagulated zinc buried in the equipment, such as a roll causes a secondary defect of the product, if the temperature exceeds 20 °C / s Fe-Zn alloy layer grows to a sufficient thickness There is a drawback to not doing it.
  • an Ni coating layer was applied to the base steel sheet by the deposition amount shown in Table 1 below by electroplating (Comparative Examples 2 to 4 were not performed). Subsequently, the base steel sheet was heated under the conditions shown in Table 1 in a reducing atmosphere loaded with a 5% H 2 -N 2 mixed gas, cooled to 400 ° C., and the plating bath inlet temperature was controlled. The plating liquid was applied by immersion in a hot dip galvanizing bath.
  • the plating adhesion evaluation was carried out to check whether the plating is buried on the tape after bending the hot-dip galvanized steel sheet 180 °, peeled when the plating is smeared, it was represented as non-peeled.

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Abstract

L'objectif de la présente invention concerne une tôle d'acier plaquée par du zinc fondu présentant une excellente résistance aux fissures dues à un bromure métallique liquide. Un aspect de la présente invention concerne une tôle d'acier plaquée par du zinc fondu présentant une excellente résistance aux fissures dues à un bromure métallique liquide, la tôle d'acier comprenant : une tôle d'acier de base présentant une microstructure dans laquelle la fraction d'austénite est supérieure ou égale à 90 % en surface ; et une couche plaquée de zinc fondu formée sur la tôle d'acier de base, la couche plaquée de zinc fondu comprenant : une couche d'alliage Fe-Zn ; et une couche de Zn formée sur la couche d'alliage Fe-Zn et la couche d'alliage Fe-Zn permet d'obtenir une tôle d'acier plaquée par du zinc fondu présentant une épaisseur de [(3,4×t)/6] ㎛ ou plus présentant une excellente résistance aux fissures dues à un bromure métallique liquide (où t est l'épaisseur de la tôle d'acier plaquée par du zinc fondu). La présente invention permet d'empêcher un phénomène de pelage d'une couche plaquée qui survient facilement dans des conditions courantes de soudage et de moulage de voitures et permet également d'obtenir une tôle d'acier plaquée par du zinc fondu dans laquelle l'apparition de fissures dues à un bromure métallique liquide est supprimée.
PCT/KR2014/012824 2013-12-25 2014-12-24 Tôle d'acier plaquée par du zinc fondu présentant une excellente résistance aux fissures dues à un bromure métallique liquide Ceased WO2015099455A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/108,263 US20160319415A1 (en) 2013-12-25 2014-12-24 Hot dip galvanized steel sheet having excellent resistance to cracking due to liquid metal embrittlement
JP2016543078A JP6317453B2 (ja) 2013-12-25 2014-12-24 耐液体金属脆化割れ性に優れた溶融亜鉛めっき鋼板
EP14875617.4A EP3088557B1 (fr) 2013-12-25 2014-12-24 Tôle d'acier galvaniser à chaud ayant une excellent résistance à la fissuration due à la fragilisation par métal liquide
CN201480071104.XA CN105849304A (zh) 2013-12-25 2014-12-24 一种抗液态金属脆裂性优异的热浸镀锌钢板

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KR10-2013-0163336 2013-12-25
KR1020130163336A KR101568543B1 (ko) 2013-12-25 2013-12-25 액체금속취화에 의한 크랙 저항성이 우수한 용융아연도금강판

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WO2015099455A8 WO2015099455A8 (fr) 2015-08-20

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JP2017510702A (ja) 2017-04-13
CN105849304A (zh) 2016-08-10
US20160319415A1 (en) 2016-11-03
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WO2015099455A8 (fr) 2015-08-20
JP6317453B2 (ja) 2018-04-25

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