WO2014068889A1 - Hot-dip galvanized steel sheet - Google Patents
Hot-dip galvanized steel sheet Download PDFInfo
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- WO2014068889A1 WO2014068889A1 PCT/JP2013/006202 JP2013006202W WO2014068889A1 WO 2014068889 A1 WO2014068889 A1 WO 2014068889A1 JP 2013006202 W JP2013006202 W JP 2013006202W WO 2014068889 A1 WO2014068889 A1 WO 2014068889A1
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- Prior art keywords
- dip galvanized
- less
- steel sheet
- hot
- hot dip
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C2/34—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
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
Definitions
- the present invention relates to a hot dip galvanized steel sheet that can be suitably used for an outer plate and an inner plate of an automobile.
- Patent Document 1 discloses a method for producing a hot-dip galvanized steel sheet having excellent slidability at the time of press work, which regulates the amount of Al in the plating layer and the amount of Al at the plating / steel sheet interface.
- Patent Document 1 does not sufficiently consider the durability of the product such as plating adhesion of a processed portion after press working and corrosion resistance after press working. Therefore, it cannot be said that these problems are completely absent.
- the hot dip galvanized steel sheet is used in the fields of automobiles, home appliances, building materials, etc., it is also required to have an excellent appearance after painting.
- the present invention has been made in view of such circumstances, and provides a hot-dip galvanized steel sheet having excellent plating adhesion after press working, excellent post-paint corrosion resistance after press working, and excellent post-paint appearance. For the purpose.
- the hot dip galvanizing process that controls the structure of the hot dip galvanized layer and forms intermetallic compounds between the steel sheet and the hot dip galvanized layer with predetermined properties, rather than simply performing the hot dip galvanized process as in the prior art.
- a hot dip galvanizing process for controlling the solidified structure and surface texture of the hot dip galvanized layer is performed.
- the hot-dip galvanized steel sheet of the present invention is, in mass%, C: 0.001% to 0.005%, Si: 0.10% or less, Mn: 0.70% to 1.50%, P: 0 0.05% or more and 0.100% or less, S: 0.01% or less, N: 0.005% or less, Al: 0.10% or less, B: 0.0015% or less, and Ti: 0 .01% or more and 0.05% or less and Nb: 0.01% or more and 0.05% or less, at least one selected from the group consisting of Fe and inevitable impurities, and substantially ferrite
- the surface roughness Ra of the surface of the hot dip galvanized layer is 0.8 ⁇ m or more and 1.6 ⁇ m or less, and the glossiness (G value) of the surface of the hot dip galvanized layer is 550.
- Zinc basal plane orientation ratio (Zn) which is the ratio of the crystal orientation of the (002) plane of Zn crystal to the crystal orientation of the (004) plane of Zn crystal on the surface of the hot dip galvanized layer. (002) / (004)) is preferably 60 or more and 90 or less.
- the hot dip galvanized steel sheet of the present invention has excellent plating adhesion after press working, excellent post-paint corrosion resistance after press working, and excellent post-paint appearance.
- the hot dip galvanized steel sheet of the present invention has a steel sheet, a hot dip galvanized layer formed on at least a part of the surface of the steel sheet, and a metal compound existing between the steel sheet and the hot dip galvanized layer.
- the steel plate used in the present invention is in mass%, C: 0.001% to 0.005%, Si: 0.10% or less, Mn: 0.70% to 1.50%, P: 0.050. %: 0.100% or less, S: 0.010% or less, N: 0.005% or less, Al: 0.10% or less, B: 0.0015% or less, and Ti: 0.01 % Or more and 0.05% or less and Nb: 0.01% or more and 0.05% or less, and the balance consists of Fe and inevitable impurities.
- the component composition will be described.
- “%” in the component composition means “% by mass” unless otherwise specified.
- C 0.001% or more and 0.005% or less
- the upper limit of the C content is specified to be 0.005%.
- the content of C is less than 0.001%, the crystal grains become coarse, and the surface of the steel sheet is likely to be rough when formed.
- the lower limit of the C content is specified to be 0.001%.
- Si 0.10% or less
- surface defects due to scale are likely to occur.
- content of Si becomes excess, formation of the intermetallic compound mentioned later may be inhibited.
- the Si content is excessive, the generation of Si nuclei is suppressed, and each crystal in the steel sheet structure becomes coarse, resulting in a problem that the plating adhesion after press working deteriorates.
- a preferable Si content is 0.02% or less.
- Mn 0.70% or more and 1.50% or less If the Mn content is less than 0.70%, a steel sheet having sufficient strength cannot be obtained. By containing a large amount of Mn in the steel sheet, the steel sheet can be strengthened, but when Mn is contained excessively, the deep drawability is lowered. Moreover, when Mn is contained excessively, formation of the intermetallic compound mentioned later is inhibited. Moreover, when Mn is contained excessively, the nucleation of Si is suppressed, and each crystal in the steel sheet structure becomes coarse, and the plating adhesion after press working deteriorates. For this reason, the upper limit of the Mn content is 1.50%. A preferable Mn content is 0.75% or more and 1.2% or less.
- S 0.010% or less
- the toughness of the welded portion deteriorates as in the case where the content of P is large.
- the upper limit of the S content is 0.010%.
- a preferable S content is 0.007% or less.
- N 0.005% or less
- Al 0.10% or less
- Al (sol. Al) and N do not impair the effects of the present invention as long as they are contained in a normal steel sheet.
- N combines with Ti to form TiN, or N combines with Al to form AlN. Therefore, the Al content is specified to be 0.10% or less, and the N content is specified to be 0.005% or less. If the Al content exceeds 0.10%, formation of an intermetallic compound described later is inhibited. On the other hand, if the Al content exceeds 0.10%, the generation of Si nuclei is suppressed, and each crystal in the steel sheet structure is coarsened, and the plating adhesion during processing deteriorates.
- the N content exceeds 0.005%, the nitride is dispersed in the ferrite grains, and the work hardening rate is lowered.
- the preferable Al content is 0.04% or less, and the preferable N content is 0.002 or less.
- B 0.0015% or less
- B is an element that contributes to strengthening of grain boundaries cleaned by forming carbides.
- the lower limit of the B content is preferably 0.0003%.
- the upper limit of the B content is 0.0015%.
- preferable content of B is 0.0003% or more and 0.0010% or less.
- Ti and Nb form carbides (TiC, NbC) in the ferrite grains.
- the work hardening rate of a steel plate is improved.
- the content of Ti or Nb is less than 0.01%, the amount of carbide of Ti or the amount of carbide of Nb is small, the dislocation motion cannot be controlled, and a sufficient work hardening rate cannot be expected.
- the Nb or Ti content exceeds 0.05%, coarse carbides are precipitated and the work hardening rate is lowered.
- the Nb or Ti content exceeds 0.05%, the grain boundaries in the steel sheet structure are cleaned, and the intermetallic compound grows excessively during the hot dip galvanizing process, resulting in poor plating adhesion.
- at least one of the Ti content and the Nb content is 0.01% or more and 0.05% or less.
- a preferable Ti content is 0.015% or more and 0.04% or less, and a preferable Nb content is 0.01% or more and 0.03% or less.
- both Ti and Nb are included, if one content is outside the above range, it is outside the scope of the present invention.
- Fe and unavoidable impurities The balance other than the above components is Fe and unavoidable impurities.
- the unavoidable impurity is, for example, O (oxygen).
- O is a typical inevitable impurity inevitably mixed.
- the content of inevitable impurities is not particularly limited, and the allowable content of inevitable impurities depends on the type of inevitable impurities. In the case of O, there is no problem if the content is 0.005% or less.
- the steel sheet structure is substantially a ferrite single phase. Since the steel sheet structure is substantially composed of a ferrite single phase, the hot dip galvanized steel sheet is excellent in workability.
- the ferrite single phase substantially includes not only the case where the entire steel sheet structure is the ferrite phase but also the case where 95% or more of the steel sheet structure is the ferrite phase. However, it is normally considered that no phase other than ferrite is generated. Note that the fact that it is substantially a ferrite single phase is confirmed by observing a cross section of the etched sample with an optical microscope.
- the hot dip galvanized layer is a hot dip galvanized layer formed by a normal hot dip galvanizing process.
- the hot-dip galvanized layer contains Al in an amount of 0.3% to 0.6% by mass.
- the hot dip galvanized layer may contain components other than Zn and Al as long as the effects of the present invention are not impaired. Examples of components other than Zn and Al include Fe, Al, Mg, and Cr.
- the Al content is less than 0.3%, it is necessary to reduce the Al concentration in the plating bath.
- the Al concentration is lowered, Fe is eluted, so that dross is deposited and appearance is deteriorated, or hard dross is dispersed in the hot dip galvanized layer.
- the workability of the hot dip galvanized steel sheet deteriorates. If the Al content exceeds 0.6%, a large amount of an oxide film of Al is formed on the surface of the hot dip galvanized layer, and the spot weldability of the hot dip galvanized steel sheet deteriorates.
- the hot-dip galvanized layer preferably has a surface roughness Ra of 0.8 to 1.6 ⁇ m. If the surface roughness Ra is less than 0.8, the oil may not be retained on the surface of the hot dip galvanized layer during pressing of the hot dip galvanized steel sheet, and workability may be poor. If the surface roughness Ra exceeds 1.6 ⁇ m, the sharpness after coating may be inferior and an excellent appearance may not be imparted to the hot-dip galvanized steel sheet after coating.
- the said surface roughness Ra means surface roughness Ra measured by the method as described in an Example.
- the glossiness (G value) of the surface of the hot dip galvanized layer is preferably 550 or more and 750 or less. If the glossiness (G value) is less than 550, the sharpness after coating may be inferior, and an excellent appearance may not be imparted to the hot-dip galvanized steel sheet after coating. If the glossiness (G value) is 750 or more, it may be too smooth, and oil may not be retained on the surface of the hot dip galvanized layer when the hot dip galvanized steel sheet is pressed, resulting in poor formability.
- the said glossiness (G value) means the glossiness (G value) measured by the method as described in an Example.
- Zinc basal plane orientation ratio (Zn (002) / (004)), which is the ratio of the crystal orientation of the (002) plane of Zn crystal to the crystal orientation of the (004) plane of Zn crystal on the surface of the hot dip galvanized layer. ) Is preferably 60 or more and 90 or less. If the orientation ratio of the bottom surface of the zinc base is less than 60, the orientation of the zinc crystals is relatively random, and the crystal size when the zinc solidifies immediately after plating becomes fine. May be inferior in moldability without being held on the surface. If the orientation ratio of the basal plane of the zinc base is more than 90, the orientation of the basal plane of the Zn crystal is too high and the crystal grains are likely to grow. As a result, the dendritic arm develops. The appearance of the steel sheet may deteriorate. Moreover, if the zinc base bottom surface orientation ratio exceeds 90, the corrosion resistance may be deteriorated.
- the zinc base bottom surface orientation ratio can be defined by the following formula.
- the zinc base bottom orientation ratio (Zn (002) / (004)) represents ⁇ (002) plane Zn crystal orientation ⁇ / ⁇ (004) plane Zn crystal orientation ⁇ .
- (I (xyz) is the Zn intensity measured by X-ray on the (xyz) plane of the sample
- I std (xyz) is the Zn intensity measured by X-ray on the (xyz) plane of the standard sample (pure Zn powder).
- the degree of orientation of the solidified structure affects the gloss, crystal size, and surface roughness (surface roughness). For this reason, it is important to control the press workability in addition to controlling the surface orientation of the hot-dip galvanized steel sheet in order to accurately control the zinc base orientation ratio.
- the zinc base bottom surface orientation ratio is in the above range, the gloss and the surface roughness Ra satisfy the above preferable range.
- the hot dip galvanized layer may be formed on at least a part of the steel plate surface. Since the hot dip galvanized layer is formed on the surface of the steel plate by a method of immersing the steel plate in a plating bath, the hot dip galvanized layer is usually formed on the entire surface of the steel plate.
- the thickness of the hot dip galvanized layer is not particularly limited.
- the thickness of the hot dip galvanized layer can be adjusted by controlling the amount of plating applied during the hot dip galvanizing process.
- Intermetallic compound is composed of an intermetallic compound consisting of at least one of an average particle diameter of 1 ⁇ m or less of Fe 2 Al 5 or FeAl 3, present in the steel sheet and hot-dip galvanizing layer. Further, the intermetallic compound contains 0.12 gm ⁇ 2 or more and 0.22 gm ⁇ 2 or less of Al. The presence of the intermetallic compound can suppress the formation of the FeZn alloy phase and ensure good plating adhesion. This effect cannot be obtained in cases other than an intermetallic compound composed of at least one of Fe 2 Al 5 or FeAl 3 . Other than these, a hard and brittle FeZn intermetallic compound may be formed, and in this case, the plating adhesion deteriorates. The presence of the intermetallic compound can be confirmed by a method of analyzing and detecting the vicinity of the interface with the steel plate in the cross section of the hot dip galvanized layer by electron beam diffraction in a transmission electron microscope.
- the average particle diameter of Fe 2 Al 5 or FeAl 3 exceeds 1 ⁇ m, the hard intermetallic compound is excessively grown, and the impact resistance characteristics of the hot dip galvanized steel sheet deteriorate. For this reason, the upper limit of the average particle diameter is 1 ⁇ m.
- the Al content in the intermetallic compound is less than 0.12 gm ⁇ 2, it is necessary to set the Al concentration in the molten zinc bath of the plating low. If the Al concentration is set low, dross precipitates and the molten zinc The appearance and workability of the plated steel sheet deteriorate. If the Al content in the intermetallic compound exceeds 0.22 gm -2 , the Al concentration in the plating bath needs to be set high. If the Al concentration is set high, an Al oxide film is formed on the surface of the hot dip galvanized layer. A large amount is formed and spot weldability deteriorates.
- the hot dip galvanized steel sheet of the present invention is excellent in plating adhesion after press working and excellent in corrosion resistance after painting of a processed part after press working. And the hot-dip galvanized steel sheet of the present invention has an excellent appearance after coating. For this reason, the hot dip galvanized steel sheet of the present invention can be applied to products having very severe processing parts such as a back door and a hood.
- the hot dip galvanized steel sheet of the present invention has a yield stress (YS) of 220 MPa or more and 320 MPa or less. If the yield stress is in the above range, the hot-dip galvanized steel sheet can be preferably applied to applications that require severe processing such as outer plates and that must ensure shape freezeability.
- a hot-dip galvanized steel sheet can be manufactured by the following method. First, steel having the above component composition is made into a slab by continuous casting, the slab is heated, and scale removal and rough rolling are performed. Next, after cooling, finish rolling, cooling, winding, pickling, and cold rolling are performed. Next, the steel sheet is annealed and hot-dip galvanized in a continuous hot-dip galvanizing facility. Next, an alloying treatment is performed as necessary.
- the heating time, heating temperature, rough rolling conditions, cooling conditions, finish rolling conditions, winding conditions, etc. when heating the slab can be appropriately set based on common technical knowledge.
- the annealing conditions of the steel sheet affect the yield stress of the hot dip galvanized steel sheet.
- the heating temperature during annealing in order to set the yield stress in the above range, it is preferable to set the heating temperature during annealing to 780 ° C. or more and 820 ° C. or less.
- the hot dip galvanizing treatment condition in order to control the Al content of the hot dip galvanized layer and allow an intermetallic compound to exist between the steel plate and the hot dip galvanized layer, the hot dip galvanizing treatment condition needs to be a specific condition. is there. Moreover, in order to make the surface state (surface roughness Ra, glossiness (G value), zinc base bottom orientation ratio) of a hot dip galvanized layer into a desired state, it is necessary to adjust the conditions of the hot dip galvanizing treatment. . Hereinafter, conditions for the hot dip galvanizing process will be described.
- the intrusion plate temperature which is the temperature of the steel plate when the annealed steel plate enters the plating bath, is not particularly limited.
- the temperature of the immersion plate is preferably a temperature of the plating bath (bath temperature) of ⁇ 20 ° C. or higher and a bath temperature of + 20 ° C. or lower. If the infiltration plate temperature is in the above range, the change in bath temperature is small, and it is easy to perform desired hot dip galvanization continuously.
- the composition of the plating bath into which the annealed steel sheet enters is not limited as long as it contains Al in addition to Zn, and may contain other components as necessary.
- the concentration of Al in the plating bath is not particularly limited. In the present invention, the Al concentration is preferably 0.16% by mass or more and 0.25% by mass or less. If the concentration of Al is 0.16% by mass or more and 0.25% by mass or less, an FeAl alloy phase is formed and formation of an FeZn alloy phase is suppressed, which is preferable.
- the glossiness can be adjusted by the Al concentration in the plating bath. When the Al concentration in the plating bath becomes low, FeZn crystals rather than FeAl are formed slightly at the interface between the steel sheet and the hot dip galvanized layer.
- a more preferable Al concentration is 0.19% by mass or more and 0.22% by mass or less.
- the temperature of the plating bath is not particularly limited.
- the bath temperature is preferably 440 ° C. or higher and 480 ° C. or lower.
- a bath temperature of 440 ° C. or higher and 480 ° C. or lower is preferable because an appropriate bath temperature can be stably secured and Zn does not solidify even if the bath temperature distribution is deteriorated.
- the solubility of the FeAl alloy phase decreases as the bath temperature decreases, the amount of FeAl alloy phase generated tends to increase.
- a more preferable range of the bath temperature is 450 ° C. or higher and 460 ° C. or lower.
- the immersion time when the steel sheet is immersed in the plating bath is not particularly limited.
- the immersion time is preferably 0.5 seconds or more and 3 seconds or less.
- the immersion time is in the above range, a desired hot dip galvanized layer is easily formed on the surface of the steel plate.
- the amount of plating adhesion is adjusted by gas jet wiping or the like.
- the plating adhesion amount is not particularly limited.
- the plating adhesion amount is preferably in the range of 20 g / m 2 or more and 120 g / m 2 or less. If the plating adhesion amount is less than 20 g / m 2 , it may be difficult to ensure corrosion resistance. On the other hand, when the plating adhesion amount exceeds 120 g / m 2 , the plating peel resistance may deteriorate.
- temper rolling is performed.
- the type of roll used for the SK treatment is not particularly limited, and an Electro-Discharge Texture roll (EDT roll), an Electron Beam Texture roll (EBT roll), a shotdal roll, a topochrome roll, or the like can be used.
- the rolling reduction rate during SK treatment is not particularly limited.
- the SK pressure ratio is preferably 0.7 to 0.9%. If the SK rolling reduction is in the above range, the surface roughness can be easily adjusted to the above preferable range. Further, if the SK rolling reduction is outside the above range, the dullness that holds the rolling oil may not be obtained, and the formability may be reduced, and the yield strength may be reduced.
- the cooling rate ( ⁇ (cooling end temperature) ⁇ (cooling start temperature) ⁇ / cooling time) after the steel sheet is pulled up from the plating bath is preferably ⁇ 5 ° C./second or more and ⁇ 30 ° C./second or less. If the cooling rate is ⁇ 5 ° C./second or less, spangles may become coarse, which is not preferable. If the cooling rate is ⁇ 30 ° C./second or more, rapid cooling is required to secure the cooling rate, resulting in a deterioration in economy. It is not preferable. On the other hand, if the cooling rate is slow, the FeAl alloy phase is decomposed and the amount of FeAl alloy phase produced is reduced.
- a more preferable range of the cooling rate is ⁇ 7 ° C./second or more and ⁇ 22 ° C./second or less.
- the cooling rate refers to an average cooling rate when the temperature is lowered from 420 ° C. to 400 ° C.
- the hot dip galvanized steel sheet of the present invention has been described.
- the use of the hot dip galvanized steel sheet of the present invention will be described.
- the hot dip galvanized steel sheet of the present invention is preferably used for applications in which a coating film is formed on the surface of the hot dip galvanized layer because it has excellent post-coating corrosion resistance after press working. Moreover, the hot-dip galvanized steel sheet of the present invention is excellent in plating adhesion even when applied to applications requiring strict workability, and does not significantly reduce corrosion resistance and mechanical properties. Examples of applications in which strict processability is required and a coating film is formed include automotive steel plates such as automobile outer plates and inner plates. The method for forming the coating film is not particularly limited. In the present invention, it is preferable that a chemical conversion treatment is performed on the surface of the hot dip galvanized layer to form a chemical conversion film, and then a coating film is formed on the chemical conversion film.
- Either a coating type or a reaction type can be used as the chemical conversion treatment liquid.
- the component contained in a chemical conversion liquid is not specifically limited, either a chromate processing liquid may be used and a chromium free chemical conversion liquid may be used.
- the chemical conversion film may be a single layer or a multilayer.
- the coating method for forming the coating film is not particularly limited. Examples of the coating method include electrodeposition coating, roll coater coating, curtain flow coating, and spray coating. Moreover, in order to dry a coating material, means, such as hot air drying, infrared heating, induction superheating, can be used.
- the black scale of the hot-rolled steel sheet having the steel composition shown in Table 1 is removed by pickling and cold-rolled at a reduction rate of 75%, and then the surface is on the entry side of the CGL (continuous hot dip galvanizing line).
- annealing was performed at an annealing temperature shown in Table 2 in an annealing furnace, and hot dip galvanizing treatment was performed under the conditions shown in Table 2.
- the average cooling rate from 420 to 400 ° C. after plating and wiping was also measured. The cooling rate is also shown in Table 2.
- SK treatment was performed under the conditions shown in Table 2 before cooling.
- the structure of the steel sheet was composed of a ferrite single phase.
- a test piece was collected from the steel plate, the cross section in the rolling direction (L cross section) was polished, etched with a nital solution, and the structure was observed and imaged using an optical microscope (magnification: 50 to 400 times). And the kind of tissue and the fraction (area%) were measured using the image analysis apparatus. All the steel plates were steel plates substantially composed of a ferrite single phase.
- the intermetallic compound composition was identified by the X-ray diffraction method after removing the zinc plating layer with fuming nitric acid. Regarding the amount, the surface of the intermetallic compound on the sample surface prepared in the same manner was dissolved in dilute hydrochloric acid and quantified by ICP. Similarly, the amount of Al in the plating layer was dissolved in dilute hydrochloric acid and determined by ICP.
- the particle size of the intermetallic compound was measured by the following method. A test piece was collected from the steel plate, and the metal structure of a cross section parallel to the rolling direction was observed with a scanning electron microscope (SEM) at a magnification of 5000 to measure the average particle size of the intermetallic compound. The measurement results are shown in Table 2.
- the surface roughness Ra of the hot dip galvanized layer was measured by the following method. In accordance with the provisions of JIS B 0601, the arithmetic average roughness Ra was measured using a stylus type surface roughness meter. The measurement results are shown in Table 2.
- the zinc base bottom surface orientation ratio is shown in Table 2.
- the resulting hot-dip galvanized steel sheet is subjected to chemical conversion treatment, electrodeposition coating, intermediate coating, and top coating to produce a hot-dip galvanized steel sheet on which a coating film has been formed and visually evaluated after coating. did. When there was no appearance defect due to plating unevenness or the like, it was evaluated as good, and when it was present, it was evaluated as defective. The evaluation results are shown in Table 1.
- the punch with a frustum diameter of 5/8 inch is heightened at 1843 g for the part subjected to frustoconical overmolding (molding equivalent to press molding) under the condition of a plate thickness reduction rate of 10%.
- An impact resistance test of dropping from 1 m was performed, and evaluation was performed by a method of peeling cellophane tape. Those with peeling were considered poor adhesion (x), and those without peeling were good adhesion ( ⁇ ). The evaluation results are shown in Table 2.
- ⁇ Cone overhang molding part was subjected to chemical treatment, electrodeposition coating, intermediate coating, and top coating, and the corrosion resistance after coating was evaluated by the following method.
- a salt spray test based on JIS Z 2371 (2000) was conducted for 10 days, and the presence or absence of swelling of the processed part after press working was evaluated. Those with blisters were judged as bad (x), and those without blisters were judged as good ( ⁇ ). The evaluation results are shown in Table 2.
- a JIS No. 5 tensile test piece is taken from the hot dip galvanized steel sheet in the direction of 90 ° with respect to the rolling direction, and a tensile test is performed under the condition that the crosshead speed is 10 mm / min (constant) in accordance with the provisions of JIS Z 2241. It was. A YS of 220 to 320 MPa was considered good. The evaluation results are shown in Table 2.
- the hot-dip galvanized steel sheet of the present invention has extremely good characteristics and does not undergo plating peeling despite being pressed. Corrosion resistance is also good.
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Abstract
Description
本発明は、自動車の外板、内板用に好適に使用可能な溶融亜鉛めっき鋼板に関するものである。 The present invention relates to a hot dip galvanized steel sheet that can be suitably used for an outer plate and an inner plate of an automobile.
近年、自動車、家電、建材等の分野において、素材鋼板に防錆性を付与した表面処理鋼板、中でも防錆性に優れた溶融亜鉛めっき鋼板が使用されている。特に欧米の自動車メーカーはめっき厚を簡単に増やせる溶融亜鉛めっき鋼板の適用により防錆性能を向上させることを考えている。また、経済成長著しい東アジア地区において自動車用鋼板の大きな需要が見込める状況である。 Recently, in the fields of automobiles, home appliances, building materials, etc., surface-treated steel sheets imparted with rust resistance to raw steel sheets, especially hot-dip galvanized steel sheets with excellent rust resistance have been used. In particular, European and American automakers are considering improving rust prevention performance by applying hot-dip galvanized steel sheets that can easily increase the plating thickness. In addition, there is a great demand for automotive steel sheets in the East Asian region where economic growth is remarkable.
また、良好な加工性が厳しく要求される自動車用鋼板の場合、プレス加工後におけるめっき密着性やプレス加工後の塗装後耐食性が良好でなければ、製品の耐久性を維持できない。 In addition, in the case of automotive steel sheets that are required to have good workability, the durability of the product cannot be maintained unless the plating adhesion after press working and the corrosion resistance after painting after press working are good.
特許文献1には、めっき層中のAl量、めっき/鋼板界面のAl量を規定する、プレス加工時の摺動性に優れた溶融亜鉛めっき鋼板の製造方法が開示されている。しかし、特許文献1では、プレス加工後における加工部のめっき密着性、プレス加工後の耐食性等の製品の耐久性が充分に考慮されていない。したがって、これらの問題が全く無いとまではいえない。 Patent Document 1 discloses a method for producing a hot-dip galvanized steel sheet having excellent slidability at the time of press work, which regulates the amount of Al in the plating layer and the amount of Al at the plating / steel sheet interface. However, Patent Document 1 does not sufficiently consider the durability of the product such as plating adhesion of a processed portion after press working and corrosion resistance after press working. Therefore, it cannot be said that these problems are completely absent.
以上の通り、従来、プレス加工後のめっき密着性やプレス加工後の塗装後耐食性が良好な鋼板は存在しない。 As described above, conventionally, there is no steel sheet having good plating adhesion after press working and post-coating corrosion resistance after press working.
また、溶融亜鉛めっき鋼板は、自動車、家電、建材等の分野において使用されることから、優れた塗装後外観を有することも求められる。 Moreover, since the hot dip galvanized steel sheet is used in the fields of automobiles, home appliances, building materials, etc., it is also required to have an excellent appearance after painting.
本発明はかかる事情に鑑みてなされたものであって、プレス加工後の優れためっき密着性、プレス加工後の優れた塗装後耐食性、且つ優れた塗装後外観を有する溶融亜鉛めっき鋼板を提供することを目的とする。 The present invention has been made in view of such circumstances, and provides a hot-dip galvanized steel sheet having excellent plating adhesion after press working, excellent post-paint corrosion resistance after press working, and excellent post-paint appearance. For the purpose.
本発明者らは上記課題を解決するために鋭意研究を重ねた。その結果、従来技術の様に単に溶融亜鉛めっき処理を行うのではなく、溶融亜鉛めっき層の構造を制御し、金属間化合物を鋼板と溶融亜鉛めっき層間に所定の性状で形成させる溶融亜鉛めっき処理を行う。好ましくは溶融亜鉛めっき層の凝固組織と表面のテクスチャーを制御する溶融亜鉛めっき処理を行うことである。このような溶融亜鉛めっき処理により、プレス加工後の優れためっき密着性、プレス加工後における加工部の優れた塗装後耐食性、且つ優れた塗装後外観を有する溶融亜鉛めっき鋼板になることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。 The present inventors have intensively studied to solve the above problems. As a result, the hot dip galvanizing process that controls the structure of the hot dip galvanized layer and forms intermetallic compounds between the steel sheet and the hot dip galvanized layer with predetermined properties, rather than simply performing the hot dip galvanized process as in the prior art. I do. Preferably, a hot dip galvanizing process for controlling the solidified structure and surface texture of the hot dip galvanized layer is performed. By such hot dip galvanizing treatment, we found that excellent plating adhesion after press working, excellent post-coating corrosion resistance of the processed part after press working, and a hot dip galvanized steel sheet having an excellent post-painting appearance, The present invention has been completed. More specifically, the present invention provides the following.
本発明の溶融亜鉛めっき鋼板は、質量%で、C:0.001%以上0.005%以下、Si:0.10%以下、Mn:0.70%以上1.50%以下、P:0.050%以上0.100%以下、S:0.01%以下、N:0.005%以下、Al:0.10%以下、B:0.0015%以下を含有し、かつ、Ti:0.01%以上0.05%以下及びNb:0.01%以上0.05%以下のうちから選択される少なくとも一種を含有し、残部がFe及び不可避的不純物の組成からなり、実質的にフェライト単相から構成される鋼板と、前記鋼板の表面の少なくとも一部に形成された、Alを質量%で0.3%以上0.6%以下含む溶融亜鉛めっき層と、前記鋼板と前記溶融亜鉛めっき層間に存在する、0.12gm-2以上0.22gm-2以下のAlを含み、かつ平均粒径1μm以下のFe2Al5もしくはFeAl3の少なくとも一種からなる金属間化合物と、を有し、降伏応力(YS)が220MPa以上320MPa以下である。 The hot-dip galvanized steel sheet of the present invention is, in mass%, C: 0.001% to 0.005%, Si: 0.10% or less, Mn: 0.70% to 1.50%, P: 0 0.05% or more and 0.100% or less, S: 0.01% or less, N: 0.005% or less, Al: 0.10% or less, B: 0.0015% or less, and Ti: 0 .01% or more and 0.05% or less and Nb: 0.01% or more and 0.05% or less, at least one selected from the group consisting of Fe and inevitable impurities, and substantially ferrite A steel plate composed of a single phase, a hot-dip galvanized layer containing Al in an amount of 0.3% or more and 0.6% or less by mass%, formed on at least part of the surface of the steel plate, the steel plate and the hot-dip zinc present in the plating layers, 0.12gm -2 least 0.22Gm - Include the following Al, and having at least one consisting of an intermetallic compound having an average particle diameter of 1μm or less of Fe 2 Al 5 or FeAl 3, the yield stress (YS) is equal to or less than 320MPa or more 220 MPa.
本発明の溶融亜鉛めっき鋼板においては、前記溶融亜鉛めっき層の表面の表面粗さRaが0.8μm以上1.6μm以下であり、前記溶融亜鉛めっき層の表面の光沢度(G値)が550以上750以下であり、前記溶融亜鉛めっき層の表面における、Zn結晶の(002)面の結晶配向性とZn結晶の(004)面の結晶配向性との比である亜鉛基底面配向率(Zn(002)/(004))が60以上90以下であることが好ましい。 In the hot dip galvanized steel sheet of the present invention, the surface roughness Ra of the surface of the hot dip galvanized layer is 0.8 μm or more and 1.6 μm or less, and the glossiness (G value) of the surface of the hot dip galvanized layer is 550. Zinc basal plane orientation ratio (Zn), which is the ratio of the crystal orientation of the (002) plane of Zn crystal to the crystal orientation of the (004) plane of Zn crystal on the surface of the hot dip galvanized layer. (002) / (004)) is preferably 60 or more and 90 or less.
本発明の溶融亜鉛めっき鋼板は、プレス加工後の優れためっき密着性、プレス加工後の優れた塗装後耐食性、且つ優れた塗装後外観を有する。 The hot dip galvanized steel sheet of the present invention has excellent plating adhesion after press working, excellent post-paint corrosion resistance after press working, and excellent post-paint appearance.
以下、本発明について具体的に説明する。なお、本発明は以下の実施形態に限定されない。 Hereinafter, the present invention will be specifically described. In addition, this invention is not limited to the following embodiment.
本発明の溶融亜鉛めっき鋼板は、鋼板と、鋼板の表面の少なくとも一部に形成された溶融亜鉛めっき層と、鋼板と溶融亜鉛めっき層間に存在する金属化合物とを有する。 The hot dip galvanized steel sheet of the present invention has a steel sheet, a hot dip galvanized layer formed on at least a part of the surface of the steel sheet, and a metal compound existing between the steel sheet and the hot dip galvanized layer.
<鋼板>
本発明で用いる鋼板は、質量%で、C:0.001%以上0.005%以下、Si:0.10%以下、Mn:0.70%以上1.50%以下、P:0.050%以上0.100%以下、S:0.010%以下、N:0.005%以下、Al:0.10%以下、B:0.0015%以下を含有し、かつ、Ti:0.01%以上0.05%以下及びNb:0.01%以上0.05%以下のうちから選択される少なくとも一種を含有し、残部がFe及び不可避的不純物からなる。以下、上記成分組成について説明する。なお、なお、本明細書において、成分組成における「%」表示は、特に断らない限り「質量%」を意味する。
<Steel plate>
The steel plate used in the present invention is in mass%, C: 0.001% to 0.005%, Si: 0.10% or less, Mn: 0.70% to 1.50%, P: 0.050. %: 0.100% or less, S: 0.010% or less, N: 0.005% or less, Al: 0.10% or less, B: 0.0015% or less, and Ti: 0.01 % Or more and 0.05% or less and Nb: 0.01% or more and 0.05% or less, and the balance consists of Fe and inevitable impurities. Hereinafter, the component composition will be described. In this specification, “%” in the component composition means “% by mass” unless otherwise specified.
C:0.001%以上0.005%以下
Cの含有量が増えると、深絞り性や延性が劣化し自動車外板用や内板用の鋼板に求められる成形性を鋼板に付与することが困難となる。このためCの含有量の上限は0.005%に規定する。一方、Cの含有量が0.001%未満では結晶粒が粗大化して、成形した際に鋼板表面に肌荒れが生じやすくなる。このため、Cの含有量の下限は0.001%に規定する。本発明で用いる鋼板の成分組成におけるCの含有量が上記範囲にあることで、鋼板組織は加工性に優れた実質的にフェライト単相となる。また、好ましいCの含有量は、0.001%以上0.004%以下である。
C: 0.001% or more and 0.005% or less When the content of C increases, deep drawability and ductility deteriorate, and the formability required for steel sheets for automobile outer sheets and inner sheets may be imparted to the steel sheets. It becomes difficult. For this reason, the upper limit of the C content is specified to be 0.005%. On the other hand, when the content of C is less than 0.001%, the crystal grains become coarse, and the surface of the steel sheet is likely to be rough when formed. For this reason, the lower limit of the C content is specified to be 0.001%. When the C content in the component composition of the steel sheet used in the present invention is in the above range, the steel sheet structure is substantially a ferrite single phase excellent in workability. Moreover, preferable content of C is 0.001% or more and 0.004% or less.
Si:0.10%以下
Siの含有量が0.10%を超えるとスケールに起因した表面欠陥が発生しやすくなる。また、Siの含有量が過剰になると、後述する金属間化合物の形成を阻害する場合がある。また、Siの含有量が過剰になると、Siの核発生が抑制され鋼板組織中の1つ1つの結晶が粗大化し、プレス加工後のめっき密着性が劣化する問題が生じる。好ましいSiの含有量は0.02%以下である。
Si: 0.10% or less When the Si content exceeds 0.10%, surface defects due to scale are likely to occur. Moreover, when content of Si becomes excess, formation of the intermetallic compound mentioned later may be inhibited. Further, when the Si content is excessive, the generation of Si nuclei is suppressed, and each crystal in the steel sheet structure becomes coarse, resulting in a problem that the plating adhesion after press working deteriorates. A preferable Si content is 0.02% or less.
Mn:0.70%以上1.50%以下
Mnの含有量が0.70%未満では充分な強度を有する鋼板が得られない。Mnを鋼板に多量に含有させることで、鋼板を高強度化できるが、Mnを過剰に含有させると深絞り性が低下する。また、Mnを過剰に含有させると、後述する金属間化合物の形成が阻害される。また、Mnを過剰に含有させると、Siの核発生が抑制され鋼板組織中の1つ1つの結晶が粗大化し、プレス加工後のめっき密着性が劣化する。このため、Mnの含有量の上限は1.50%とする。また、好ましいMnの含有量は0.75%以上1.2%以下である。
Mn: 0.70% or more and 1.50% or less If the Mn content is less than 0.70%, a steel sheet having sufficient strength cannot be obtained. By containing a large amount of Mn in the steel sheet, the steel sheet can be strengthened, but when Mn is contained excessively, the deep drawability is lowered. Moreover, when Mn is contained excessively, formation of the intermetallic compound mentioned later is inhibited. Moreover, when Mn is contained excessively, the nucleation of Si is suppressed, and each crystal in the steel sheet structure becomes coarse, and the plating adhesion after press working deteriorates. For this reason, the upper limit of the Mn content is 1.50%. A preferable Mn content is 0.75% or more and 1.2% or less.
P:0.050%以上0.100%以下
Pの含有量が0.050%未満では、鋼板の加工性が良好にならず、また、降伏応力(YS)等の機械特性が所望の水準を満たさない。Pの含有量が0.100%を超えると溶接部の靱性が劣化したり、延性が劣化したりする。好ましいPの含有量は0.050%以上0.085%以下である。
P: 0.050% or more and 0.100% or less If the P content is less than 0.050%, the workability of the steel sheet is not good, and the mechanical properties such as yield stress (YS) are at a desired level. I do not meet. If the P content exceeds 0.100%, the toughness of the welded portion deteriorates or the ductility deteriorates. P content is preferably 0.050% or more and 0.085% or less.
S:0.010%以下
Sの含有量が多いと、Pの含有量が多い場合と同様に溶接部の靭性が劣化する。このためSの含有量の上限は0.010%とする。好ましいSの含有量は0.007%以下である。
S: 0.010% or less When the content of S is large, the toughness of the welded portion deteriorates as in the case where the content of P is large. For this reason, the upper limit of the S content is 0.010%. A preferable S content is 0.007% or less.
N:0.005%以下、Al:0.10%以下
Al(sol.Al)とNは、通常の鋼板が含有する量であれば本発明の効果を損なわない。また、Nは、Tiと結合してTiNを形成したり、Alと結合してAlNを形成したりする。そこで、Alの含有量を0.10%以下、Nの含有量を0.005%以下に規定する。Alの含有量が0.10%を超えると、後述する金属間化合物の形成が阻害される。また、Alの含有量が0.10%を超えると、Siの核発生が抑制され鋼板組織中の1つ1つの結晶が粗大化し、加工時のめっき密着性が劣化する。また、Nの含有量が0.005%を超えると窒化物がフェライト粒内に分散して加工硬化率が低下する。好ましいAlの含有量は0.04%以下であり、好ましいNの含有量は0.002以下である。
N: 0.005% or less, Al: 0.10% or less Al (sol. Al) and N do not impair the effects of the present invention as long as they are contained in a normal steel sheet. N combines with Ti to form TiN, or N combines with Al to form AlN. Therefore, the Al content is specified to be 0.10% or less, and the N content is specified to be 0.005% or less. If the Al content exceeds 0.10%, formation of an intermetallic compound described later is inhibited. On the other hand, if the Al content exceeds 0.10%, the generation of Si nuclei is suppressed, and each crystal in the steel sheet structure is coarsened, and the plating adhesion during processing deteriorates. On the other hand, when the N content exceeds 0.005%, the nitride is dispersed in the ferrite grains, and the work hardening rate is lowered. The preferable Al content is 0.04% or less, and the preferable N content is 0.002 or less.
B:0.0015%以下
Bは、炭化物を形成して清浄化された粒界の強化に寄与する元素である。この効果を得る観点からは、Bの含有量の下限は0.0003%であることが好ましい。しかしながら、B含有量が0.0015%を超えると、固溶強化により加工硬化率が低下する。また、Bは再結晶焼鈍時における表面の選択酸化を促進する。そのため、Bの含有量の上限は0.0015%とする。また、好ましいBの含有量は0.0003%以上0.0010%以下である。
B: 0.0015% or less B is an element that contributes to strengthening of grain boundaries cleaned by forming carbides. From the viewpoint of obtaining this effect, the lower limit of the B content is preferably 0.0003%. However, if the B content exceeds 0.0015%, the work hardening rate decreases due to solid solution strengthening. Further, B promotes selective oxidation of the surface during recrystallization annealing. Therefore, the upper limit of the B content is 0.0015%. Moreover, preferable content of B is 0.0003% or more and 0.0010% or less.
Ti:0.01%以上0.05%以下及びNb:0.01%以上0.05%以下のうちから選択される少なくとも一種
TiやNbは、フェライト粒内で炭化物(TiC、NbC)を形成することにより、鋼板の加工硬化率を向上させる。ただし、TiやNbの含有量が0.01%未満では、Tiの炭化物量やNbの炭化物量が少なく、転位運動の制御ができず、十分な加工硬化率の上昇を望めない。一方、NbやTi含有量が0.05%を超えると、粗大な炭化物が析出し、加工硬化率が低下する。また、NbやTi含有量が0.05%を超えると、鋼板組織中の粒界が清浄化されて溶融亜鉛めっき処理時に金属間化合物が過剰に成長してめっき密着性が劣化する。このため、Ti及びNbの併用又は単独使用に関わらず、Tiの含有量、Nbの含有量は少なくとも一方が0.01%以上0.05%以下とする。好ましいTiの含有量は0.015%以上0.04%以下であり、好ましいNbの含有量は0.01%以上0.03%以下である。なお、TiとNbの両方を含む場合に、一方の含有量が上記範囲外であれば、本発明の範囲外である。
At least one selected from Ti: 0.01% to 0.05% and Nb: 0.01% to 0.05% Ti and Nb form carbides (TiC, NbC) in the ferrite grains. By doing, the work hardening rate of a steel plate is improved. However, when the content of Ti or Nb is less than 0.01%, the amount of carbide of Ti or the amount of carbide of Nb is small, the dislocation motion cannot be controlled, and a sufficient work hardening rate cannot be expected. On the other hand, when the Nb or Ti content exceeds 0.05%, coarse carbides are precipitated and the work hardening rate is lowered. On the other hand, if the Nb or Ti content exceeds 0.05%, the grain boundaries in the steel sheet structure are cleaned, and the intermetallic compound grows excessively during the hot dip galvanizing process, resulting in poor plating adhesion. For this reason, regardless of the combined use or single use of Ti and Nb, at least one of the Ti content and the Nb content is 0.01% or more and 0.05% or less. A preferable Ti content is 0.015% or more and 0.04% or less, and a preferable Nb content is 0.01% or more and 0.03% or less. In addition, when both Ti and Nb are included, if one content is outside the above range, it is outside the scope of the present invention.
Feおよび不可避的不純物
上記した成分以外の残部は、Fe及び不可避的不純物である。ここで不可避的不純物とは、例えばO(酸素)である。Oは不可避的に混入する代表的な不可避的不純物である。不可避的不純物の含有量は特に限定されず、許容される不可避的不純物の含有量は不可避的不純物の種類にもよる。Oの場合には含有量が0.005%以下であれば問題が無い。
Fe and unavoidable impurities The balance other than the above components is Fe and unavoidable impurities. Here, the unavoidable impurity is, for example, O (oxygen). O is a typical inevitable impurity inevitably mixed. The content of inevitable impurities is not particularly limited, and the allowable content of inevitable impurities depends on the type of inevitable impurities. In the case of O, there is no problem if the content is 0.005% or less.
鋼板組織
鋼板組織は実質的にフェライト単相である。鋼板組織が実質的にフェライト単相から構成されることで、溶融亜鉛めっき鋼板は加工性に優れる。ここで、実質的にフェライト単相には、鋼板組織の全てがフェライト相である場合の他、鋼板組織の95%以上がフェライト相である場合も含まれる。ただし、通常はフェライト以外の相が生成しないと考えられる。なお、実質的にフェライト単相であることは、光学顕微鏡でエッチングした試料断面を観察して確認する。
Steel sheet structure The steel sheet structure is substantially a ferrite single phase. Since the steel sheet structure is substantially composed of a ferrite single phase, the hot dip galvanized steel sheet is excellent in workability. Here, the ferrite single phase substantially includes not only the case where the entire steel sheet structure is the ferrite phase but also the case where 95% or more of the steel sheet structure is the ferrite phase. However, it is normally considered that no phase other than ferrite is generated. Note that the fact that it is substantially a ferrite single phase is confirmed by observing a cross section of the etched sample with an optical microscope.
<溶融亜鉛めっき層>
溶融亜鉛めっき層とは、通常の溶融亜鉛めっき処理によって形成される溶融亜鉛めっき層である。また、溶融亜鉛めっき層は、Alを質量%で0.3%以上0.6%以下含む。本発明においては、溶融亜鉛めっき層にZn、Al以外の成分を、本発明の効果を害さない範囲で含んでもよい。Zn、Al以外の成分としてはFe、Al、Mg、Cr等が挙げられる。
<Hot galvanized layer>
The hot dip galvanized layer is a hot dip galvanized layer formed by a normal hot dip galvanizing process. The hot-dip galvanized layer contains Al in an amount of 0.3% to 0.6% by mass. In the present invention, the hot dip galvanized layer may contain components other than Zn and Al as long as the effects of the present invention are not impaired. Examples of components other than Zn and Al include Fe, Al, Mg, and Cr.
Alの含有量が0.3%未満の場合、めっき浴中のAl濃度を低くする必要がある。上記Al濃度が低くなるとFeの溶出があるため、ドロスが析出して外観性が悪化したり、硬質のドロスが溶融亜鉛めっき層中に分散したりする。ドロスが溶融亜鉛めっき層中に分散すると溶融亜鉛めっき鋼板の加工性が劣化する。Alの含有量が0.6%超えだと溶融亜鉛めっき層表面にAlの酸化皮膜が多量に形成されて、溶融亜鉛めっき鋼板のスポット溶接性が劣化する。 When the Al content is less than 0.3%, it is necessary to reduce the Al concentration in the plating bath. When the Al concentration is lowered, Fe is eluted, so that dross is deposited and appearance is deteriorated, or hard dross is dispersed in the hot dip galvanized layer. When dross is dispersed in the hot dip galvanized layer, the workability of the hot dip galvanized steel sheet deteriorates. If the Al content exceeds 0.6%, a large amount of an oxide film of Al is formed on the surface of the hot dip galvanized layer, and the spot weldability of the hot dip galvanized steel sheet deteriorates.
溶融亜鉛めっき層は、溶融亜鉛めっき層の表面の表面粗さRaが0.8μm以上1.6μm以下であることが好ましい。表面粗さRaが0.8未満だと溶融亜鉛めっき鋼板のプレス時に油が溶融亜鉛めっき層の表面に保持されず加工性に劣る場合がある。表面粗さRaが1.6μm超えだと塗装後鮮鋭性が劣り優れた外観を塗装後の溶融亜鉛めっき鋼板に付与できない場合がある。なお、上記表面粗さRaは、実施例に記載の方法で測定された表面粗さRaを意味する。 The hot-dip galvanized layer preferably has a surface roughness Ra of 0.8 to 1.6 μm. If the surface roughness Ra is less than 0.8, the oil may not be retained on the surface of the hot dip galvanized layer during pressing of the hot dip galvanized steel sheet, and workability may be poor. If the surface roughness Ra exceeds 1.6 μm, the sharpness after coating may be inferior and an excellent appearance may not be imparted to the hot-dip galvanized steel sheet after coating. In addition, the said surface roughness Ra means surface roughness Ra measured by the method as described in an Example.
溶融亜鉛めっき層の表面の光沢度(G値)が550以上750以下であることが好ましい。上記光沢度(G値)が550未満であると塗装後鮮鋭性が劣り塗装後の溶融亜鉛めっき鋼板に優れた外観を付与できない場合がある。光沢度(G値)が750以上だと平滑すぎて、溶融亜鉛めっき鋼板のプレス時に油が溶融亜鉛めっき層の表面に保持されず成形性に劣る場合がある。なお、上記光沢度(G値)は実施例に記載の方法で測定された光沢度(G値)を意味する。 The glossiness (G value) of the surface of the hot dip galvanized layer is preferably 550 or more and 750 or less. If the glossiness (G value) is less than 550, the sharpness after coating may be inferior, and an excellent appearance may not be imparted to the hot-dip galvanized steel sheet after coating. If the glossiness (G value) is 750 or more, it may be too smooth, and oil may not be retained on the surface of the hot dip galvanized layer when the hot dip galvanized steel sheet is pressed, resulting in poor formability. In addition, the said glossiness (G value) means the glossiness (G value) measured by the method as described in an Example.
溶融亜鉛めっき層の表面における、Zn結晶の(002)面の結晶配向性とZn結晶の(004)面の結晶配向性との比である亜鉛基底面配向率(Zn(002)/(004))が60以上90以下であることが好ましい。亜鉛基底面配向率が60未満だと亜鉛結晶の配向が比較的ランダムであり、めっき直後に亜鉛が凝固する際の結晶サイズが細かくなるため、溶融亜鉛めっき層の表面が平滑すぎてプレス時に油が該表面に保持されずに成形性に劣る場合がある。亜鉛基底面配向率が90超えだとZn結晶の基底面の配向が高すぎて結晶粒が成長しやすく、結果としてデンドライドアームが発達するため、塗装後鮮鋭性が劣り塗装後の溶融亜鉛めっき鋼板の外観が悪化する可能性がある。また、亜鉛基底面配向率が90超えだと耐食性も劣化する可能性がある。ここで亜鉛基底面配向率は以下の式で規定できる。 Zinc basal plane orientation ratio (Zn (002) / (004)), which is the ratio of the crystal orientation of the (002) plane of Zn crystal to the crystal orientation of the (004) plane of Zn crystal on the surface of the hot dip galvanized layer. ) Is preferably 60 or more and 90 or less. If the orientation ratio of the bottom surface of the zinc base is less than 60, the orientation of the zinc crystals is relatively random, and the crystal size when the zinc solidifies immediately after plating becomes fine. May be inferior in moldability without being held on the surface. If the orientation ratio of the basal plane of the zinc base is more than 90, the orientation of the basal plane of the Zn crystal is too high and the crystal grains are likely to grow. As a result, the dendritic arm develops. The appearance of the steel sheet may deteriorate. Moreover, if the zinc base bottom surface orientation ratio exceeds 90, the corrosion resistance may be deteriorated. Here, the zinc base bottom surface orientation ratio can be defined by the following formula.
亜鉛基底面配向率(Zn(002)/(004))は{(002)面のZn結晶配向性}/{(004)面のZn結晶配向性}を表す。また、(I(xyz)はサンプルの(xyz)面におけるX線で測定したZn強度、Istd(xyz)は標準サンプル(純Zn粉末)の(xyz)面におけるX線で測定したZn強度を意味する)
上記のようにして亜鉛基底面配向率を規定すれば、Znはhcp構造をとり通常は基底面に配向し易く、どの程度結晶がランダムに配向したかが分かる。この凝固組織の配向程度は、光沢、結晶サイズ、表面での粗度(表面粗さ)に影響する。このため、亜鉛基底配向率を正確に制御することは、溶融亜鉛めっき鋼板の表面性状を調整する際に重要であることに加えて、プレス加工性を制御する際にも重要である。なお、亜鉛基底面配向率が上記範囲にあれば、光沢や表面粗さRaは上記好ましい範囲を満たす。
The zinc base bottom orientation ratio (Zn (002) / (004)) represents {(002) plane Zn crystal orientation} / {(004) plane Zn crystal orientation}. Further, (I (xyz) is the Zn intensity measured by X-ray on the (xyz) plane of the sample, and I std (xyz) is the Zn intensity measured by X-ray on the (xyz) plane of the standard sample (pure Zn powder). means)
If the zinc basal plane orientation ratio is defined as described above, Zn has an hcp structure and is usually easily oriented to the basal plane, and it can be understood how much crystals are randomly oriented. The degree of orientation of the solidified structure affects the gloss, crystal size, and surface roughness (surface roughness). For this reason, it is important to control the press workability in addition to controlling the surface orientation of the hot-dip galvanized steel sheet in order to accurately control the zinc base orientation ratio. In addition, if the zinc base bottom surface orientation ratio is in the above range, the gloss and the surface roughness Ra satisfy the above preferable range.
また、溶融亜鉛めっき層は、鋼板表面の少なくとも一部に形成されればよい。溶融亜鉛めっき層は、鋼板をめっき浴に浸漬する方法で鋼板表面に形成されるため、通常、鋼板表面の全体に溶融亜鉛めっき層が形成される。 Further, the hot dip galvanized layer may be formed on at least a part of the steel plate surface. Since the hot dip galvanized layer is formed on the surface of the steel plate by a method of immersing the steel plate in a plating bath, the hot dip galvanized layer is usually formed on the entire surface of the steel plate.
また、溶融亜鉛めっき層の厚みは特に限定されない。溶融亜鉛めっき層の厚みは、溶融亜鉛めっき処理の際のめっき付着量を制御することで調整することができる。 Further, the thickness of the hot dip galvanized layer is not particularly limited. The thickness of the hot dip galvanized layer can be adjusted by controlling the amount of plating applied during the hot dip galvanizing process.
<金属間化合物>
金属間化合物は、平均粒径1μm以下のFe2Al5もしくはFeAl3の少なくとも一種からなる金属間化合物から構成され、鋼板と溶融亜鉛めっき層間に存在する。また、金属間化合物は、0.12gm-2以上0.22gm-2以下のAlを含む。上記金属間化合物が存在することでFeZn合金相の形成を抑制して良好なめっき密着性が確保できる。この効果はFe2Al5もしくはFeAl3の少なくとも一種からなる金属間化合物以外の場合には得られない。これら以外では、硬くて脆いFeZn金属間化合物が生成する場合があり、この場合めっき密着性が劣化する。なお、金属間化合物が存在していることの確認は、溶融亜鉛めっき層の断面における鋼板との界面付近を透過電子顕微鏡中で、電子線回折によって解析して検出する方法で行うことができる。
<Intermetallic compound>
Intermetallic compound is composed of an intermetallic compound consisting of at least one of an average particle diameter of 1μm or less of Fe 2 Al 5 or FeAl 3, present in the steel sheet and hot-dip galvanizing layer. Further, the intermetallic compound contains 0.12 gm −2 or more and 0.22 gm −2 or less of Al. The presence of the intermetallic compound can suppress the formation of the FeZn alloy phase and ensure good plating adhesion. This effect cannot be obtained in cases other than an intermetallic compound composed of at least one of Fe 2 Al 5 or FeAl 3 . Other than these, a hard and brittle FeZn intermetallic compound may be formed, and in this case, the plating adhesion deteriorates. The presence of the intermetallic compound can be confirmed by a method of analyzing and detecting the vicinity of the interface with the steel plate in the cross section of the hot dip galvanized layer by electron beam diffraction in a transmission electron microscope.
Fe2Al5やFeAl3の平均粒径が1μm超えだと硬質の金属間化合物が過剰成長していることになり、溶融亜鉛めっき鋼板の耐衝撃特性が劣化する。このため、上記平均粒径の上限は1μmとする。 If the average particle diameter of Fe 2 Al 5 or FeAl 3 exceeds 1 μm, the hard intermetallic compound is excessively grown, and the impact resistance characteristics of the hot dip galvanized steel sheet deteriorate. For this reason, the upper limit of the average particle diameter is 1 μm.
金属間化合物中のAlの含有量が0.12gm-2未満だと、めっきの溶融亜鉛浴中のAl濃度を低く設定する必要があり、上記Al濃度を低く設定するとドロスが析出して溶融亜鉛めっき鋼板の外観性や加工性が劣化する。金属間化合物中のAlの含有量が0.22gm-2超えだとめっき浴中のAl濃度を高く設定する必要があり、上記Al濃度を高く設定すると溶融亜鉛めっき層表面にAlの酸化皮膜が多量に形成されてスポット溶接性が劣化する。 If the Al content in the intermetallic compound is less than 0.12 gm −2, it is necessary to set the Al concentration in the molten zinc bath of the plating low. If the Al concentration is set low, dross precipitates and the molten zinc The appearance and workability of the plated steel sheet deteriorate. If the Al content in the intermetallic compound exceeds 0.22 gm -2 , the Al concentration in the plating bath needs to be set high. If the Al concentration is set high, an Al oxide film is formed on the surface of the hot dip galvanized layer. A large amount is formed and spot weldability deteriorates.
<溶融亜鉛めっき鋼板の物性>
本発明の溶融亜鉛めっき鋼板は、プレス加工後のめっき密着性に優れ、プレス加工後における加工部の塗装後耐食性に優れる。そして、本発明の溶融亜鉛めっき鋼板は、優れた塗装後外観を有する。このため、本発明の溶融亜鉛めっき鋼板は、バックドアやフードなどの非常に厳しい加工部位を有する製品にも適用可能である。
<Physical properties of hot-dip galvanized steel sheet>
The hot dip galvanized steel sheet of the present invention is excellent in plating adhesion after press working and excellent in corrosion resistance after painting of a processed part after press working. And the hot-dip galvanized steel sheet of the present invention has an excellent appearance after coating. For this reason, the hot dip galvanized steel sheet of the present invention can be applied to products having very severe processing parts such as a back door and a hood.
また、本発明の溶融亜鉛めっき鋼板は降伏応力(YS)が220MPa以上320MPa以下である。降伏応力が上記範囲にあれば、主に外板等の厳しい加工が要求される用途であり且つ形状凍結性を確保しなければならない用途にも溶融亜鉛めっき鋼板を好ましく適用できる。 Moreover, the hot dip galvanized steel sheet of the present invention has a yield stress (YS) of 220 MPa or more and 320 MPa or less. If the yield stress is in the above range, the hot-dip galvanized steel sheet can be preferably applied to applications that require severe processing such as outer plates and that must ensure shape freezeability.
<溶融亜鉛めっき鋼板の製造方法>
続いて、溶融亜鉛めっき鋼板の製造方法について説明する。例えば、以下の方法で溶融亜鉛めっき鋼板を製造可能である。先ず、上記のような成分組成を有する鋼を連続鋳造によりスラブとし、該スラブを加熱し、スケール除去および粗圧延を施す。次いで、冷却した後、仕上げ圧延し、冷却し、巻取り、次いで、酸洗、冷間圧延を行う。次いで、連続式溶融亜鉛めっき設備において、鋼板の焼鈍および溶融亜鉛めっき処理を行う。次いで、必要に応じて合金化処理を行う。
<Method for producing hot-dip galvanized steel sheet>
Then, the manufacturing method of a hot dip galvanized steel plate is demonstrated. For example, a hot-dip galvanized steel sheet can be manufactured by the following method. First, steel having the above component composition is made into a slab by continuous casting, the slab is heated, and scale removal and rough rolling are performed. Next, after cooling, finish rolling, cooling, winding, pickling, and cold rolling are performed. Next, the steel sheet is annealed and hot-dip galvanized in a continuous hot-dip galvanizing facility. Next, an alloying treatment is performed as necessary.
スラブを加熱する際の加熱時間、加熱温度、粗圧延の条件、冷却条件、仕上げ圧延の条件、巻取りの条件等は、技術常識に基づいて適宜設定可能である。 The heating time, heating temperature, rough rolling conditions, cooling conditions, finish rolling conditions, winding conditions, etc. when heating the slab can be appropriately set based on common technical knowledge.
また、鋼板の焼鈍の条件は、溶融亜鉛めっき鋼板の降伏応力に影響を与える。本発明においては、降伏応力を上記範囲に設定するために、焼鈍の際の加熱温度を780℃以上820℃以下に設定することが好ましい。 Also, the annealing conditions of the steel sheet affect the yield stress of the hot dip galvanized steel sheet. In the present invention, in order to set the yield stress in the above range, it is preferable to set the heating temperature during annealing to 780 ° C. or more and 820 ° C. or less.
本発明においては、溶融亜鉛めっき層のAl含有量を制御し、鋼板と溶融亜鉛めっき層との間に金属間化合物を存在させるために、溶融亜鉛めっき処理の条件を特定の条件にする必要がある。また、溶融亜鉛めっき層の表面状態(表面粗さRa、光沢度(G値)、亜鉛基底面配向率)を所望の状態にするためにも、溶融亜鉛めっき処理の条件を調整する必要がある。以下、溶融亜鉛めっき処理の条件について説明する。 In the present invention, in order to control the Al content of the hot dip galvanized layer and allow an intermetallic compound to exist between the steel plate and the hot dip galvanized layer, the hot dip galvanizing treatment condition needs to be a specific condition. is there. Moreover, in order to make the surface state (surface roughness Ra, glossiness (G value), zinc base bottom orientation ratio) of a hot dip galvanized layer into a desired state, it is necessary to adjust the conditions of the hot dip galvanizing treatment. . Hereinafter, conditions for the hot dip galvanizing process will be described.
焼鈍後の鋼板がめっき浴に進入する際の鋼板の温度である浸入板温は、特に限定されない。本発明において、上記浸入板温はめっき浴の温度(浴温)-20℃以上浴温+20℃以下であることが好ましい。浸入板温が上記範囲にあれば、浴温の変化が小さく、所望の溶融亜鉛めっき処理を連続して行いやすい。 The intrusion plate temperature, which is the temperature of the steel plate when the annealed steel plate enters the plating bath, is not particularly limited. In the present invention, the temperature of the immersion plate is preferably a temperature of the plating bath (bath temperature) of −20 ° C. or higher and a bath temperature of + 20 ° C. or lower. If the infiltration plate temperature is in the above range, the change in bath temperature is small, and it is easy to perform desired hot dip galvanization continuously.
焼鈍後の鋼板が浸入するめっき浴の組成はZn以外にAlを含むものであればよく、必要に応じて他の成分が含まれていてもよい。めっき浴中のAlの濃度は特に限定されない。本発明において、上記Al濃度は0.16質量%以上0.25質量%以下であることが好ましい。Alの濃度が0.16質量%以上0.25質量%以下であればFeAl合金相が形成されてFeZn合金相の形成が抑制されるために好ましい。光沢度はめっき浴中のAl濃度により調整可能である。めっき浴中のAl濃度が低くなると、鋼板と溶融亜鉛めっき層の間の界面にFeAlではなくFeZn結晶が僅かに形成される。このFeZn結晶がZn凝固核発生サイトとなることで多数の亜鉛結晶が生成し、亜鉛結晶配向がランダム化することで配向率が低下する傾向にある。その結果、Al濃度が低いほど、デンドライド状のZn結晶成長が抑制されて、表面の凹凸が低減して平滑化するため、光沢度が上昇する。より好ましいAlの濃度は0.19質量%以上0.22質量%以下である。 The composition of the plating bath into which the annealed steel sheet enters is not limited as long as it contains Al in addition to Zn, and may contain other components as necessary. The concentration of Al in the plating bath is not particularly limited. In the present invention, the Al concentration is preferably 0.16% by mass or more and 0.25% by mass or less. If the concentration of Al is 0.16% by mass or more and 0.25% by mass or less, an FeAl alloy phase is formed and formation of an FeZn alloy phase is suppressed, which is preferable. The glossiness can be adjusted by the Al concentration in the plating bath. When the Al concentration in the plating bath becomes low, FeZn crystals rather than FeAl are formed slightly at the interface between the steel sheet and the hot dip galvanized layer. When this FeZn crystal becomes a Zn solidification nucleus generation site, a large number of zinc crystals are generated, and the orientation rate tends to decrease due to randomization of the zinc crystal orientation. As a result, as the Al concentration is lower, dendritic Zn crystal growth is suppressed, and surface unevenness is reduced and smoothed, so that the glossiness increases. A more preferable Al concentration is 0.19% by mass or more and 0.22% by mass or less.
また、めっき浴の温度(浴温)は特に限定されない。本発明において、上記浴温は440℃以上480℃以下が好ましい。浴温が440℃以上480℃以下であれば、適度な浴温を安定して確保でき浴温分布が劣化してもZnが凝固しないという理由で好ましい。また、浴温が低下するとFeAl合金相の溶解度が低下するため、FeAl合金相の生成量が増加傾向である。より好ましい浴温の範囲は450℃以上460℃以下である。 Further, the temperature of the plating bath (bath temperature) is not particularly limited. In the present invention, the bath temperature is preferably 440 ° C. or higher and 480 ° C. or lower. A bath temperature of 440 ° C. or higher and 480 ° C. or lower is preferable because an appropriate bath temperature can be stably secured and Zn does not solidify even if the bath temperature distribution is deteriorated. Moreover, since the solubility of the FeAl alloy phase decreases as the bath temperature decreases, the amount of FeAl alloy phase generated tends to increase. A more preferable range of the bath temperature is 450 ° C. or higher and 460 ° C. or lower.
鋼板をめっき浴への浸漬させる際の浸漬時間は特に限定されない。本発明において、上記浸漬時間は0.5秒以上3秒以下であることが好ましい。浸漬時間が上記範囲にあることで、鋼板の表面に所望の溶融亜鉛めっき層を形成しやすい。 The immersion time when the steel sheet is immersed in the plating bath is not particularly limited. In the present invention, the immersion time is preferably 0.5 seconds or more and 3 seconds or less. When the immersion time is in the above range, a desired hot dip galvanized layer is easily formed on the surface of the steel plate.
鋼板をめっき浴から引き上げた直後にガスジェットワイピング等でめっき付着量を調整する。本発明においてめっき付着量は特に限定されない。本発明において、めっき付着量は20g/m2以上120g/m2以下の範囲であることが好ましい。めっき付着量が20g/m2未満では耐食性の確保が困難になる場合がある。一方、めっき付着量が120g/m2を超えると耐めっき剥離性が劣化する場合がある。 Immediately after lifting the steel plate from the plating bath, the amount of plating adhesion is adjusted by gas jet wiping or the like. In the present invention, the plating adhesion amount is not particularly limited. In the present invention, the plating adhesion amount is preferably in the range of 20 g / m 2 or more and 120 g / m 2 or less. If the plating adhesion amount is less than 20 g / m 2 , it may be difficult to ensure corrosion resistance. On the other hand, when the plating adhesion amount exceeds 120 g / m 2 , the plating peel resistance may deteriorate.
上記のようにしてめっき付着量を調整後、調質圧延(SK処理)を行う。SK処理に用いるロールの種類は特に限定されず、Electro-Discharge Textureロール(EDTロール)、Electron Beam Textureロール(EBTロール)、ショットダルロール、トポクロムロール等を使用可能である。 After adjusting the plating adhesion amount as described above, temper rolling (SK treatment) is performed. The type of roll used for the SK treatment is not particularly limited, and an Electro-Discharge Texture roll (EDT roll), an Electron Beam Texture roll (EBT roll), a shotdal roll, a topochrome roll, or the like can be used.
SK処理の際の圧下率(SK圧下率(%))も特に限定されない。本発明においてSK圧化率は0.7~0.9%であることが好ましい。SK圧下率が上記範囲にあれば、表面粗さを上記好ましい範囲に調整しやすい。また、SK圧下率が上記範囲外であると、圧延油を保持するダル目がつかずに成形性が低下する場合があり、また、降伏強度も低下する場合がある。 The rolling reduction rate during SK treatment (SK rolling reduction rate (%)) is not particularly limited. In the present invention, the SK pressure ratio is preferably 0.7 to 0.9%. If the SK rolling reduction is in the above range, the surface roughness can be easily adjusted to the above preferable range. Further, if the SK rolling reduction is outside the above range, the dullness that holds the rolling oil may not be obtained, and the formability may be reduced, and the yield strength may be reduced.
鋼板をめっき浴から引き上げた後の冷却速度({(冷却終了温度)-(冷却開始温度)}/冷却時間)は、-5℃/秒以上-30℃/秒以下であることが好ましい。冷却速度が-5℃/秒以下であるとスパングルが粗大化する場合があるため好ましくなく、-30℃/秒以上は冷却速度を確保するために急冷しなければならず経済性が劣化するため好ましくない。また、冷却速度が遅いとFeAl合金相が分解してFeAl合金相の生成量が低下する。より好ましい冷却速度の範囲は-7℃/秒以上-22℃/秒以下である。なお、ここで、冷却速度とは420℃から400℃まで温度を降下させる際の平均の冷却速度を指す。 The cooling rate ({(cooling end temperature) − (cooling start temperature)} / cooling time) after the steel sheet is pulled up from the plating bath is preferably −5 ° C./second or more and −30 ° C./second or less. If the cooling rate is −5 ° C./second or less, spangles may become coarse, which is not preferable. If the cooling rate is −30 ° C./second or more, rapid cooling is required to secure the cooling rate, resulting in a deterioration in economy. It is not preferable. On the other hand, if the cooling rate is slow, the FeAl alloy phase is decomposed and the amount of FeAl alloy phase produced is reduced. A more preferable range of the cooling rate is −7 ° C./second or more and −22 ° C./second or less. Here, the cooling rate refers to an average cooling rate when the temperature is lowered from 420 ° C. to 400 ° C.
以上の通り、本発明の溶融亜鉛めっき鋼板を説明したが、以下では本発明の溶融亜鉛めっき鋼板の使用について説明する。 As described above, the hot dip galvanized steel sheet of the present invention has been described. Hereinafter, the use of the hot dip galvanized steel sheet of the present invention will be described.
本発明の溶融亜鉛めっき鋼板は、プレス加工後の塗装後耐食性に優れるため、溶融亜鉛めっき層の表面に塗膜が形成される用途に使用されることが好ましい。また、本発明の溶融亜鉛めっき鋼板は、厳しい加工性が要求される用途に適用してもめっき密着性に優れ、耐食性や機械特性も大幅に低下することは無い。厳しい加工性が要求され且つ塗膜が形成される用途としては、自動車の外板、内板等の自動車用鋼板が挙げられる。塗膜の形成方法は特に限定されない。本発明においては、溶融亜鉛めっき層の表面に化成処理を施し、化成皮膜を形成した後、この化成皮膜上に塗膜を形成することが好ましい。 The hot dip galvanized steel sheet of the present invention is preferably used for applications in which a coating film is formed on the surface of the hot dip galvanized layer because it has excellent post-coating corrosion resistance after press working. Moreover, the hot-dip galvanized steel sheet of the present invention is excellent in plating adhesion even when applied to applications requiring strict workability, and does not significantly reduce corrosion resistance and mechanical properties. Examples of applications in which strict processability is required and a coating film is formed include automotive steel plates such as automobile outer plates and inner plates. The method for forming the coating film is not particularly limited. In the present invention, it is preferable that a chemical conversion treatment is performed on the surface of the hot dip galvanized layer to form a chemical conversion film, and then a coating film is formed on the chemical conversion film.
化成処理液としては、塗布型、反応型のいずれも使用可能である。また、化成処理液に含まれる成分も特に限定されず、クロメート処理液を使用してもよいし、クロムフリー化成処理液を使用してもよい。また、化成皮膜は単層であってもよいし、複層であってもよい。 Either a coating type or a reaction type can be used as the chemical conversion treatment liquid. Moreover, the component contained in a chemical conversion liquid is not specifically limited, either a chromate processing liquid may be used and a chromium free chemical conversion liquid may be used. Moreover, the chemical conversion film may be a single layer or a multilayer.
塗膜を形成するための塗装方法は特に限定しない。塗装方法としては電着塗装、ロールコーター塗装、カーテンフロー塗装、スプレー塗装等が挙げられる。また、塗料を乾燥させるために、熱風乾燥、赤外線加熱、誘導過熱等の手段を用いることができる。 The coating method for forming the coating film is not particularly limited. Examples of the coating method include electrodeposition coating, roll coater coating, curtain flow coating, and spray coating. Moreover, in order to dry a coating material, means, such as hot air drying, infrared heating, induction superheating, can be used.
以下、実施例により本発明を説明する。なお、本発明は以下の実施例に限定されない。 Hereinafter, the present invention will be described with reference to examples. The present invention is not limited to the following examples.
表1に示した鋼組成からなる熱延鋼板の黒皮スケールを酸洗で除去して、圧下率75%で冷間圧延し、その後表面をCGL(連続式溶融亜鉛めっきライン)の入側で脱脂前処理した後に焼鈍炉で、表2に示す焼鈍温度で焼鈍し、表2に記載の条件で溶融亜鉛めっき処理した。めっき・ワイピング後の420~400℃までの平均冷却速度も測定した。冷却速度も表2に示した。なお、めっき浴から鋼板を引き上げ、ガスジェットワイピングによりめっき付着量を調整した後、冷却前に表2に示す条件でSK処理を行った。 The black scale of the hot-rolled steel sheet having the steel composition shown in Table 1 is removed by pickling and cold-rolled at a reduction rate of 75%, and then the surface is on the entry side of the CGL (continuous hot dip galvanizing line). After degreasing pretreatment, annealing was performed at an annealing temperature shown in Table 2 in an annealing furnace, and hot dip galvanizing treatment was performed under the conditions shown in Table 2. The average cooling rate from 420 to 400 ° C. after plating and wiping was also measured. The cooling rate is also shown in Table 2. In addition, after pulling up the steel plate from the plating bath and adjusting the plating adhesion amount by gas jet wiping, SK treatment was performed under the conditions shown in Table 2 before cooling.
鋼板の組織がフェライト単相から構成されることを以下の方法で確認した。鋼板から試験片を採取し、圧延方向断面(L断面)を研磨し、ナイタール液でエッチングして、光学顕微鏡(倍率:50~400倍)を用いて、組織を観察し、撮像した。そして、画像解析装置を用いて組織の種類、分率(面積%)を測定した。全ての鋼板が実質的にフェライト単相から構成される鋼板であった。 It was confirmed by the following method that the structure of the steel sheet was composed of a ferrite single phase. A test piece was collected from the steel plate, the cross section in the rolling direction (L cross section) was polished, etched with a nital solution, and the structure was observed and imaged using an optical microscope (magnification: 50 to 400 times). And the kind of tissue and the fraction (area%) were measured using the image analysis apparatus. All the steel plates were steel plates substantially composed of a ferrite single phase.
金属間化合物組成は亜鉛めっき層を発煙硝酸で除去したものの表面をX線回折法で同定した。量については同様にして作成したサンプル表面の金属間化合物の表面を希塩酸で溶解してICPで定量した。めっき層中のAl量についても同様に希塩酸で溶解してICPで定量した。 The intermetallic compound composition was identified by the X-ray diffraction method after removing the zinc plating layer with fuming nitric acid. Regarding the amount, the surface of the intermetallic compound on the sample surface prepared in the same manner was dissolved in dilute hydrochloric acid and quantified by ICP. Similarly, the amount of Al in the plating layer was dissolved in dilute hydrochloric acid and determined by ICP.
金属間化合物の粒径の測定を以下の方法で行った。鋼板から試験片を採取して、圧延方向に平行な断面の金属組織を、走査型電子顕微鏡(SEM)を用いて5000倍で観察し、金属間化合物の平均粒径を測定した。測定結果を表2に示した。 The particle size of the intermetallic compound was measured by the following method. A test piece was collected from the steel plate, and the metal structure of a cross section parallel to the rolling direction was observed with a scanning electron microscope (SEM) at a magnification of 5000 to measure the average particle size of the intermetallic compound. The measurement results are shown in Table 2.
溶融亜鉛めっき層の表面粗さRaの測定は以下の方法で行った。JIS B 0601の規定に準拠し、触針式表面粗さ計を用いて、算術平均粗さRaを測定した。測定結果を表2に示した。 The surface roughness Ra of the hot dip galvanized layer was measured by the following method. In accordance with the provisions of JIS B 0601, the arithmetic average roughness Ra was measured using a stylus type surface roughness meter. The measurement results are shown in Table 2.
光沢度(G値)の測定は、光沢度計を用いて行った。測定結果を表2に示した。 Glossiness (G value) was measured using a gloss meter. The measurement results are shown in Table 2.
X線回折装置を用いて、溶融亜鉛めっき層表面のZn結晶の(002)面の結晶配向性とZn結晶の(004)面の結晶配向性を測定し、亜鉛基底面配向率(Zn(002)/(004))を導出した。亜鉛基底面配向率を表2に示した。 Using an X-ray diffractometer, the crystal orientation of the (002) plane of the Zn crystal on the surface of the hot dip galvanized layer and the crystal orientation of the (004) plane of the Zn crystal are measured, and the zinc base bottom orientation ratio (Zn (002 ) / (004)). The zinc base bottom surface orientation ratio is shown in Table 2.
得られた溶融亜鉛めっき鋼板について、化成処理、電着塗装、中塗り、上塗りの総合塗装を実施して塗膜が形成された溶融亜鉛めっき鋼板を製造し、目視にて塗装後外観性を評価した。めっきムラなどが原因となる外観不良がない場合は良好、ある場合には不良と評価した。評価結果を表1に示した。 The resulting hot-dip galvanized steel sheet is subjected to chemical conversion treatment, electrodeposition coating, intermediate coating, and top coating to produce a hot-dip galvanized steel sheet on which a coating film has been formed and visually evaluated after coating. did. When there was no appearance defect due to plating unevenness or the like, it was evaluated as good, and when it was present, it was evaluated as defective. The evaluation results are shown in Table 1.
プレス加工後における加工部のめっき密着性は、板厚減少率10%の条件で円錐台張り出し成形(プレス成形に相当する成形)した部分について、1843gで撃芯径5/8inchのポンチを高さ1mから落下させる耐衝撃性試験を実施し、セロハンテープ剥離する方法で評価した。剥離があるものを密着不良(×)、無いものを密着良好(○)とした。評価結果を表2に示した。 As for the plating adhesion of the processed part after press working, the punch with a frustum diameter of 5/8 inch is heightened at 1843 g for the part subjected to frustoconical overmolding (molding equivalent to press molding) under the condition of a plate thickness reduction rate of 10%. An impact resistance test of dropping from 1 m was performed, and evaluation was performed by a method of peeling cellophane tape. Those with peeling were considered poor adhesion (x), and those without peeling were good adhesion (◯). The evaluation results are shown in Table 2.
円錐張り出し成型した部分を化成処理、電着塗装、中塗り、上塗りの総合塗装を実施し、塗装後耐食性を次の方法で評価した。JIS Z 2371(2000年)に基づく塩水噴霧試験を10日間行い、プレス加工後における加工部の膨れ有無を評価した。膨れが有るものを不良(×)、膨れが無いものを良好(○)とした。評価結果を表2に示した。 ¡Cone overhang molding part was subjected to chemical treatment, electrodeposition coating, intermediate coating, and top coating, and the corrosion resistance after coating was evaluated by the following method. A salt spray test based on JIS Z 2371 (2000) was conducted for 10 days, and the presence or absence of swelling of the processed part after press working was evaluated. Those with blisters were judged as bad (x), and those without blisters were judged as good (◯). The evaluation results are shown in Table 2.
溶融亜鉛めっき鋼板から、圧延方向に対して90°方向にJIS5号引張試験片を採取し、JIS Z 2241の規定に準拠してクロスヘッド速度が10mm/min(一定)の条件で引張試験を行った。YSが220~320MPaのものを良好とした。評価結果を表2に示した。 A JIS No. 5 tensile test piece is taken from the hot dip galvanized steel sheet in the direction of 90 ° with respect to the rolling direction, and a tensile test is performed under the condition that the crosshead speed is 10 mm / min (constant) in accordance with the provisions of JIS Z 2241. It was. A YS of 220 to 320 MPa was considered good. The evaluation results are shown in Table 2.
表2から明らかなように、本発明の溶融亜鉛めっき鋼板はプレス加工したにもかかわらず特性が極めて良好でありめっき剥離が起こらない。耐食性も良好である。 As is apparent from Table 2, the hot-dip galvanized steel sheet of the present invention has extremely good characteristics and does not undergo plating peeling despite being pressed. Corrosion resistance is also good.
Claims (2)
前記鋼板の表面の少なくとも一部に形成された、Alを質量%で0.3%以上0.6%以下含む溶融亜鉛めっき層と、
前記鋼板と前記溶融亜鉛めっき層間に存在する、0.12gm-2以上0.22gm-2以下のAlを含み、かつ平均粒径1μm以下のFe2Al5もしくはFeAl3の少なくとも一種からなる金属間化合物と、を有し、
降伏応力(YS)が220MPa以上320MPa以下である溶融亜鉛めっき鋼板。 In mass%, C: 0.001% to 0.005%, Si: 0.10% or less, Mn: 0.70% to 1.50%, P: 0.050% to 0.100% , S: 0.010% or less, N: 0.005% or less, Al: 0.10% or less, B: 0.0015% or less, and Ti: 0.01% or more and 0.05% or less And Nb: containing at least one selected from 0.01% to 0.05%, the balance being a composition of Fe and inevitable impurities, and a steel plate substantially composed of a ferrite single phase;
Formed on at least a part of the surface of the steel sheet, a hot-dip galvanized layer containing Al by 0.3% to 0.6% by mass,
Between the steel sheet and the hot-dip galvanized layer, between 0.12 gm −2 and 0.22 gm −2 of Al and having an average particle size of 1 μm or less and consisting of at least one of Fe 2 Al 5 or FeAl 3 And having a compound,
A hot-dip galvanized steel sheet having a yield stress (YS) of 220 MPa or more and 320 MPa or less.
前記溶融亜鉛めっき層の表面の光沢度(G値)が550以上750以下であり、
前記溶融亜鉛めっき層の表面における、Zn結晶の(002)面の結晶配向性とZn結晶の(004)面の結晶配向性との比である亜鉛基底面配向率(Zn(002)/(004))が60以上90以下であることを特徴とする請求項1に記載の溶融亜鉛めっき鋼板。 The surface roughness Ra of the surface of the hot dip galvanized layer is 0.8 μm or more and 1.6 μm or less,
The glossiness (G value) of the surface of the hot dip galvanized layer is 550 or more and 750 or less,
Zinc basal plane orientation ratio (Zn (002) / (004), which is the ratio of the crystal orientation of the (002) plane of Zn crystal to the crystal orientation of the (004) plane of Zn crystal on the surface of the hot dip galvanized layer. The hot dip galvanized steel sheet according to claim 1, wherein)) is 60 or more and 90 or less.
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- 2013-10-21 CN CN201380056703.XA patent/CN104755647B/en active Active
- 2013-10-21 MX MX2015005403A patent/MX348834B/en active IP Right Grant
- 2013-10-21 IN IN2531DEN2015 patent/IN2015DN02531A/en unknown
- 2013-10-21 WO PCT/JP2013/006202 patent/WO2014068889A1/en not_active Ceased
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- 2013-10-28 TW TW102138903A patent/TWI511875B/en not_active IP Right Cessation
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| JP2002173754A (en) * | 2000-09-29 | 2002-06-21 | Kawasaki Steel Corp | Hot-dip galvanized steel sheet and method for producing the same |
| WO2011161833A1 (en) * | 2010-06-21 | 2011-12-29 | 新日本製鐵株式会社 | Hot-dip al-coated steel sheet with excellent thermal blackening resistance and process for production of same |
| WO2013047812A1 (en) * | 2011-09-30 | 2013-04-04 | 新日鐵住金株式会社 | High-strength hot-dip galvanized steel sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016030171A1 (en) * | 2014-08-25 | 2016-03-03 | Voestalpine Stahl Gmbh | Micro-alloyed steel and assembled blanks made of micro-alloyed steel and press-hardened steel |
| CN104195434A (en) * | 2014-09-22 | 2014-12-10 | 武汉钢铁(集团)公司 | Hot galvanized high-strength steel with 390MPa tensile strength for internal structural member of saloon car and production method of hot galvanized high-strength steel |
| KR20170054512A (en) * | 2014-10-17 | 2017-05-17 | 제이에프이 스틸 가부시키가이샤 | High-strength hot-dip-galvanized steel sheet |
| CN106795612A (en) * | 2014-10-17 | 2017-05-31 | 杰富意钢铁株式会社 | High-strength hot-dip galvanized steel sheet |
| WO2016059743A1 (en) * | 2014-10-17 | 2016-04-21 | Jfeスチール株式会社 | Hot-dip-galvanized steel sheet |
| JP5907323B1 (en) * | 2014-10-17 | 2016-04-26 | Jfeスチール株式会社 | High strength hot dip galvanized steel sheet |
| JP5907324B1 (en) * | 2014-10-17 | 2016-04-26 | Jfeスチール株式会社 | High strength hot dip galvanized steel sheet |
| JP6037056B2 (en) * | 2014-10-17 | 2016-11-30 | Jfeスチール株式会社 | Hot-dip galvanized steel sheet |
| WO2016059742A1 (en) * | 2014-10-17 | 2016-04-21 | Jfeスチール株式会社 | High-strength hot-dip-galvanized steel sheet |
| WO2016059741A1 (en) * | 2014-10-17 | 2016-04-21 | Jfeスチール株式会社 | High-strength hot-dip-galvanized steel sheet |
| EP3178960A4 (en) * | 2014-10-17 | 2017-08-02 | JFE Steel Corporation | High-strength hot-dip-galvanized steel sheet |
| EP3178961A4 (en) * | 2014-10-17 | 2017-09-13 | JFE Steel Corporation | High-strength hot-dip-galvanized steel sheet |
| US9963771B2 (en) | 2014-10-17 | 2018-05-08 | Jfe Steel Corporation | High-strength galvanized steel sheet |
| US9994939B2 (en) | 2014-10-17 | 2018-06-12 | Jfe Steel Corporation | High-strength galvanized steel sheet |
| KR101897054B1 (en) | 2014-10-17 | 2018-09-10 | 제이에프이 스틸 가부시키가이샤 | High-strength galvanized steel sheet |
| CN106795612B (en) * | 2014-10-17 | 2019-06-04 | 杰富意钢铁株式会社 | High strength hot dip galvanized steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104755647A (en) | 2015-07-01 |
| JP2014088605A (en) | 2014-05-15 |
| IN2015DN02531A (en) | 2015-09-11 |
| TW201434617A (en) | 2014-09-16 |
| CN104755647B (en) | 2016-10-26 |
| MX2015005403A (en) | 2015-08-05 |
| TWI511875B (en) | 2015-12-11 |
| MX348834B (en) | 2017-06-30 |
| KR101718469B1 (en) | 2017-03-21 |
| JP5825244B2 (en) | 2015-12-02 |
| KR20150060904A (en) | 2015-06-03 |
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