WO2015005191A1 - めっき性、加工性、および耐遅れ破壊特性に優れた高強度めっき鋼板、並びにその製造方法 - Google Patents
めっき性、加工性、および耐遅れ破壊特性に優れた高強度めっき鋼板、並びにその製造方法 Download PDFInfo
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- WO2015005191A1 WO2015005191A1 PCT/JP2014/067663 JP2014067663W WO2015005191A1 WO 2015005191 A1 WO2015005191 A1 WO 2015005191A1 JP 2014067663 W JP2014067663 W JP 2014067663W WO 2015005191 A1 WO2015005191 A1 WO 2015005191A1
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- steel sheet
- less
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- oxide layer
- average depth
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
- C23C8/18—Oxidising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12958—Next to Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
Definitions
- the present invention relates to a high-strength plated steel sheet having a tensile strength of 980 MPa or more and excellent in plateability, workability including both bending workability and hole expansibility, and delayed fracture resistance, and a method for producing the same.
- the plated steel sheet of the present invention includes both hot-dip galvanized steel sheets and alloyed hot-dip galvanized steel sheets.
- Hot-dip galvanized steel sheets and alloyed hot-dip galvanized steel sheets which are widely used in the fields of automobiles and transportation equipment, are not only high-strength, but also workability of bending workability and hole expansibility (stretch flangeability), and delay resistance It is required to have excellent fracture characteristics. Further, it is required to have excellent impact resistance.
- Si and Mn are easily oxidizable elements, and wettability of hot dip galvanizing is significantly deteriorated by Si oxide or Mn oxide formed on the surface, resulting in problems such as non-plating.
- Patent Document 1 discloses a hot-dip galvanized steel sheet having a tensile strength of 590 MPa or more and excellent bendability and corrosion resistance of a processed part. Specifically, in Patent Document 1, in order to suppress the occurrence of bending cracks and damage to the plating film due to the internal oxide layer formed on the steel plate side from the interface between the steel plate and the plating layer, the growth of the internal oxide layer is suppressed. Therefore, the growth of the decarburized layer is remarkably accelerated. Further, a near-surface structure is disclosed in which the thickness of the internal oxide layer in the ferrite region formed by decarburization is controlled to be thin.
- Patent Document 2 discloses a hot-dip galvanized steel sheet having a fatigue strength, hydrogen embrittlement resistance (synonymous with delayed fracture resistance), and a tensile strength excellent in bendability of 770 MPa or more.
- the steel plate portion is configured to have a soft layer that is in direct contact with the interface with the plating layer, and a soft layer that has ferrite with a maximum area ratio structure.
- the thickness D of the soft layer and the depth d from the plating / base metal interface of the oxide containing one or more of Si and Mn existing in the steel sheet surface layer portion are d / 4 ⁇ D ⁇ 2d.
- a hot-dip galvanized steel sheet that satisfies the requirements is disclosed.
- JP 2011-231367 A Japanese Patent No. 4943558
- the present invention has been made in view of the above circumstances, and its purpose is excellent in plating property, workability of bending workability and hole expansibility, and delayed fracture resistance, and also in shock absorption resistance.
- An object is to provide an excellent hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet of 980 MPa or more, and a method for producing the same.
- the high-strength galvanized steel sheet having a tensile strength of 980 MPa or more according to the present invention that has been able to solve the above problems is a galvanized steel sheet having a hot-dip galvanized layer or an alloyed hot-dip galvanized layer on the surface of the base steel sheet, (1)
- the base steel sheet is, in mass%, C: 0.05 to 0.25%, Si: 0.5 to 2.5%, Mn: 2.0 to 4%, P: more than 0%.
- the base steel sheet further comprises, in mass%, Cr: more than 0% and 1% or less, Mo: more than 0% and 1% or less, and B: more than 0% and 0.01% or less. It contains at least one selected from
- the base steel sheet further comprises, in mass%, Ti: more than 0% and 0.2% or less, Nb: more than 0% and 0.2% or less, and V: more than 0% and 0.2%. It contains at least one selected from the group consisting of:
- the base steel sheet further contains at least one selected from the group consisting of Cu: 1% or less and Ni: 1% or less in mass%.
- the average depth d of the internal oxide layer and the average depth D of the soft layer satisfy a relationship of D> 2d.
- the manufacturing method of the present invention that has solved the above-mentioned problems is a method for manufacturing the high-strength plated steel sheet according to any one of the above, and a hot-rolled steel sheet that satisfies the above-described components in the steel at 600 ° C.
- the step of soaking in the range from Ac 3 point to Ac 3 point + 100 ° C. in the reduction zone is a method for manufacturing the high-strength plated steel sheet according to any one of the above, and a hot-rolled steel sheet that satisfies the above-described components in the steel at 600 ° C.
- another manufacturing method of the present invention that can solve the above-mentioned problems is a method for manufacturing the high-strength plated steel sheet according to any one of the above, and a hot-rolled steel sheet that satisfies the above-described components in the steel, A hot rolling step of winding at a temperature of 500 ° C. or higher, a step of keeping the temperature at a temperature of 500 ° C.
- a step of oxidizing at an air-fuel ratio of 0.9 to 1.4 in the oxidation zone and a step of soaking in the range of Ac 3 point to Ac 3 point + 100 ° C. in the reduction zone are included. It has a gist.
- the plated steel sheet of the present invention includes an internal oxide layer containing at least one oxide selected from the group consisting of Si and Mn from the interface between the plating layer and the base steel sheet to the base steel sheet side, and a region of the internal oxide layer. And a hard layer mainly composed of martensite and bainite other than the soft layer.
- the average depth d of the internal oxide layer is controlled to be 4 ⁇ m or more to increase the hydrogen. Because it is used as a trap site, hydrogen embrittlement can be effectively suppressed, and a high-strength plated steel sheet with a tensile strength of 980 MPa or more excellent in all of bending workability, hole expansibility workability and delayed fracture resistance can be obtained. It is done.
- the relationship between the average depth d of the internal oxide layer and the average depth D of the soft layer including the region of the internal oxide layer is appropriately controlled, bending workability and delayed fracture resistance are particularly good. Increased further.
- FIG. 1 is a diagram schematically illustrating a layer configuration from the interface between a plating layer and a base steel plate to the base steel plate side in the plated steel plate of the present invention.
- FIG. 2 is an explanatory diagram for measuring the average depth d of the internal oxide layer in the plated steel sheet of the present invention.
- FIG. 3 is a diagram for explaining the measurement position of the Vickers hardness used for determining the average depth D of the soft layer.
- the inventors of the present invention have a high strength of 980 MPa or more in a base steel plate rich in Si and Mn, and are excellent in all of plating properties, workability, delayed fracture resistance, and shock absorption.
- investigations have been made focusing on the layer structure from the interface between the plating layer and the base steel sheet to the base steel sheet side.
- the internal oxide layer can function as a hydrogen trap site, and hydrogen embrittlement can be effectively suppressed, so that the intended purpose can be achieved.
- the average depth of the internal oxide layer The present invention was completed by finding that bending workability and delayed fracture resistance can be further enhanced by appropriately controlling the relationship between d and the average depth D of the soft layer including the region of the internal oxide layer. .
- the plated steel sheet includes both a hot dip galvanized steel sheet and an alloyed hot dip galvanized steel sheet.
- a base steel plate means the steel plate before a hot-dip galvanized layer and an alloying hot-dip galvanized layer are formed, and is distinguished from the said plated steel plate.
- high strength means that the tensile strength is 980 MPa or more.
- excellent workability means excellent bending workability and hole expansibility.
- excellent workability when these characteristics are measured by the method described in the examples described later, those satisfying the acceptance criteria of the examples are referred to as “excellent workability”.
- the plated steel sheet of the present invention has a hot dip galvanized layer or an alloyed hot dip galvanized layer (hereinafter sometimes represented by a plated layer) on the surface of the base steel sheet.
- the characteristic part of the present invention is that it has the following layer configurations (A) to (C) in order from the interface between the base steel plate and the plating layer toward the base steel plate side.
- the average depth d of the internal oxide layer 3 is 4 ⁇ m or more and less than the average depth D of the soft layer described in (B) described later.
- (B) Soft layer including the internal oxide layer, where the thickness of the base steel sheet is t, the Vickers hardness satisfies 90% or less of the Vickers hardness at t / 4 part of the base steel sheet.
- the average depth D of the soft layer is 20 ⁇ m or more.
- the layer structure of the plated steel sheet according to the present invention on the base steel sheet 2 side is from the interface between the plating layer 1 and the base steel sheet 2 toward the base steel sheet 2 side, (C) hard layer 5 located in the inside 6 on the base steel plate 2 side from the layer 4.
- the soft layer 4 of (B) includes the internal oxide layer 3 of (A).
- the hard layer 5 should just exist in the inside 6, and the presence form of the inside 6 will not ask
- the portion directly in contact with the interface between the plating layer 1 and the base steel plate 2 has an internal oxide layer 3 having an average depth d of 4 ⁇ m or more.
- the average depth means the average depth from the interface, and a detailed measurement method thereof will be described with reference to FIG.
- the internal oxide layer 3 is composed of an oxide containing at least one of Si and Mn, and a Si and Mn depletion layer in which Si and Mn form an oxide to form a solid solution Si or a small amount of solid solution Mn. .
- the greatest feature is that the average depth d of the internal oxide layer 3 is controlled to be 4 ⁇ m or more.
- the internal oxide layer can be used as a hydrogen trap site, hydrogen embrittlement can be suppressed, and bending workability, hole expansibility, and delayed fracture resistance are improved.
- the oxidizable elements are fixed as oxides inside the base steel sheet surface layer, and by reducing the oxidizable elements dissolved in the base steel sheet surface layer, A method for preventing the formation of an oxide film on the surface of the base steel plate is also known.
- the use of at least one oxide selected from the group consisting of Si and Mn is effective in improving the deterioration of bendability and hole expansibility due to crystallization.
- the above oxide is useful as a hydrogen trap site that prevents hydrogen from entering the base steel sheet during reduction, and can improve bendability, hole expansibility, and delayed fracture resistance.
- the average depth d of the internal oxide layer containing the oxide is as thick as 4 ⁇ m or more.
- the upper limit of the average depth d of the internal oxide layer is at least less than the average depth D of the soft layer (B) described later.
- the upper limit of d is preferably 30 ⁇ m or less.
- the t is more preferably 18 ⁇ m or less, and still more preferably 16 ⁇ m or less.
- said d is 6 micrometers or more, and it is more preferable that it is 8 micrometers or more.
- the average depth d of the internal oxide layer is preferably controlled so as to satisfy the relational expression of D> 2d in relation to the average depth D of the soft layer (B) described later. This further improves the bending workability and delayed fracture resistance, particularly the bending workability.
- the oxide existing depth d and the soft layer thickness substantially correspond to the average depth d of the internal oxide layer and the average depth D of the soft layer described in the present invention.
- D a hot dip galvanized steel sheet satisfying d / 4 ⁇ D ⁇ 2d is disclosed, and the control directivity is completely different from the relational expression (D> 2d) defined in the present invention.
- Patent Document 2 describes that the range of the oxide depth d is controlled while basically satisfying the relationship of d / 4 ⁇ D ⁇ 2d described above.
- the average depth d of the internal oxide layer is controlled to be thicker than 4 ⁇ m.
- this does not describe the effect of the present invention that the action as a hydrogen trap site is effectively exhibited and the bending workability, hole expansibility, and delayed fracture resistance are improved.
- the average depth of the internal oxide layer in the cold rolled steel sheet before passing through the continuous hot dip galvanizing line is 4 ⁇ m or more. It is necessary to control. Details will be described later in the column of the manufacturing method. That is, as shown in the examples described later, the internal oxide layer after pickling and cold rolling is succeeded to the internal oxide layer in the plated steel sheet finally obtained after passing through the plating line.
- the soft layer 4 is a layer including the region of the internal oxide layer 3 of the above (A) and has a Vickers hardness of the base steel plate 2. It satisfies 90% or less of the Vickers hardness at t / 4 part. A detailed method for measuring the Vickers hardness will be described in the column of Examples described later.
- the soft layer is a soft structure having a Vickers hardness lower than that of the hard layer (C) described later, and is excellent in deformability, so that the bending workability is particularly improved. That is, at the time of bending, the base steel plate surface layer portion becomes a starting point of cracking, but the bending workability is particularly improved by forming a predetermined soft layer on the base steel plate surface layer as in the present invention. Furthermore, by forming the soft layer, it is possible to prevent the oxide in (A) from becoming a starting point of cracking during bending, and it is possible to enjoy only the above-described merit as a hydrogen trap site. As a result, not only bending workability but also delayed fracture resistance is further improved.
- the average depth D of the soft layer is set to 20 ⁇ m or more.
- the T is preferably 22 ⁇ m or more, and more preferably 24 ⁇ m or more.
- the upper limit is preferably set to 100 ⁇ m or less.
- the D is more preferably 60 ⁇ m or less.
- the hard layer is formed on the base steel plate 2 side of the soft layer 4 of (B) and has a structure mainly composed of martensite and bainite. Is done.
- the martensite of the hard layer 5 may be tempered.
- “mainly” means that the total area ratio of bainite and martensite is 80 area% or more with respect to the entire structure when the structure fraction is measured by the method described in the examples described later. It means that the area ratio of ferrite to the structure is 0 area% or more and 5 area% or less.
- the higher the total area ratio of bainite and martensite in the hard layer is, the better, and preferably 93 area% or more.
- the smaller the area ratio of ferrite the better. 5 area% or less is preferable, 3 area% or less is more preferable, and most preferably 0 area%.
- the hard layer may contain a structure that can be inevitably mixed in production, for example, residual ⁇ , pearlite, and the like as long as the effects of the present invention are not impaired.
- the above structure is 15 area% or less at the maximum, and the smaller the better.
- the organization is described as “Others” in Table 2 to be described later.
- the hard layer mainly composed of bainite and martensite is formed by suppressing the ratio of the soft ferrite to a maximum of 5% by area or less. Further, in the hard layer, since the ferrite ratio is suppressed, the yield ratio (YR) is increased, and the shock absorption is improved.
- a soft phase for example, ferrite
- a hard phase for example, martensite and bainite. Therefore, in order to suppress the crack, it is necessary to reduce the hardness difference between the soft phase and the hard phase. Therefore, in the present invention, the hard steel layer mainly composed of bainite and martensite is formed by suppressing the ratio of the soft ferrite to a maximum of 5% by area or less. Further, in the hard layer, since the ferrite ratio is suppressed, the yield ratio (YR) is increased, and the shock absorption is improved.
- the hard layer in this invention should just contain a bainite and a martensite as mentioned above, and each ratio of a bainite and a martensite is not limited at all.
- both the aspect which is comprised only from bainite and does not contain martensite at all; conversely, the aspect comprised only from martensite and does not contain bainite at all are included in the scope of the present invention. From the above viewpoint, in the examples described later, bainite and martensite are not observed separately, only the total area is measured, and the results are shown in Table 3.
- the plated steel sheet of the present invention has C: 0.05 to 0.25%, Si: 0.5 to 2.5%, Mn: 2.0 to 4%, P: more than 0% and 0.1% or less, S : More than 0% and 0.05% or less, Al: 0.01 to 0.1%, and N: more than 0% and 0.01% or less, with the balance being iron and inevitable impurities.
- C 0.05 to 0.25%
- C is an element important for increasing the strength of steel due to the improvement of hardenability and the effect of hardening of martensite.
- the lower limit of the C amount is set to 0.05% or more.
- the minimum with the preferable amount of C is 0.08% or more, More preferably, it is 0.10% or more.
- the upper limit of C content is set to 0.25%.
- the upper limit with preferable C amount is 0.2% or less, More preferably, it is 0.18% or less.
- Si 0.5 to 2.5%
- Si is an element that increases the strength of steel by solid solution strengthening and is effective in improving workability. Moreover, it produces an internal oxide layer and has an action of suppressing hydrogen embrittlement.
- the lower limit of the Si amount is 0.5% or more.
- the minimum with the preferable amount of Si is 0.75% or more, More preferably, it is 1% or more.
- Si is a ferrite-forming element, and when Si is added excessively, the formation of ferrite cannot be suppressed, the hardness difference between the soft phase and the hard phase increases, and the workability decreases.
- the upper limit of the Si amount is set to 2.5%.
- the upper limit with the preferable amount of Si is 2% or less, More preferably, it is 1.8% or less.
- Mn 2.0-4% Mn is an element that improves hardenability, suppresses ferrite and bainite, generates martensite, and contributes to high strength.
- the lower limit of the amount of Mn is set to 2.0% or more.
- the minimum with the preferable amount of Mn is 2.3% or more, More preferably, it is 2.5% or more.
- the upper limit of the Mn amount is 4%.
- the upper limit with the preferable amount of Mn is 3.5% or less.
- P more than 0% and 0.1% or less P is an element useful for strengthening steel as a solid solution strengthening element.
- the lower limit of the P amount is set to more than 0%.
- the upper limit is made 0.1% or less.
- the amount of P is preferably as small as possible, preferably 0.03% or less, more preferably 0.015% or less.
- S more than 0% and 0.05% or less S is an element that is unavoidably contained, and forms sulfides such as MnS, which may cause cracks and deteriorate workability. Therefore, the upper limit of the S amount is set to 0.05% or less.
- the amount of S should be small, preferably 0.01% or less, more preferably 0.008% or less.
- Al acts as a deoxidizer. Further, Al combines with N to become AlN, and the workability and delayed fracture resistance are improved by making the austenite grain size finer.
- the lower limit of the Al amount is set to 0.01% or more.
- the minimum with preferable Al amount is 0.02% or more, More preferably, it is 0.03% or more.
- the upper limit of Al content is 0.1%.
- the upper limit with the preferable amount of Al is 0.08% or less, More preferably, it is 0.05% or less.
- N more than 0% and 0.01% or less N is an element inevitably contained, but if it is contained excessively, workability deteriorates.
- B boron
- BN precipitates are generated and inhibit the effect of improving the hardenability by B. Therefore, it is better to reduce N as much as possible. Therefore, the upper limit of the N amount is 0.01% or less.
- the upper limit with preferable N amount is 0.008% or less, More preferably, it is 0.005% or less.
- the plated steel sheet of the present invention contains the above components, with the balance being iron and inevitable impurities.
- Cr more than 0% and less than 1%
- Mo more than 0% and less than 1%
- B more than 0% and less than 0.01%.
- the preferable lower limit of the Cr amount is set to 0.01% or more. However, if Cr is added excessively, the plating property is lowered. Moreover, Cr carbide
- the preferable lower limit of the Mo amount is 0.01% or more.
- the preferable upper limit of Mo is 1% or less. More preferably, it is 0.5% or less, More preferably, it is 0.3% or less.
- the preferable lower limit of the B amount is set to 0.0002% or more. More preferably, it is 0.0010% or more. However, when the amount of B becomes excessive, the hot workability deteriorates, so the preferable upper limit of the amount of B is made 0.01% or less. More preferably, it is 0.0070% or less, More preferably, it is 0.0050% or less.
- the preferable lower limit of each of Ti, Nb, and V is set to 0.01% or more.
- the preferable upper limit of each element is set to 0.2% or less. Any element is more preferably 0.15% or less, and still more preferably 0.10% or less.
- At least one selected from the group consisting of Cu: more than 0% and not more than 1% and Ni: more than 0% and not more than 1% is an element effective for increasing the strength. These elements may be added alone or in combination.
- the preferable lower limit of Cu and Ni is set to 0.01% or more.
- the preferable upper limit of each element is 1% or less. Any element is more preferably 0.8% or less, and still more preferably 0.5% or less.
- the production method of the present invention includes a first method in which pickling is performed immediately after hot rolling without holding the heat, and a second method in which pickling is performed after warming after hot rolling.
- the lower limit of the hot rolling coiling temperature is different between the first method (without heat retention) and the second method (with heat retention), but the other steps are the same. Details will be described below.
- the first production method according to the present invention includes a hot rolling process, a pickling process, a cold rolling process, an oxidation process, a reduction process, and a plating process in a continuous molten Zn plating line (CGL (Continuous Galvanizing Line)). Broadly divided. And the characteristic part of this invention is a hot rolling step for obtaining a hot rolled steel sheet in which an internal oxide layer is formed by winding a steel sheet satisfying the above-mentioned components in the steel at a temperature of 600 ° C. or higher, and an average depth of the internal oxide layer.
- Hot rolling may be performed according to a conventional method.
- the heating temperature is preferably about 1150 to 1300 ° C.
- the finish rolling temperature is preferably controlled to about 850 to 950 ° C.
- the coiling temperature after hot rolling it is important to control the coiling temperature after hot rolling to 600 degreeC or more.
- an internal oxide layer can be formed on the base steel plate surface.
- the coiling temperature is less than 600 ° C.
- the internal oxide layer is not sufficiently generated.
- the strength of the hot-rolled steel sheet is increased, and the cold-rollability is reduced.
- a preferable winding temperature is 620 ° C. or higher, and more preferably 640 ° C. or higher.
- the upper limit is preferably made 750 ° C. or lower.
- the hot-rolled steel sheet thus obtained is pickled and cold-rolled so that the average depth d of the internal oxide layer remains at 4 ⁇ m or more. It is known to control the thickness of the internal oxide layer by controlling the pickling conditions. Specifically, the thickness of the desired internal oxide layer is determined according to the type and concentration of the pickling solution used. What is necessary is just to control the temperature of pickling, time, etc. appropriately so that it can ensure.
- mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid can be used.
- the concentration and temperature of the pickling solution are high and the pickling time is long, the internal oxide layer tends to dissolve and become thin. Conversely, if the concentration and temperature of the pickling solution are low and the pickling time is short, removal of the black skin scale layer by pickling becomes insufficient. Therefore, for example, when hydrochloric acid is used, it is recommended to control the concentration to about 3 to 20%, the temperature to 60 to 90 ° C., and the time to about 35 to 200 seconds.
- the number of pickling tanks is not particularly limited, and a plurality of pickling tanks may be used.
- a pickling inhibitor such as an amine, that is, an inhibitor, a pickling accelerator, or the like may be added to the pickling solution.
- cold rolling is performed so that the average depth d of the internal oxide layer remains 4 ⁇ m or more.
- the cold rolling conditions are preferably controlled so that the cold rolling rate is in the range of about 20 to 70%.
- oxidation is performed in an oxidation zone at an air-fuel ratio of 0.9 to 1.4.
- the air-fuel ratio means a flow rate ratio between combustion gas and air.
- CO gas is used.
- the air-fuel ratio is preferably controlled to 1.0 or more and 1.2 or less.
- the preferable lower limit of the oxidation temperature is 500 ° C. or higher, more preferably 750 ° C. or higher.
- the upper limit of the oxidation temperature is 900 ° C. or lower, more preferably 850 ° C. or lower.
- the oxide film is reduced in a hydrogen atmosphere in the reduction zone.
- it is necessary to heat in an austenite single phase region, and soaking is performed in a range of Ac 3 point to Ac 3 point + 100 ° C. If the soaking temperature is lower than the Ac 3 point, the ferrite becomes excessive, while if it exceeds the Ac 3 point + 100 ° C., the austenite becomes coarse and the workability deteriorates.
- a preferable soaking temperature is Ac 3 point + 15 ° C. or higher and Ac 3 point + 85 ° C. or lower.
- the Ac 3 point is calculated based on the following equation (i).
- [] represents the content (% by mass) of each element. This equation is described in “Leslie Steel Material Science” (published by Maruzen Co., Ltd., William C. Leslie, p273).
- the atmosphere of the reduction zone contains hydrogen and nitrogen, and the hydrogen concentration is preferably controlled in the range of about 5 to 25% by volume.
- the dew point is preferably controlled at -30 to -60 ° C.
- the holding time at the time of soaking is not particularly limited, and for example, it is preferably controlled to about 10 to 100 seconds, particularly about 10 to 80 seconds.
- the average cooling rate during cooling is preferably controlled to 5 ° C./second or more so as to suppress the formation of ferrite. More preferably, it is 8 ° C./second or more.
- the upper limit of the average cooling rate is not particularly limited, but it is preferable to control the temperature to about 100 ° C./second or less in consideration of the ease of control of the base steel sheet temperature and the equipment cost.
- a more preferable average cooling rate is 50 ° C./second or less, and further preferably 30 ° C./second or less.
- the cooling stop temperature may be up to a temperature range in which ferrite is not generated. For example, it is preferable to cool to 550 ° C. or lower.
- the minimum with a preferable cooling stop temperature is 450 degreeC or more, for example, More preferably, it is 460 degreeC or more, More preferably, it is 470 degreeC or more.
- the cooling method is not limited to the above.
- the cooling when heating to the plating bath temperature at the time of hot dip galvanization after cooling, the cooling may be performed below the above-described preferable cooling stop temperature. For example, No. in Table 1 described later. See 11. Or after cooling to predetermined temperature, you may cool with water. No. in Table 1 to be described later. See 12.
- hot dip galvanizing is performed according to a conventional method.
- the method of hot dip galvanizing is not particularly limited, and for example, the preferred lower limit of the plating bath temperature is 400 ° C. or higher, more preferably 440 ° C. or higher.
- the upper limit with the said preferable plating bath temperature is 500 degrees C or less, More preferably, it is 470 degrees C or less.
- the composition of the plating bath is not particularly limited, and a known hot dip galvanizing bath may be used.
- the cooling conditions after hot dip galvanizing are not particularly limited, and for example, the average cooling rate to room temperature is preferably controlled to about 1 ° C./second or more, more preferably 5 ° C./second or more.
- the upper limit of the above average cooling rate is not particularly defined, it is preferably controlled to about 50 ° C./second or less in consideration of the ease of control of the base steel sheet temperature and the equipment cost.
- the average cooling rate is preferably 40 ° C./second or less, more preferably 30 ° C./second or less.
- alloying treatment may be performed by a conventional method, whereby an alloyed hot-dip galvanized steel sheet is obtained.
- the conditions for the alloying treatment are not particularly limited. For example, after performing hot dip galvanization under the above conditions, hold at about 500 to 600 ° C., particularly about 530 to 580 ° C. for about 5 to 30 seconds, particularly about 10 to 25 seconds. It is preferable to do so. If it is below the above range, alloying is insufficient. On the other hand, if it exceeds the above range, alloying may proceed excessively and the plating layer may be peeled off. Furthermore, it becomes easy to produce ferrite.
- the alloying treatment may be performed using, for example, a heating furnace, a direct fire, or an infrared heating furnace.
- the heating means is also not particularly limited, and for example, conventional means such as gas heating, induction heater heating, that is, heating by a high frequency induction heating device can be adopted.
- an alloyed hot-dip galvanized steel sheet is obtained by cooling according to a conventional method.
- the average cooling rate to room temperature is preferably controlled to about 1 ° C./second or more.
- the second production method includes a hot rolling step of winding a hot-rolled steel sheet satisfying the above-described components in the steel at a temperature of 500 ° C. or higher, a step of keeping the temperature at a temperature of 500 ° C. or higher for 80 minutes or more, In the step of pickling and cold rolling so that the average depth d of the internal oxide layer remains 4 ⁇ m or more, in the oxidation zone, in the oxidation zone with an air-fuel ratio of 0.9 to 1.4, in the reduction zone, And soaking in the range of Ac 3 point to Ac 3 point + 100 ° C. in this order.
- the lower limit of the coiling temperature after hot rolling is set to 500 ° C. or more, and the heat retaining step is provided after the hot rolling step. Only the first manufacturing method is different. Therefore, only the difference will be described below.
- the first manufacturing method may be referred to.
- the reason why the heat retaining step is provided as described above is that the temperature can be maintained for a long time in the temperature range that can be oxidized, and the lower limit of the coiling temperature range in which a desired internal oxide layer can be obtained can be expanded. There is also an advantage that the uniformity of the base steel sheet can be improved by reducing the temperature difference between the surface layer and the inside of the base steel sheet.
- the coiling temperature after hot rolling is controlled to 500 ° C. or higher.
- the temperature can be set lower than 600 ° C. which is the lower limit of the winding temperature in the first manufacturing method described above.
- a preferable winding temperature is 540 ° C. or higher, more preferably 570 ° C. or higher.
- the preferable upper limit of coiling temperature is the same as the 1st manufacturing method mentioned above, and it is preferable to set it as 750 degrees C or less.
- the hot-rolled steel sheet thus obtained is kept at a temperature of 500 ° C. or more for 80 minutes or more. Thereby, a desired internal oxide layer can be obtained. It is preferable to keep the hot-rolled steel sheet in a heat-insulating device, for example, so that the above-mentioned effect due to heat insulation is effectively exhibited.
- the said apparatus used for this invention will not be specifically limited if comprised with the heat insulating raw material, For example, a ceramic fiber etc. are used preferably as such a raw material.
- a preferred temperature is 540 ° C. or higher, more preferably 560 ° C. or higher.
- a preferable time is 100 minutes or more, More preferably, it is 120 minutes or more.
- it is preferable to control the upper limit of the said temperature and time to about 700 degrees C or less and 500 minutes or less when pickling property, productivity, etc. are considered.
- the plated steel sheet of the present invention obtained by the above-described production method is further subjected to various coatings and coating ground treatments, for example, chemical conversion treatment such as phosphate treatment; organic coating treatment, for example, formation of an organic coating such as a film laminate. May be.
- various coatings and coating ground treatments for example, chemical conversion treatment such as phosphate treatment; organic coating treatment, for example, formation of an organic coating such as a film laminate. May be.
- paint used for various coatings known resins such as epoxy resin, fluorine resin, silicon acrylic resin, polyurethane resin, acrylic resin, polyester resin, phenol resin, alkyd resin, melamine resin, and the like can be used. From the viewpoint of corrosion resistance, an epoxy resin, a fluororesin, and a silicon acrylic resin are preferable.
- a curing agent may be used together with the resin.
- the paint may also contain known additives such as coloring pigments, coupling agents, leveling agents, sensitizers, antioxidants, UV stabilizers, flame retardants and the like.
- the form of paint is not particularly limited, and any form of paint such as solvent-based paint, water-based paint, water-dispersed paint, powder paint, and electrodeposition paint can be used.
- the coating method is not particularly limited, and a dipping method, a roll coater method, a spray method, a curtain flow coater method, an electrodeposition coating method, and the like can be used. What is necessary is just to set suitably the thickness of coating layers, such as a plating layer, an organic membrane
- the high-strength plated steel sheet of the present invention is ultra-high-strength and excellent in workability (bending workability and hole expandability) and delayed fracture resistance. It can be used for collision parts such as members and crash boxes, pillars such as center pillar reinforcements, body components such as roof rail reinforcements, side sills, floor members, and kick parts.
- the balance was iron and inevitable impurity slabs heated to 1250 ° C., hot rolled to 2.4 mm at a finish rolling temperature of 900 ° C., and then wound up at the temperature shown in Table 2.
- the hot-rolled steel sheet thus obtained was pickled under the following conditions and then cold-rolled at a cold rolling rate of 50%.
- the plate thickness after cold rolling is 1.2 mm.
- annealing oxidation, reduction
- cooling were performed under the conditions shown in Table 2 in a continuous molten Zn plating line.
- the temperature of the oxidation furnace installed in the continuous molten Zn plating line was controlled to 800 ° C.
- the hydrogen concentration in the reduction furnace was 20% by volume
- the balance was nitrogen and inevitable impurities, dew point: ⁇ 45 ° C.
- the holding times at the soaking temperature shown in Table 2 were all 50 seconds.
- No. 10 after cooling to the cooling stop temperature of 200 ° C. shown in Table 2, it was heated to 460 ° C. and then immersed in a galvanizing bath to obtain a GA steel sheet in the same manner as described above.
- No. 11 as shown in Table 2, after cooling to 600 ° C. at an average cooling rate of 10 ° C./sec, water cooling (WQ (Water-Quenching)), and then heating to 460 ° C. and then immersing in a galvanizing bath. In the same manner as above, a GA steel sheet was obtained.
- WQ Water-Quenching
- the average depth of the internal oxide layer was measured not only on the plated steel sheet but also on the base steel sheet after pickling and cold rolling for reference. This is to confirm that the desired average depth of the internal oxide layer has already been obtained in the cold-rolled steel sheet before annealing by controlling the coiling temperature and pickling conditions after hot rolling. It is.
- Pulse sputtering frequency 50Hz
- Anode diameter (analysis area): Diameter 6 mm
- Discharge power 30W
- Ar gas pressure 2.5 hPa
- the position where the Zn content and the Fe content from the surface of the plating layer 1 are equal is defined as the interface between the plating layer 1 and the base steel plate 2.
- the average value of the O amount at each measurement position at a depth of 40 to 50 ⁇ m from the surface of the plating layer is the average value of the bulk O amount, which is 0.02% higher than that, that is, the O amount ⁇ (the bulk O amount)
- the average value + 0.02%) was defined as the internal oxide layer, and the maximum depth was defined as the internal oxide layer depth.
- a similar test was performed using three test pieces, and the average was defined as the average depth d of the internal oxide layer.
- Interval between measurement points that is, the distance between x and x in FIG. 3 was at least 15 ⁇ m.
- a material having a tensile strength TS of 980 MPa or more was evaluated as high strength (pass). Moreover, it evaluated that the thing whose YR is 60% or more is excellent in impact-resistant absorbency (pass).
- bending workability was evaluated for each tensile strength TS. Details are as follows. Note that bending workability was not evaluated for TS not satisfying the acceptable standard of 980 MPa or more (indicated as-in Table 3). When TS is 980 MPa or more and less than 1080 MPa, Rmin / t ⁇ 1.0 is satisfied, and when TS is 1080 MPa or more and less than 1180 MPa, Rmin / t ⁇ 1.5 is satisfied and when TS is 1180 MPa or more, Rmin / t ⁇ 2 .50 passed
- No. 1 to 11, 18, 20, 23, 25, and 27 are examples that satisfy the requirements of the present invention, including strength, workability [bending workability and hole expansibility ( ⁇ )], delayed fracture resistance, impact characteristics, All of the plating properties were good.
- the average depth d of the internal oxide layer and the average depth D of the soft layer satisfy the relationship of D> 2d (that is, the value of “D> 2d” in Table 2 exceeds 1).
- bending workability was improved.
- ⁇ also increased.
- No. No. 12 is an example with a large amount of C, and bending workability, ⁇ , and delayed fracture resistance were deteriorated.
- No. No. 13 is an example in which the amount of Si is small, the internal oxide layer is not sufficiently formed, and bending workability, ⁇ , and delayed fracture resistance are deteriorated.
- No. No. 14 is an example in which the amount of Mn is small. Since the hardenability is poor, an excessive amount of ferrite is generated, and the total amount of (B + M) is also small. As a result, TS and YR decreased, and ⁇ also decreased.
- No. No. 15 is an example in which the average cooling rate after soaking is slow. Excessive ferrite was generated during cooling, and the total amount of (B + M) was reduced, and the desired hard layer could not be obtained. As a result, TS and YR were lowered and ⁇ was lowered.
- No. No. 22 is also an example in which the average cooling rate after soaking is slow. Since ferrite was excessively generated during cooling, YR was lowered, and ⁇ , bending workability, and delayed fracture resistance were lowered.
- No. 16 and 17 are examples in which the coiling temperature at the time of hot rolling is low, and since the average depth of the internal oxide layer after pickling and cold rolling is shallow, the average depth d of the internal oxide layer after plating, The average depth D has also become shallower. As a result, bending workability, delayed fracture resistance, and plating properties decreased.
- No. No. 19 had a low air-fuel ratio in the oxidation furnace, an iron oxide film was not sufficiently formed, and the plating property was lowered. In addition, since the soft layer was not sufficiently formed, bending workability and delayed fracture resistance were also deteriorated.
- No. No. 21 is an example where the soaking temperature is low, annealing was performed in a two-phase region, ferrite was excessively generated, the total amount of (B + M) was reduced, and a desired hard layer could not be obtained. Therefore, YR was lowered, and ⁇ , bending workability, and delayed fracture resistance were lowered.
- No. No. 24 is an example in which the pickling time is long, and the internal oxide layer was dissolved, and the desired average depth d of the internal oxide layer and the average depth D of the soft layer were not obtained and became shallow. As a result, bending workability, delayed fracture resistance, and plating properties decreased.
- No. No. 26 is an example in which the coiling temperature at the time of hot rolling is low, and since the average depth of the internal oxide layer after pickling and cold rolling is shallow, the average depth d of the internal oxide layer after plating and the average depth of the soft layer D also became shallower. As a result, bending workability, delayed fracture resistance, and plating properties decreased.
- No. No. 28 is an example in which the heat retention time is insufficient, and since the average depth of the internal oxide layer after pickling and cold rolling is shallow, the average depth d of the internal oxide layer after plating and the average depth D of the soft layer also became shallower. As a result, bending workability, delayed fracture resistance, and plating properties decreased.
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Abstract
Description
(A)内部酸化層:SiおよびMnよりなる群から選択される少なくとも一種の酸化物を含む層である。内部酸化層3の平均深さdは、4μm以上、後記する(B)に記載の軟質層の平均深さD未満である。
(B)軟質層:上記内部酸化層を含み、上記素地鋼板の板厚をtとしたとき、ビッカース硬さが、上記素地鋼板のt/4部におけるビッカース硬さの90%以下を満足する。軟質層の平均深さDは、20μm以上である。
(C)硬質層:マルテンサイトとベイナイトを主体とする組織で構成される。ここで「主体とする」とは、後記する実施例の記載の方法で組織分率を測定したとき、ベイナイトとマルテンサイトの合計面積率が80面積%以上であり、且つ、フェライトの面積率が0面積%以上、5面積%以下のものを意味する。
まず、めっき層1と素地鋼板2の界面に直接接する部分は、平均深さdが4μm以上の内部酸化層3を有する。ここで、平均深さとは、上記界面からの平均深さを意味し、その詳細な測定方法は、後記する実施例の欄において図2を用いて説明する。
本発明において軟質層4は、図1に示すように、上記(A)の内部酸化層3の領域を含む層であって、且つ、ビッカース硬さが、素地鋼板2のt/4部におけるビッカース硬さの90%以下を満足するものである。上記ビッカース硬さの詳細な測定方法は、後記する実施例の欄で説明する。
本発明において硬質層は、図1に示すように、上記(B)の軟質層4の素地鋼板2側に形成され、且つ、マルテンサイトとベイナイトを主体とする組織で構成される。上記硬質層5のマルテンサイトは焼き戻しされていても良い。ここで「主体とする」とは、後記する実施例の記載の方法で組織分率を測定したとき、全組織に対する、ベイナイトとマルテンサイトの合計面積率が80面積%以上であり、且つ、全組織に対するフェライトの面積率が0面積%以上5面積%以下のものを意味する。硬質層のベイナイトとマルテンサイトの合計面積率は多い程良く、好ましくは93面積%以上である。一方、フェライトの面積率は少ない程良く、5面積%以下が好ましく、3面積%以下がより好ましく、最も好ましくは0面積%である。
Cは、焼入れ性を向上させ、またマルテンサイトの硬質化効果により、鋼の高強度化に重要な元素である。このような効果を有効に発揮させるため、C量の下限を0.05%以上とする。C量の好ましい下限は0.08%以上であり、より好ましくは0.10%以上である。しかし、Cを過剰に添加すると、軟質相と硬質相の硬度差が大きくなり、加工性および耐遅れ破壊特性が低下するため、C量の上限を0.25%とする。C量の好ましい上限は0.2%以下であり、より好ましくは0.18%以下である。
Siは固溶強化により鋼の強度を高め、加工性向上にも有効な元素である。また、内部酸化層を生成し、水素脆化の抑制作用も有する。このような効果を有効に発揮させるため、Si量の下限を0.5%以上とする。Si量の好ましい下限は0.75%以上であり、より好ましくは1%以上である。しかし、Siはフェライト生成元素であり、Siを過剰に添加すると、フェライトの生成を抑制できず、軟質相と硬質相の硬度差が大きくなり、加工性が低下する。更には、めっき性も悪くなるため、Si量の上限を2.5%とする。Si量の好ましい上限は2%以下であり、より好ましくは1.8%以下である。
Mnは、焼入れ性向上元素であり、フェライトおよびベイナイトを抑制し、マルテンサイトを生成させて高強度化に寄与する。このような効果を有効に発揮させるため、Mn量の下限を2.0%以上とする。Mn量の好ましい下限は2.3%以上であり、より好ましくは2.5%以上である。しかし、Mnを過剰に添加すると、めっき性が低下し、また偏析も著しくなる。更に、Pの粒界偏析を助長する虞がある。そのため、Mn量の上限を4%とする。Mn量の好ましい上限は3.5%以下である。
Pは、固溶強化元素として鋼の強化に有用な元素である。このような効果を有効に発揮させるため、P量の下限を0%超とする。しかし、過剰に添加すると、加工性のほか、溶接性、靱性を劣化させる虞があるため、その上限を0.1%以下とする。P量は少ない方が良く、好ましくは0.03%以下、より好ましくは0.015%以下である。
Sは、不可避的に含有する元素であり、MnSなどの硫化物を形成し、割れの起点なり、加工性を劣化させる虞がある。そのため、S量の上限を0.05%以下とする。S量は少ない方が良く、好ましくは0.01%以下、より好ましくは0.008%以下である。
Alは、脱酸剤として作用する。またAlはNと結合してAlNとなり、オーステナイト粒径の微細化により加工性および耐遅れ破壊特性も向上する。このような作用を有効に発揮させるため、Al量の下限を0.01%以上とする。Al量の好ましい下限は0.02%以上であり、より好ましくは0.03%以上である。しかし、Alを過剰に添加すると、アルミナなどの介在物が増加して加工性が劣化するほか、靱性も劣化するようになる。そのため、Al量の上限を0.1%とする。Al量の好ましい上限は0.08%以下であり、より好ましくは0.05%以下である。
Nは、不可避的に含有する元素であるが、過剰に含まれると加工性が劣化する。また、鋼中にB(ホウ素)を添加した場合には、BN析出物が生成し、Bによる焼入れ性向上作用を阻害するため、Nはできるだけ低減する方が良い。そのため、N量の上限を0.01%以下とする。N量の好ましい上限は0.008%以下であり、より好ましくは0.005%以下である。
これらの元素は、鋼板の強度上昇に有効な元素である。これらの元素は単独で添加しても良いし、二種以上を併用しても良い。
これらの元素は、組織微細化による加工性および耐遅れ破壊特性向上に有効な元素である。これらの元素は単独で添加しても良いし、二種以上を併用しても良い。
CuおよびNiは、高強度化に有効な元素である。これらの元素は単独で添加しても良いし、併用しても良い。
本発明に係る第一の製造方法は、熱延工程と、酸洗、冷延工程と、連続溶融Znめっきライン(CGL(Continuous Galvanizing Line))での酸化工程、還元工程、およびめっき工程とに大別される。そして本発明の特徴部分は、上記鋼中成分を満足する鋼板を、600℃以上の温度で巻取ることにより内部酸化層を形成した熱延鋼板を得る熱延工程と、内部酸化層の平均深さdが4μm以上残るように酸洗・冷間圧延する工程と、酸化帯にて、0.9~1.4の空燃比で酸化する工程と、還元帯にて、Ac3点~Ac3点+100℃の範囲で均熱する工程と、を、この順序で含むところにある。
Ac3(℃)=910-203×[C]1/2-15.2×[Ni]+44.7×[Si]+104×[V]+31.5×[Mo]+13.1×[W]-{30×[Mn]+11×[Cr]+20×[Cu]-700×[P]-400×[Al]-120×[As]-400×[Ti]} ・・・(i)
本発明に係る第二の製造方法は、上記鋼中成分を満足する熱延鋼板を、500℃以上の温度で巻取る熱延工程と、500℃以上の温度で80分以上保温する工程と、内部酸化層の平均深さdが4μm以上残るように酸洗・冷間圧延する工程と、酸化帯にて、0.9~1.4の空燃比で酸化する工程と、還元帯にて、Ac3点~Ac3点+100℃の範囲で均熱する工程と、を、この順序で含む。前述した第一の製造方法と対比すると、上記第二の製造方法では、熱延後巻取温度の下限を500℃以上にしたこと、熱延工程の後に保温工程を設けたことの二点でのみ上記第一の製造方法と相違する。よって、以下では、当該相違点のみ説明する。上記第一の製造方法と一致する工程は、上記第一の製造方法を参照すればよい。
酸洗液:10%塩酸、温度:82℃、酸洗時間:表2のとおり。
めっき鋼板の板幅をWとしたとき、W/4部からサイズ50mm×50mmの試験片を採取した後、グロー放電発光分析法(GD-OES(Glow Discharge-Optical Emission Spectroscopy))にて、めっき層表面からのO量、Fe量、およびZn量をそれぞれ分析し、定量した。詳細には、堀場製作所製GD-PROFILER2型GDA750のGD-OES装置を用いて、上記試験片の表面を、Arグロー放電領域内で高周波スパッタリングし、スパッタされるO、Fe、Znの各元素のArプラズマ内における発光線を連続的に分光することによって、素地鋼板の深さ方向における各元素量プロファイル測定した。スパッタ条件は以下のとおりであり、測定領域は、めっき層表面から深さ50μmまでとした。
パルススパッタ周波数:50Hz
アノード径(分析面積):直径6mm
放電電力:30W
Arガス圧:2.5hPa
酸洗・冷間圧延後の素地鋼板を用いたこと以外は上記(1)と同様にして、内部酸化層の平均深さを算出した。
めっき鋼板の板幅W方向に対して垂直な断面であるW/4部を露出させ、サイズ20mm×20mmの試験片を採取した後、樹脂に埋め込み、めっき層と素地鋼板の界面から素地鋼板の板厚t内部に向かってビッカース硬さを測定した。測定はビッカース硬度計を用い、荷重3gfにて行った。詳細には図3に示すように、めっき層と母材の界面から板厚内部深さ10μmの測定位置から、板厚内部に向かって5μmピッチごとに測定を行い、深さ100μmまでビッカース硬さを測定した。測定点同士の間隔;すなわち図3中、×と×の距離は、最低でも15μm以上とした。各深さでn=1ずつビッカース硬さを測定し、板厚内部方向の硬さ分布を調査した。更に、素地鋼板のt/4部におけるビッカース硬さも同様にして測定した。t/4部と比較してビッカース硬さが90%以下の領域を軟質層とし、その深さを計算した。同様の処理を、同じ試験片で3箇所実施し、その平均を軟質層の平均深さDとした。
めっき鋼板の板幅W方向に対して垂直な断面であるW/4部を露出させ、この断面を研磨し、更に電解研磨した後、ナイタールで腐食させたものをSEM(Scanning Electron Microscope)観察した。観察位置は素地鋼板の板厚をtとしたときt/4位置とし、観察倍率は2000倍、観察領域は40μm×40μmとした。SEMで撮影した金属組織写真を画像解析し、マルテンサイトとベイナイト(両者は区別せず)、およびフェライトの面積率を夫々測定した。表3中、α=フェライト、(B+M)=(ベイナイト+マルテンサイト)を意味する。また、表3中、「その他」の組織の面積分率は、100面積%から、マルテンサイトとベイナイト、およびフェライトの各面積率を引いて算出した。観察は任意に3視野について行い、平均値を算出した。
めっき鋼板の圧延方向に垂直な方向と試験片の長手方向が平行になるようにJIS 13号B引張試験片を採取し、JIS Z2241に従ってC方向の引張強度(TS)および降伏応力(YS)を測定した。TSおよびYSより、降伏比YR(YS/TS)を算出した。
めっき鋼板の圧延方向に垂直な方向と試験片の長手方向が平行になるようにめっき鋼板から切り出した20mm×70mmの試験片を用意し、曲げ稜線が長手方向となるように90°V曲げ試験を行った。曲げ半径Rを適宜変化させて試験を実施し、試験片に割れが発生することなく曲げ加工できる最小曲げ半径Rminを求めた。
TSが980MPa以上、1080MPa未満の場合、Rmin/t<1.0を合格
TSが1080MPa以上、1180MPa未満の場合、Rmin/t<1.5を合格
TSが1180MPa以上の場合、Rmin/t<2.50を合格
めっき鋼板の板幅W方向に対して垂直な断面であるW/4部を露出させ、150mm(W)×30mm(L)の試験片を切り出し、最小曲げ半径にてU曲げ加工を行った後、ボルトで締め付け、U曲げ加工試験片の外側表面に1000MPaの引張応力を負荷した。引張応力の測定は、U曲げ加工試験片の外側に歪ゲージを貼り付け、歪を引張応力に換算して行った。その後、U曲げ加工試験片のエッジ部をマスキングし、電気化学的に水素をチャージさせた。水素チャージは、試験片を、0.1M-H2SO4(pH=3)と0.01M-KSCNの混合溶液中に浸漬し、室温且つ100μA/mm2の定電流の条件で行なった。
日本鉄鋼連盟規格JFST1001に準じて穴拡げ試験を実施し、λを測定した。詳細には、めっき鋼板に直径10mmの穴を打ち抜いた後、周囲を拘束した状態で60°円錐のポンチを穴に押し込み、亀裂発生限界における穴の直径を測定した。下記式から限界穴拡げ率λ(%)を求め、λが25%以上を合格、すなわち穴拡げ性に優れると評価した。限界穴拡げ率λ(%)={(Df-D0)/D0}×100
式中、Dfは亀裂発生限界における穴の直径(mm)、D0は初期穴の直径(mm)
めっき鋼板の外観を目視で観察し、不めっきが観察されない場合を合格、すなわち、めっき性に優れると評価した。
2 素地鋼板
3 内部酸化層
4 軟質層
5 硬質層
6 内部
Claims (5)
- 素地鋼板の表面に、溶融亜鉛めっき層または合金化溶融亜鉛めっき層を有するめっき鋼板であって、
(1)前記素地鋼板は、質量%で、
C :0.05~0.25%、
Si:0.5~2.5%、
Mn:2.0~4%、
P :0%超0.1%以下、
S :0%超0.05%以下、
Al:0.01~0.1%、および
N :0%超0.01%以下を含有し、
残部が鉄および不可避不純物からなり、
(2)前記素地鋼板と前記めっき層との界面から素地鋼板側に向って順に、
SiおよびMnよりなる群から選択される少なくとも一種の酸化物を含む内部酸化層と、
前記内部酸化層を含む層であって、且つ、前記素地鋼板の板厚をtとしたとき、ビッカース硬さが、前記素地鋼板のt/4部におけるビッカース硬さの90%以下を満足する軟質層と、
マルテンサイトとベイナイトを主体とする組織で構成される硬質層と、
を有し、且つ、
前記軟質層の平均深さDが20μm以上、および
前記内部酸化層の平均深さdが4μm以上、前記D未満
を満足し、引張強度が980MPa以上である高強度めっき鋼板。 - 前記素地鋼板が、更に、質量%で、
Cr:0%超1%以下、
Mo:0%超1%以下、
B :0%超0.01%以下、
Ti:0%超0.2%以下、
Nb:0%超0.2%以下、
V :0%超0.2%以下
Cu:0%超1%以下、および
Ni:0%超1%以下、
よりなる群から選択される少なくとも一種を含有するものである請求項1に記載の高強度めっき鋼板。 - 前記内部酸化層の平均深さdと前記軟質層の平均深さDは、D>2dの関係を満足する請求項1または2に記載の高強度めっき鋼板。
- 請求項1または2に記載の高強度めっき鋼板を製造する方法であって、
前記素地鋼板の鋼中成分を満足する鋼板を、600℃以上の温度で巻取る熱延工程と、内部酸化層の平均深さdが4μm以上残るように酸洗・冷間圧延する工程と、酸化帯にて、0.9~1.4の空燃比で酸化する工程と、還元帯にて、Ac3点~Ac3点+100℃の範囲で均熱する工程を、この順序で含む高強度めっき鋼板の製造方法。 - 請求項1または2に記載の高強度めっき鋼板を製造する方法であって、
前記素地鋼板の鋼中成分を満足する鋼板を、500℃以上の温度で巻取る熱延工程と、500℃以上の温度で80分以上保温する工程と、内部酸化層の平均深さdが4μm以上残るように酸洗・冷間圧延する工程と、酸化帯にて、0.9~1.4の空燃比で酸化する工程と、還元帯にて、Ac3点~Ac3点+100℃の範囲で均熱する工程を、この順序で含む高強度めっき鋼板の製造方法。
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EP3358032A4 (en) * | 2015-10-02 | 2019-04-10 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | GALVANIZED STEEL SHEET FOR HOT PRESSING AND METHOD FOR PRODUCING HOT PRESSED MOLDED ARTICLE |
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WO2017105064A1 (ko) * | 2015-12-15 | 2017-06-22 | 주식회사 포스코 | 표면품질 및 점 용접성이 우수한 고강도 용융아연도금강판 및 그 제조방법 |
US10900097B2 (en) | 2015-12-15 | 2021-01-26 | Posco | High-strength hot-dip galvanized steel sheet having excellent surface quality and spot weldability |
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Also Published As
Publication number | Publication date |
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KR20160030295A (ko) | 2016-03-16 |
US20160160335A1 (en) | 2016-06-09 |
CN105324506A (zh) | 2016-02-10 |
MX2016000266A (es) | 2016-04-20 |
EP3020842A1 (en) | 2016-05-18 |
KR101754543B1 (ko) | 2017-07-06 |
JP2015034334A (ja) | 2015-02-19 |
EP3020842A4 (en) | 2017-03-15 |
EP3020842B1 (en) | 2019-03-13 |
CN105324506B (zh) | 2018-02-09 |
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