WO2010061957A1 - 溶融亜鉛めっき鋼板およびその製造方法 - Google Patents
溶融亜鉛めっき鋼板およびその製造方法 Download PDFInfo
- Publication number
- WO2010061957A1 WO2010061957A1 PCT/JP2009/070208 JP2009070208W WO2010061957A1 WO 2010061957 A1 WO2010061957 A1 WO 2010061957A1 JP 2009070208 W JP2009070208 W JP 2009070208W WO 2010061957 A1 WO2010061957 A1 WO 2010061957A1
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- WO
- WIPO (PCT)
- Prior art keywords
- steel sheet
- steel plate
- hot
- plating
- galvanized
- Prior art date
Links
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 29
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 126
- 239000010959 steel Substances 0.000 claims abstract description 126
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 60
- 239000010410 layer Substances 0.000 claims abstract description 51
- 239000002344 surface layer Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims description 91
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- 229910052760 oxygen Inorganic materials 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 31
- 238000005246 galvanizing Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000005275 alloying Methods 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 description 25
- 230000003647 oxidation Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 23
- 239000007789 gas Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 201000006705 Congenital generalized lipodystrophy Diseases 0.000 description 9
- 230000001737 promoting effect Effects 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 241000316887 Saissetia oleae Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- -1 and further Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 241000252073 Anguilliformes Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- 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
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
-
- 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.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
- Y10T428/12618—Plural oxides
-
- 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]
-
- 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]
-
- 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
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
-
- 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
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
Definitions
- the present invention relates to a hot-dip galvanized steel sheet that is excellent in workability and uses a steel sheet containing Si and Mn as a base material and a method for producing the same.
- a hot dip galvanized steel sheet uses a thin steel sheet obtained by hot rolling or cold rolling a slab as a base material, and this base steel plate is called a continuous hot dip galvanizing line (hereinafter referred to as CGL) having an annealing furnace. ) By recrystallization annealing and hot dip galvanizing. In the case of an alloyed hot-dip galvanized steel sheet, it is manufactured after further hot-dip galvanizing treatment.
- the heating furnace type of the CGL annealing furnace there are a DFF (direct fire) type, a NOF (non-oxidation) type, an all-radiant tube type, etc., but in recent years, it is easy to operate and pick-up hardly occurs.
- the construction of CGLs equipped with an all-radiant tube type heating furnace is increasing for reasons such as the ability to produce high-quality plated steel sheets at low cost.
- DFF (direct fire) type and NOF (non-oxidation) type all radiant tube type heating furnaces do not have an oxidation step immediately before annealing, so about steel plates containing oxidizable elements such as Si and Mn. It is disadvantageous in terms of securing plating properties.
- Patent Document 1 and Patent Document 2 specify a heating temperature in a reduction furnace by a relational expression with a water vapor partial pressure, and a dew point.
- a technique for internally oxidizing the surface layer of the base material by increasing the thickness is disclosed.
- cracks are likely to occur during processing, and the plating peel resistance is reduced. Also, a decrease in corrosion resistance is observed.
- Patent Document 3 not only the oxidizing gases H 2 O and O 2, but also the CO 2 concentration is simultaneously defined, so that the surface layer of the base material immediately before plating is internally oxidized to suppress external oxidation and thereby the appearance of plating.
- a technique for improving the above is disclosed.
- cracks are likely to occur during processing due to the presence of the internal oxide, and the plating peel resistance is reduced. Also, a decrease in corrosion resistance is observed.
- CO 2 may cause problems such as in-furnace contamination and carburizing on the steel sheet surface, resulting in changes in mechanical properties.
- the present invention has been made in view of such circumstances, and uses a steel sheet containing Si and Mn as a base material, and a high-strength hot-dip galvanized steel sheet having excellent resistance to plating peeling during high processing and a method for producing the same.
- the purpose is to provide.
- the present invention is as follows.
- Si and Mn are contained in the Fe crystal grains within 1 ⁇ m from the Fe crystal grain boundary.
- One or more selected oxides are present in total of 0.01 to 0.5 g / m 2 per side, and in the region immediately below the galvanized layer from the surface of the underlying steel plate to 10 ⁇ m, 1 ⁇ m from the Fe crystal grain boundary.
- a method for producing a hot-dip galvanized steel sheet which performs hot-dip galvanizing so that the intermediate oxygen partial pressure (Po 2 ) satisfies the following formula (1). ⁇ 12 + 0.5 ⁇ [Si] + 0.2 ⁇ [Mn] ⁇ LogPo 2 ⁇ ⁇ 4 (1) However, indicating the [Si], [Mn], respectively, in steel Si, Mn content (mass%), Po 2 is oxygen partial pressure (Pa).
- the steel plate is further heated to a temperature of 450 ° C. or more and 550 ° C. or less to perform alloying treatment, and the Fe content of the plating layer is 7 to 15% by mass.
- the manufacturing method of the hot-dip galvanized steel sheet to make into a range [5] By mass%, C: 0.01 to 0.15%, Si: 0.001 to 2.0%, Mn: 0.1 to 3.0%, Al: 0.001 to 1.0% , P: 0.005 to 0.060%, S ⁇ 0.01%, with the balance being 20 to 120 g / m 2 on one side of the surface of the steel plate made of Fe and inevitable impurities
- the steel plate surface layer portion within 100 ⁇ m from the surface of the underlying steel plate has a galvanized layer, and one or more oxides selected from Fe, Si, Mn, Al, and P are total.
- the present inventors have studied a method for solving the problem by a new method not confined to the conventional idea. As a result, it has excellent anti-plating resistance at the time of high processing by performing more advanced control over the structure and structure of the surface layer of the underlying steel sheet directly under the plating layer, which may be the starting point of cracks during high processing. It has been found that a high-strength hot-dip galvanized steel sheet can be obtained.
- the high-strength hot-dip galvanized steel sheet is a steel sheet having a tensile strength TS of 340 MPa or more. Further, the high-strength hot-dip galvanized steel sheet of the present invention includes a plated steel sheet (hereinafter sometimes referred to as GI) that is not subjected to alloying after the hot-dip galvanizing process, and a plated steel sheet (hereinafter referred to as GA) that is subjected to the alloying process. In some cases).
- GI plated steel sheet
- GA plated steel sheet
- C 0.01 to 0.15%
- C improves workability by forming martensite or the like as a steel structure.
- 0.01% or more is necessary.
- the C content is 0.01% or more and 0.15% or less.
- Si 0.001 to 2.0% Si is an element effective for strengthening steel to obtain a good material, and 0.001% or more is necessary to obtain the intended strength of the present invention. If Si is less than 0.001%, the strength within the scope of application of the present invention cannot be obtained, and there is no particular problem with respect to resistance to plating peeling during high processing. On the other hand, if it exceeds 2.0%, it is difficult to improve the resistance to plating peeling during high processing. Therefore, the Si amount is set to 0.001% or more and 2.0% or less.
- Mn 0.1 to 3.0%
- Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 0.1% or more. On the other hand, if it exceeds 3.0%, it becomes difficult to ensure weldability and plating adhesion, and to ensure a balance between strength and ductility. Therefore, the amount of Mn is 0.1% or more and 3.0% or less.
- Al 0.001 to 1.0% Since Al is an element that is more easily thermodynamically oxidized than Si and Mn, it forms a complex oxide with Si and Mn. Compared with the case where Al is not contained, the inclusion of Al has an effect of promoting the internal oxidation of Si and Mn immediately below the surface layer of the base steel sheet (also referred to as “base iron”). This effect is obtained at 0.001% or more. On the other hand, if it exceeds 1.0%, the cost increases. Therefore, the Al content is 0.001% or more and 1.0% or less.
- P 0.005 to 0.060%
- P is one of the elements inevitably contained, and in order to reduce it to less than 0.005%, there is a concern about an increase in cost, so the content is made 0.005% or more.
- P exceeds 0.060% weldability deteriorates. Furthermore, the surface quality deteriorates.
- plating adhesion deteriorates during non-alloying treatment, and a desired degree of alloying cannot be achieved unless the alloying treatment temperature is raised during alloying treatment.
- the P content is 0.005% or more and 0.060% or less.
- S ⁇ 0.01% S is one of the elements inevitably contained. Although a lower limit is not specified, 0.01% or less is preferable because weldability deteriorates when contained in a large amount.
- B 0.001 to 0.005%
- Nb 0.005 to 0.05%
- Ti 0.005 to 0.05%
- Cr 0.001
- Cr, Mo, Nb, Cu, and Ni are used alone or in combination of two or more, and when the annealing atmosphere is a humid atmosphere containing a relatively large amount of H 2 O, Since it has an effect of promoting internal oxidation and suppressing surface concentration, it may be added not for improving mechanical properties but for obtaining good plating adhesion.
- the reason for limiting the appropriate addition amount in the case of adding these elements is as follows.
- B 0.001 to 0.005%
- B amount shall be 0.001% or more and 0.005% or less.
- Nb 0.005 to 0.05% If Nb is less than 0.005%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Mo. On the other hand, if it exceeds 0.05%, the cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.05% or less.
- Ti 0.005 to 0.05% If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, the plating adhesion deteriorates. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.05% or less.
- Cr 0.001 to 1.0%
- Cr is less than 0.001
- Cr amount shall be 0.001% or more and 1.0% or less.
- Mo 0.05 to 1.0% If Mo is less than 0.05%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Nb, Ni or Cu. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Mo content is 0.05% or more and 1.0% or less.
- Cu 0.05 to 1.0% If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual ⁇ phase and the effect of improving the plating adhesion when combined with Ni or Mo. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.0% or less.
- Ni 0.05 to 1.0%
- Ni 0.05 to 1.0%
- Ni 0.05 to 1.0%
- it exceeds 1.0% cost increases. Therefore, when it contains, Ni amount shall be 0.05% or more and 1.0% or less.
- the remainder other than the above is Fe and inevitable impurities.
- the total amount of the oxide (hereinafter referred to as internal oxidation amount) can be measured by “impulse furnace melting-infrared absorption method”.
- the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 ⁇ m or more.
- the oxygen concentration in the base metal is measured as the measured oxygen concentration, and the oxygen concentration in the steel in the thickness direction of the high-tensile steel plate after continuous annealing is measured.
- the amount of oxygen after internal oxidation was OI.
- the difference between OI and OH was calculated using the oxygen amount OI after internal oxidation of the high-tensile steel plate thus obtained and the oxygen amount OH contained in the base material, and the single-sided unit area (that was 1 m 2) value converted into the amount per (g / m 2) the amount of internal oxidation.
- the plating peeling-proof improvement effect is recognized because the said oxide exists in the steel plate surface layer part within 100 micrometers from the base steel plate surface just under a plating layer. Therefore, there is no problem even if the oxide grows in a region exceeding 100 ⁇ m immediately below the plating layer (plating / underlying steel plate interface). However, in order to grow the oxide in a region exceeding 100 ⁇ m, it is necessary to make the heating temperature higher, so that it is difficult to achieve both mechanical properties.
- a crystalline oxide containing Si and Mn is precipitated in Fe crystal grains within 1 ⁇ m from the Fe crystal grain boundary in the region immediately below the galvanized layer and 10 ⁇ m from the surface of the underlying steel plate. ing.
- the grain boundary diffusion of easily oxidizable elements in the steel can be suppressed, but the intragranular diffusion may not be sufficiently suppressed. Therefore, it is necessary to oxidize not only within the grain boundary but also within the grain.
- a crystalline oxide containing Si and Mn is precipitated in Fe crystal grains within 1 ⁇ m from the Fe crystal grain boundary of the base steel sheet in a region from immediately below the plating layer to 10 ⁇ m.
- the amount of solid solution Si and Mn in the ground iron grains in the vicinity of the oxide is reduced by depositing the oxide in the ground steel grains. As a result, concentration on the surface due to intragranular diffusion of Si and Mn can be suppressed.
- the upper limit is set to 1 ⁇ m from the grain boundary.
- Fe, Si, Mn, Al, P, and further, B, Nb, Ti, Cr, Mo are formed on the steel plate surface layer portion within 100 ⁇ m from the surface of the base steel plate immediately below the galvanized layer.
- a crystalline oxide containing Si and Mn is precipitated in Fe crystal grains within 1 ⁇ m from the Fe crystal grain boundary.
- At least one kind selected from Fe, Si, Mn, Al, P, and further, B, Nb, Ti, Cr, Mo, Cu, Ni is formed on the steel sheet surface layer portion within 100 ⁇ m from the surface of the base steel sheet.
- the above oxide is formed in an amount of 0.01 to 0.5 g / m 2 per side, and Si and Fe are within 1 ⁇ m from the Fe crystal grain boundary of the underlying steel plate in the region from directly below the plating layer to 10 ⁇ m.
- the temperature in the annealing furnace is 600 ° C. or more and 900 ° C. when performing hot dip galvanizing after annealing in CGL having an all radiant tube type heating furnace in the annealing furnace.
- the oxygen partial pressure (Po 2 ) in the atmosphere needs to satisfy the following formula (1). ⁇ 12 + 0.5 ⁇ [Si] + 0.2 ⁇ [Mn] ⁇ LogPo 2 ⁇ ⁇ 4 (1)
- Po 2 oxygen partial pressure (Pa).
- the oxygen partial pressure (Po 2 ) in the atmosphere is controlled, and the temperature range satisfying the above formula is 600 ° C. or higher and 900 ° C. or lower.
- the surface concentration of Si (and / or Mn) increases in proportion to the amount of Si (and / or Mn) in the steel.
- Si (and / or Mn) in the steel shifts to internal oxidation, so that the amount of surface enrichment decreases as the oxygen potential in the atmosphere increases. Therefore, it is necessary to increase the oxygen potential in the atmosphere in proportion to the amount of Si (and / or Mn) in the steel.
- the proportionality factor for the amount of Si in steel is 0.5
- the proportionality factor for the amount of Mn in steel is 0.2.
- the intercept is also known to be -12.
- the upper limit of LogPo 2 is set to ⁇ 4, and the lower limit is set to ⁇ 12 + 0.5 ⁇ [Si] + 0.2 ⁇ [Mn].
- the lower limit is set to ⁇ 12 + 0.5 ⁇ [Si] + 0.2 ⁇ [Mn].
- LogPo 2 is a of H 2 O from the dew point, it is possible to calculate the equilibrium calculated from a control value of concentration of H 2, in controlling the LogPo 2, instead of measuring and controlling LogPo 2 directly, H 2 O As a result, it is preferable to control LogPo 2 by controlling the H 2 concentration.
- Method of measuring between H 2 O and concentration of H 2 from the dew point are not particularly limited.
- a predetermined amount of gas is sampled, and the dew point is measured with a dew point measuring device (Due Cup or the like) to determine the H 2 O partial pressure.
- the H 2 concentration is measured with a commercially available H 2 densitometer.
- the partial pressures of H 2 O and H 2 are calculated from the concentration ratio.
- Po 2 is high, N 2 —H 2 gas is blown to reduce the dew point or increase the H 2 gas concentration.
- Po 2 is low, N 2 —H 2 gas containing a large amount of water vapor is blown to increase the dew point or a small amount of O 2 gas is mixed.
- the base steel sheet on which the Si and Mn-based composite oxide grows is preferably a soft and highly workable ferrite phase.
- the surface of the steel sheet has a galvanized layer having a plating adhesion amount of 20 to 120 g / m 2 on one side. If it is less than 20 g / m 2 , it becomes difficult to ensure corrosion resistance. On the other hand, if it exceeds 120 g / m 2 , the plating peel resistance deteriorates.
- the degree of alloying is preferably 7 to 15% when the alloying treatment is performed by heating to a temperature of 450 ° C. or higher and 550 ° C. or lower. If it is less than 7%, unevenness in alloying and flaking properties deteriorate. On the other hand, if it exceeds 15%, the plating peel resistance deteriorates.
- the steel having the above chemical components After hot rolling the steel having the above chemical components, it is cold rolled at a rolling reduction of 40 to 80%, and then annealed and hot dip galvanized in a continuous hot dip galvanizing facility having an all radiant tube type heating furnace. I do.
- the oxygen partial pressure in the atmosphere (Po 2 ) satisfies the following formula (1) in the annealing furnace temperature range of 600 ° C. to 900 ° C. I will do it. This is the most important requirement in the present invention.
- the conditions for hot rolling are not particularly limited. It is preferable to perform pickling after hot rolling. The black scale formed on the surface in the pickling process is removed, and then cold-rolled.
- Cold rolling is performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, if the rolling reduction exceeds 80%, the steel sheet is a high-strength steel sheet, so that not only the rolling cost is increased, but also the surface concentration during annealing increases, so the plating characteristics deteriorate.
- the cold-rolled steel sheet is annealed in a CGL having an all-radiant tube type heating furnace in the annealing furnace, and then subjected to hot dip galvanizing treatment or further alloying treatment.
- a heating process is performed in which the steel sheet is heated to a predetermined temperature in a heating zone before the heating furnace, and a soaking process is performed in which the temperature is maintained at a predetermined temperature for a predetermined time in the soaking zone after the heating furnace.
- At least one oxide selected from Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, and Ni is formed on the surface layer of the steel sheet within 100 ⁇ m from the surface of the underlying steel sheet.
- the oxygen partial pressure (Po 2 ) in the atmosphere in the temperature range of 600 ° C. to 900 ° C. in the annealing furnace is as follows. It is necessary to satisfy Formula (1). Therefore, when Po 2 is high in CGL, N 2 —H 2 gas is blown in to reduce the dew point or increase the H 2 gas concentration.
- a method for performing the hot dip galvanizing treatment may be a conventional method.
- the steel sheet is heated to 450 ° C. or higher and 550 ° C. or lower to perform the alloying treatment, and the Fe content of the plating layer is 7 to 15% by mass. It is preferable to do so.
- the hot-rolled steel sheet having the steel composition shown in Table 1 was pickled and the black scale was removed, followed by cold rolling under the conditions shown in Table 2 to obtain a cold-rolled steel sheet having a thickness of 1.0 mm.
- the cold-rolled steel sheet obtained above was charged into a CGL equipped with an all-radiant tube type heating furnace in an annealing furnace.
- CGL Po 2 in the annealing atmosphere is controlled and passed as shown in Table 2, heated to 850 ° C. in a heating zone, kept soaked at 850 ° C. in the soaking zone, and annealed, then 460 ° C.
- Hot dip galvanizing treatment was performed in an Al-containing Zn bath.
- the atmosphere in the annealing furnace may be considered to be almost uniform including the heating furnace and the soaking furnace. Further, the oxygen partial pressure and temperature were measured by sucking atmospheric gas from the central part in the annealing furnace (actually, the part on the operation side (0p side) 1 m from the furnace bottom).
- N 2 gas flows pipe humidified by heating water tank was placed in N 2, by introducing H 2 gas to N 2 gas humidified
- the dew point of the atmosphere was controlled by mixing and introducing it into the furnace.
- the H 2 % of the atmosphere was controlled by adjusting the amount of H 2 gas introduced into the N 2 gas with a gas valve.
- a 0.14% Al-containing Zn bath was used for the production of GA, and a 0.18% Al-containing Zn bath was used for the production of GI.
- the adhesion amount was adjusted to 40 g / m 2 , 70 g / m 2 or 140 g / m 2 (adhesion amount per side) by gas wiping, and GA was alloyed.
- the hot-dip galvanized steel sheets (GA and GI) obtained as described above were examined for appearance (plating appearance), plating peeling resistance during high processing, and workability. Also, the amount of oxide (internal oxidation amount) existing in the surface layer of the underlying steel sheet up to 100 ⁇ m directly below the plating layer, and the crystalline oxide containing Si and Mn existing in the surface layer of the underlying steel sheet up to 10 ⁇ m immediately below the plating layer The intragranular precipitate immediately below the plating layer at a position within 1 ⁇ m from the morphology, growth location, and grain boundary was measured. The measurement method and evaluation criteria are shown below.
- Appearance was judged as good appearance (symbol ⁇ ) when there was no appearance defect such as non-plating or alloying unevenness, and when it was present, it was judged as poor appearance (symbol x).
- ⁇ Plating resistance> With respect to the plating peel resistance at the time of high processing, in GA, it is required to suppress the plating peeling at the bent portion when the plated steel sheet is bent at an acute angle exceeding 90 °.
- the bent portion when bent by 120 ° is peeled off with tape, the amount of peeling per unit length is measured by fluorescent X-rays, and the number of Zn counts is measured according to the following criteria.
- the plating peel resistance was good (symbol ⁇ ), and those of 3 or more were evaluated as poor plating peel resistance (symbol x).
- Fluorescent X-ray Zn count Rank 0 to less than 500: 1 (good) 500 or more and less than 1000: 2 1000 or more and less than ⁇ 2000: 3 2000 or more and less than ⁇ 3000: 4 3000 or more: 5 (poor)
- GI Fluorescent X-ray Zn count: Rank 0 to less than 500: 1 (good) 500 or more and less than 1000: 2 1000 or more and less than ⁇ 2000: 3 2000 or more and less than ⁇ 3000: 4 3000 or more: 5 (poor)
- GI Fluorescent X-ray Zn count: Rank 0 to less than 500: 1 (good) 500 or more and less than 1000: 2 1000 or more and less than ⁇ 2000: 3 2000 or more and less than ⁇ 3000: 4 3000 or more: 5 (poor)
- TS tensile strength
- El elongation
- the amount of internal oxidation is measured by “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the base material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 ⁇ m or more.
- the oxygen concentration in the base metal is measured as the measured oxygen concentration, and the oxygen concentration in the steel in the thickness direction of the high-tensile steel plate after continuous annealing is measured.
- the amount of oxygen after internal oxidation was OI.
- the oxide containing Si and Mn When the oxide containing Si and Mn was observed in one or more of the five places, it was judged that the oxide containing Si and Mn was precipitated. Whether or not the growth site of internal oxidation is ferrite was examined by the cross-sectional SEM for the presence or absence of the second phase, and when the second layer was not observed, it was determined as ferrite. Further, in the region from directly under the plating layer to 10 ⁇ m, the oxide containing Si and Mn in Fe crystal grains within 1 ⁇ m from the grain boundary of the base steel plate is extracted by extracting the precipitated oxide by the extraction replica method. The same method was used.
- GI and GA examples of the present invention produced by the method of the present invention are workability despite being high-strength steel sheets containing a large amount of oxidizable elements such as Si and Mn. In addition, it has excellent anti-plating resistance during high processing and a good plating appearance. On the other hand, in the comparative example, any one or more of plating appearance, workability, and resistance to plating peeling during high processing is inferior.
- the hot-dip galvanized steel sheet of the present invention is excellent in workability, plating peeling resistance and strength at the time of high processing, and can be used as a surface-treated steel sheet for reducing the weight and strength of an automobile body itself.
- the steel sheet can be applied in a wide range of fields, such as home appliances and building materials, as a surface-treated steel sheet provided with rust-preventive properties.
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Abstract
Description
[2]質量%で、C:0.01~0.15%、Si:0.001~2.0%、Mn:0.1~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含み、さらに、B:0.001~0.005%、Nb:0.005~0.05%、Ti:0.005~0.05%、Cr:0.001~1.0%、Mo:0.05~1.0%、Cu:0.05~1.0%、Ni:0.05~1.0%の中から選ばれる1種以上の元素を含有し、残部がFeおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が20~120g/m2の亜鉛めっき層を有し、該亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、P、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる1種以上の酸化物が合計で片面あたり0.01~0.5g/m2存在し、前記亜鉛めっき層直下の、下地鋼板表面から10μmまでの領域においては、Fe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物が存在する溶融亜鉛めっき鋼板。
[3]前記[1]または[2]に記載の鋼板を連続式溶融亜鉛めっき設備において焼鈍および溶融亜鉛めっき処理を行うに際し、焼鈍炉内温度が600℃以上900℃以下の温度域において、雰囲気中酸素分圧(Po2)が、下記の式(1)を満足するように溶融亜鉛めっき処理を行う溶融亜鉛めっき鋼板の製造方法。
−12+0.5×[Si]+0.2×[Mn] ≦ LogPo2 ≦ −4 ……(1)
但し、[Si]、[Mn]はそれぞれ、鋼中Si、Mn量(質量%)、Po2は酸素分圧(Pa)を示す。
[4]前記[3]において、溶融亜鉛めっき処理後、さらに、450℃以上550℃以下の温度に鋼板を加熱して合金化処理を施し、めっき層のFe含有量を7~15質量%の範囲にする溶融亜鉛めっき鋼板の製造方法。
[5]質量%で、C:0.01~0.15%、Si:0.001~2.0%、Mn:0.1~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が20~120g/m2の亜鉛めっき層を有し、該亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、Pのうちから選ばれる1種以上の酸化物が合計で片面あたり0.01~0.5g/m2存在し、前記亜鉛めっき層直下の、下地鋼板表面から10μmまでの領域においては、粒界から1μm以内の地鉄粒内に結晶性Si、Mn系複合酸化物が存在することを特徴とする高強度溶融亜鉛めっき鋼板。
C:0.01~0.15%
Cは、鋼組織としてマルテンサイトなどを形成させることで加工性を向上させる。そのためには0.01%以上必要である。一方、0.15%を越えると溶接性が劣化する。したがって、C量は0.01%以上0.15%以下とする。
Siは鋼を強化して良好な材質を得るのに有効な元素であり、本発明の目的とする強度を得るためには0.001%以上が必要である。Siが0.001%未満では本発明の適用範囲とする強度が得られず、高加工時の耐めっき剥離性についても特に問題とならない。一方、2.0%を越えると高加工時の耐めっき剥離性の改善が困難である。したがって、Si量は0.001%以上2.0%以下とする。
Mnは鋼の高強度化に有効な元素である。機械特性や強度を確保するためは0.1%以上含有させることが必要である。一方、3.0%を越えると溶接性やめっき密着性の確保、強度と延性のバランスの確保が困難になる。したがって、Mn量は0.1%以上3.0%以下とする。
AlはSi、Mnに比べ熱力学的に酸化し易い元素であるため、Si、Mnと複合酸化物を形成する。Alが含有されない場合に比べ、Alを含有することで下地鋼板(「地鉄」とも呼ぶ)表層直下におけるSi、Mnの内部酸化を促進する効果を有する。この効果は0.001%以上で得られる。一方、1.0%を越えるとコストアップになる。したがって、Al量は0.001%以上1.0%以下とする。
Pは不可避的に含有される元素のひとつであり、0.005%未満にするためには、コストの増大が懸念されるため、0.005%以上とする。一方、Pが0.060%を越えて含有されると溶接性が劣化する。さらに、表面品質が劣化する。また、非合金化処理時にはめっき密着性が劣化し、合金化処理時には合金化処理温度を上昇させないと所望の合金化度とすることができない。また所望の合金化度とするために合金化処理温度を上昇させると延性が劣化すると同時に合金化めっき皮膜の密着性が劣化するため、所望の合金化度と、良好な延性、合金化めっき皮膜を両立させることができない。したがって、P量は0.005%以上0.060%以下とする。
Sは不可避的に含有される元素のひとつである。下限は規定しないが、多量に含有されると溶接性が劣化するため0.01%以下が好ましい。
これらの元素を添加する場合における適正添加量の限定理由は以下の通りである。
Bは0.001%未満では焼き入れ促進効果が得られにくい。一方、0.005%超えではめっき密着性が劣化する。よって、含有する場合、B量は0.001%以上0.005%以下とする。但し言うまでもなく機械的特性改善上添加する必要がないと判断される場合は添加する必要はない。
Nbは0.005%未満では強度調整の効果やMoとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、0.05%越えではコストアップを招く。よって、含有する場合、Nb量は0.005%以上0.05%以下とする。
Tiは0.005%未満では強度調整の効果が得られにくい。一方、0.05%越えではめっき密着性の劣化を招く。よって、含有する場合、Ti量は0.005%以上0.05%以下とする。
Crは0.001未満では焼き入れ性や焼鈍雰囲気がH2Oを比較的多量に含むような湿潤雰囲気である場合の内部酸化促進効果が得られにくい。一方、1.0%越えではCrが表面濃化するため、めっき密着性や溶接性が劣化する。よって、含有する場合、Cr量は0.001%以上1.0%以下とする。
Moは0.05%未満では強度調整の効果やNb、またはNiやCuとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、1.0%越えではコストアップを招く。よって、含有する場合、Mo量は0.05%以上1.0%以下とする。
Cuは0.05%未満では残留γ相形成促進効果やNiやMoとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、1.0%越えではコストアップを招く。よって、含有する場合、Cu量は0.05%以上1.0%以下とする。
Niは0.05%未満では残留γ相形成促進効果やCuとMoとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、1.0%越えではコストアップを招く。よって、含有する場合、Ni量は0.05%以上1.0%以下とする。
鋼中に多量のSiおよびMnが添加された溶融亜鉛めっき鋼板において、高加工時の耐めっき剥離性を満足させるためには、高加工時の割れなどの起点になる可能性があるめっき層直下の下地鋼板表層の組織、構造のより高度な制御が必要である。
そこで、本発明では、具体的に、まず、めっき性を確保するために焼鈍工程において酸素ポテンシャルを高める制御をする。酸素ポテンシャルを高めることで易酸化性元素であるSiやMn等がめっき直前に予め内部酸化し下地鋼板表層部におけるSi、Mnの活量が低下する。そして、これらの元素の外部酸化が抑制され、結果的にめっき性及び耐めっき剥離性が改善する。さらに、この改善効果は、亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部にFe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる少なくとも1種以上の酸化物を片面あたり0.01g/m2以上形成することで認められる。一方、0.5g/m2以上形成させてもこの効果は飽和するため、上限は0.5g/m2とする。
内部酸化物が粒界にのみ存在し、粒内に存在しない場合、鋼中の易酸化性元素の粒界拡散は抑制できるが、粒内拡散は十分に抑制できない場合がある。したがって、粒界のみならず粒内でも内部酸化させる必要がある。具体的には、めっき層直下から10μmまでの領域において、下地鋼板のFe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物を析出させる。地鉄粒内に酸化物が析出することで、酸化物近傍の地鉄粒内の固溶Si、Mnの量が減少する。その結果、Si、Mnの粒内拡散による表面への濃化を抑制することができる。
以上より、本発明においては、亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる1種以上の酸化物合計で片面あたり0.01~0.5g/m2とする。また、めっき層直下の、下地鋼板表面から10μmまでの領域において、Fe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物を析出させる。
する必要がある。
−12+0.5×[Si]+0.2×[Mn] ≦ LogPo2 ≦ −4 ……(1)
但し、[Si]、[Mn]はそれぞれ、鋼中Si、Mn量(質量%)、Po2は酸素分圧(Pa)を示す。
なお、LogPo2は露点からのH2Oと、H2濃度の制御値から平衡計算で算出できるため、LogPo2を制御するにあたっては、LogPo2を直接測定し制御するのではなく、H2OとH2濃度を制御することで結果としてLogPo2を制御するのが好ましい。なお、LogPo2は以下の式(2)により算出できる。
Po2=(PH2O/PH2)2×exp(ΔG/RT) ……(2)
(ΔG:GibbsのFree Energy、R:気体定数、T:温度)
露点からのH2OとH2濃度の測定方法は特に限定しない。例えば、所定量のガスをサンプリングし、それを露点計測装置(Due Cupなど)により露点を測定し、H2O分圧を求める。同様に、市販のH2濃度計によりH2濃度を測定する。または、雰囲気内の圧力を測定すれば、濃度比からH2O、H2の分圧が算出される。
Po2が高い場合には、N2−H2ガスを吹き込み露点を低下させるか、H2ガス濃度を増加させる。一方、Po2が低い場合には、水蒸気を多く含むN2−H2ガスを吹き込み、露点を増加させるか、または、O2ガスを微量混合させる。
−12+0.5×[Si]+0.2×[Mn] ≦ LogPo2 ≦ −4 ……(1)
但し、[Si]、[Mn]はそれぞれ、鋼中Si、Mn量(質量%)、Po2は酸素分圧(Pa)を示す。
熱間圧延後は酸洗処理を行うのが好ましい。酸洗工程で表面に生成した黒皮スケールを除去し、しかる後冷間圧延する。
オールラジアントチューブ型の加熱炉では、加熱炉前段の加熱帯で鋼板を所定温度まで加熱する加熱工程を行い、加熱炉後段の均熱帯で所定温度に所定時間保持する均熱工程を行う。
下地鋼板表面から100μm以内の鋼板表層部にFe、Si、Mn、Al、P、さらには、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる少なくとも1種以上の酸化物を片面あたり0.01~0.5g/m2形成させ、めっき層直下の、下地鋼板表面から10μmまでの領域において、Fe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物を析出させるために、上述したように、溶融亜鉛めっき処理する際には、焼鈍炉内の600℃以上900℃以下の温度域の雰囲気中酸素分圧(Po2)が、下記の式(1)を満足する必要がある。ゆえに、CGLにおいて、Po2が高い場合には、N2−H2ガスを吹き込み露点を低下させるか、H2ガス濃度を増加させる。一方、Po2が低い場合には、水蒸気を多く含むN2−H2ガスを吹き込み、露点を増加させるか、または、O2ガスを微量混合させる等を行う。これらの操作により、H2OとH2濃度を制御し、結果としてLogPo2を制御する。
−12+0.5×[Si]+0.2×[Mn] ≦ LogPo2 ≦ −4 ……(1)
但し、[Si]、[Mn]はそれぞれ、鋼中Si、Mn量(質量%)、Po2は酸素分圧(Pa)を示す。
なお、H2の体積分率が10%未満では還元による活性化効果が得られず耐めっき剥離性が劣化する。上限は特に規定しないが、75%越えではコストがかかり、かつ効果が飽和する。よって、コストの点からH2の体積分率は75%以下が好ましい。
溶融亜鉛めっき処理を行う方法は、常法でよい。
溶融亜鉛めっき処理に引き続き合金化処理を行うときは、溶融亜鉛めっきしたのち、450℃以上550℃以下に鋼板を加熱して合金化処理を施し、めっき層のFe含有量が7~15質量%になるよう行うのが好ましい。
表1に示す鋼組成からなる熱延鋼板を酸洗し、黒皮スケールを除去した後、表2に示す条件にて冷間圧延し、厚さ1.0mmの冷延鋼板を得た。
なお、雰囲気の露点の制御については、N2中に設置した水タンクを加熱して加湿したN2ガスが流れる配管を予め別途設置し、加湿したN2ガス中にH2ガスを導入して混合し、これを炉内に導入することで雰囲気の露点を制御した。雰囲気のH2%の制御は、N2ガス中へ導入するH2ガス量をガスバルブで調整することで行った。
また、GAの製造には0.14%Al含有Zn浴を、GIの製造には0.18%Al含有Zn浴を用いた。付着量はガスワイピングにより40g/m2、70g/m2または140g/m2(片面あたり付着量)に調節し、GAは合金化処理した。
外観性は、不めっきや合金化ムラなどの外観不良が無い場合は外観良好(記号○)、ある場合は外観不良(記号×)と判定した。
高加工時の耐めっき剥離性は、GAではめっき鋼板を、90°を越えて鋭角に曲げたときの曲げ加工部のめっき剥離の抑制が要求される。本実施例では120°曲げした場合の曲げ加工部をテープ剥離し、単位長さ当たりの剥離量を蛍光X線によりZnカウント数を測定し、下記の基準に照らして、ランク1、2のものを耐めっき剥離性が良好(記号○)、3以上のものを耐めっき剥離性が不良(記号×)と評価した。
蛍光X線Znカウント数:ランク
0−500未満:1(良)
500以上−1000未満:2
1000以上−2000未満:3
2000以上−3000未満:4
3000以上:5(劣)
GIでは、衝撃試験時の耐めっき剥離性が要求される。ボールインパクト試験を行い、加工部をテープ剥離し、めっき層の剥離有無を目視判定した。
○:めっき層の剥離無し
×:めっき層が剥離
<加工性>
加工性は、JIS5号片を作成し引っ張り強度(TS(MPa))と伸び(El(%))を測定し、TS x El≧22000のものを良好、TS x El<22000のものを不良とした。
内部酸化量は、「インパルス炉溶融−赤外線吸収法」により測定する。ただし、母材(すなわち焼鈍を施す前の高張力鋼板)に含まれる酸素量を差し引く必要があるので、本発明では、連続焼鈍後の高張力鋼板の両面の表層部を100μm以上研磨して鋼中酸素濃度を測定し、その測定値を母材に含まれる酸素量OHとし、また、連続焼鈍後の高張力鋼板の板厚方向全体での鋼中酸素濃度を測定して、その測定値を内部酸化後の酸素量OIとした。このようにして得られた高張力鋼板の内部酸化後の酸素量OIと、母材に含まれる酸素量OHとを用いて、OIとOHの差(=OI−OH)を算出し、さらに片面単位面積(すなわち1m2)当たりの量に換算した値(g/m2)を内部酸化量とした。
めっき層を溶解除去後、その断面をSEMで観察し、粒内析出物の電子線回折で非晶質、結晶性の別を調査し、同じくEDX、EELSで組成を決定した。粒内析出物が結晶性で、SiおよびMnが主成分である場合にSi及びMnを含む酸化物であると判定した。視野倍率は5000~20000倍で、各々5箇所調査した。5箇所の内、1箇所以上にSi及びMnを含む酸化物が観察された場合、Si及びMnを含む酸化物が析出していると判断した。内部酸化の成長箇所がフェライトであるか否かは、断面SEMで第2相の有無を調査し、第2層が認められないときはフェライトと判定した。また、めっき層直下から10μmまでの領域において、下地鋼板の結晶粒界から1μm以内のFe結晶粒内のSi及びMnを含む酸化物は、断面を抽出レプリカ法で析出酸化物を抽出し上記の同様の手法で決定した。
一方、比較例では、めっき外観、加工性、高加工時の耐めっき剥離性のいずれか一つ以上が劣る。
Claims (5)
- 質量%で、C:0.01~0.15%、Si:0.001~2.0%、Mn:0.1~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が20~120g/m2の亜鉛めっき層を有し、該亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、Pのうちから選ばれる1種以上の酸化物が合計で片面あたり0.01~0.5g/m2存在し、前記亜鉛めっき層直下の、下地鋼板表面から10μmまでの領域においては、Fe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物が存在する溶融亜鉛めっき鋼板。
- 質量%で、C:0.01~0.15%、Si:0.001~2.0%、Mn:0.1~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含み、さらに、B:0.001~0.005%、Nb:0.005~0.05%、Ti:0.005~0.05%、Cr:0.001~1.0%、Mo:0.05~1.0%、Cu:0.05~1.0%、Ni:0.05~1.0%の中から選ばれる1種以上の元素を含有し、残部がFeおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が20~120g/m2の亜鉛めっき層を有し、該亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、P、B、Nb、Ti、Cr、Mo、Cu、Niのうちから選ばれる1種以上の酸化物が合計で片面あたり0.01~0.5g/m2存在し、前記亜鉛めっき層直下の、下地鋼板表面から10μmまでの領域においては、Fe結晶粒界から1μm以内のFe結晶粒内にSi及びMnを含む結晶性の酸化物が存在する溶融亜鉛めっき鋼板。
- 請求項1または2に記載の鋼板を連続式溶融亜鉛めっき設備において焼鈍および溶融亜鉛めっき処理を行うに際し、焼鈍炉内温度が600℃以上900℃以下の温度域において、雰囲気中酸素分圧(Po2)が、下記の式(1)を満足するように溶融亜鉛めっき処理を行う溶融亜鉛めっき鋼板の製造方法。
−12+0.5×[Si]+0.2×[Mn] ≦ LogPo2 ≦ −4 ……(1)
但し、[Si]、[Mn]はそれぞれ、鋼中Si、Mn量(質量%)、Po2は酸素分圧(Pa)を示す。 - 溶融亜鉛めっき処理後、さらに、450℃以上550℃以下の温度に鋼板を加熱して合金化処理を施し、めっき層のFe含有量を7~15質量%の範囲にする請求項3に記載の溶融亜鉛めっき鋼板の製造方法。
- 質量%で、C:0.01~0.15%、Si:0.001~2.0%、Mn:0.1~3.0%、Al:0.001~1.0%、P:0.005~0.060%、S≦0.01%を含有し、残部がFeおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が20~120g/m2の亜鉛めっき層を有し、該亜鉛めっき層の直下の、下地鋼板表面から100μm以内の鋼板表層部には、Fe、Si、Mn、Al、Pのうちから選ばれる1種以上の酸化物が合計で片面あたり0.01~0.5g/m2存在し、前記亜鉛めっき層直下の、下地鋼板表面から10μmまでの領域においては、粒界から1μm以内の地鉄粒内に結晶性Si、Mn系複合酸化物が存在することを特徴とする高強度溶融亜鉛めっき鋼板。
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EP2412842A4 (en) | 2014-07-09 |
EP2412842A1 (en) | 2012-02-01 |
JP5663833B2 (ja) | 2015-02-04 |
EP2412842B1 (en) | 2018-10-17 |
US9074275B2 (en) | 2015-07-07 |
CN102227513A (zh) | 2011-10-26 |
KR20110088551A (ko) | 2011-08-03 |
CA2742661C (en) | 2013-03-26 |
BRPI0922830B1 (pt) | 2019-08-13 |
CA2742661A1 (en) | 2010-06-03 |
US20110217569A1 (en) | 2011-09-08 |
BRPI0922830A2 (pt) | 2018-02-06 |
JP2010126758A (ja) | 2010-06-10 |
CN102227513B (zh) | 2013-09-25 |
TWI419982B (zh) | 2013-12-21 |
TW201030158A (en) | 2010-08-16 |
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