TWI396754B - 外觀優異之高強度熔融鍍鋅鋼板之製造方法 - Google Patents
外觀優異之高強度熔融鍍鋅鋼板之製造方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims description 70
- 239000010959 steel Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title description 13
- 238000005096 rolling process Methods 0.000 claims description 60
- 238000000137 annealing Methods 0.000 claims description 41
- 238000007747 plating Methods 0.000 claims description 37
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 30
- 239000008397 galvanized steel Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 16
- 238000005097 cold rolling Methods 0.000 claims description 15
- 238000005098 hot rolling Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 210000001161 mammalian embryo Anatomy 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 description 32
- 238000005121 nitriding Methods 0.000 description 26
- 230000007547 defect Effects 0.000 description 24
- 238000000465 moulding Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000005728 strengthening Methods 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000005275 alloying Methods 0.000 description 7
- 238000005246 galvanizing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- -1 MnS are formed Chemical class 0.000 description 1
- 241000220259 Raphanus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0405—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing of ferrous alloys
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0426—Hot rolling
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0436—Cold rolling
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0473—Final recrystallisation annealing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- 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
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—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
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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- 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
- C21D2211/005—Ferrite
Description
本發明係關於適合作為汽車內板及外板之外觀優異的高強度熔融鍍鋅鋼板及其製造方法。
近年來,CO2
的排出限制嚴格化,且經由汽車的輕量化,使得燃料費用提高的必要性變大,並且發展出將高強度鋼板應用於汽車構件使其薄身化。隨著應用範圍變廣,於高強度熔融鍍鋅鋼板中對於成形性和表面品質的要求亦變嚴格。因此,由成形性及耐蝕性的觀點而言,多使用將C及N析出固定之所謂在IF鋼中添加固熔強化元素的高強度熔融鍍鋅鋼板(專利文獻1)。作為熔融鍍鋅鋼板之表面品質惡化的要因,已知有因基鐵表層之Fe-Si氧化物和SiO2
等之Si氧化物的析出,而發生鍍敷斑和未鍍敷,以及熱軋時生成的銹皮在酸洗及冷軋後部分殘存,變成鍍敷斑之銹皮性的表面缺陷。又,於退火中發生不均勻氮化時,會有加壓成形時引起不均勻變形,而在製品表面產生凹凸等並且成為條紋狀之缺陷的情況。
作為解決此等問題者,已揭示表面性狀和加壓成形性優異的半極低碳鋼板及其製造方法(專利文獻2)。又,作為熱軋時有效之除銹技術,已揭示表面性狀良好之熱軋鋼板的製造方法(專利文獻3)。又,作為抑制退火時之氮化技術,已揭示於鋼板的退火過程中防止侵氮法(專利文獻4)。
專利文獻1:日本專利特開2007-169739號公報
專利文獻2:日本專利第4044795號公報
專利文獻3:日本專利特開平6-269840號公報
專利文獻4:日本專利特開昭48-48318號公報
專利文獻1之技術,並非提供改善鍍敷鋼板之外觀品質的發明。
專利文獻2之技術中,因為C量較多,且C及N以合金析出物型式固定,故必須添加大量生成碳氮化物的元素Nb及Ti,因此,藉由退火中之氮化使加壓成形後發生條紋狀缺陷的可能性高。又,其並非提供關於銹皮性之表面缺陷的發明。
專利文獻3之技術中,必須將精軋機入側再加熱,導致能量成本的增加。又,在粗軋製時發生銹皮的咬入,於存在缺陷原因之情形中,使再加熱的效果受到限定。
專利文獻4之技術,係為低碳鋼之分批退火時的防止氮化技術,並非提供關於極低碳且高強度鋼板之連續退火時之氮化行為的發明。
如此,於以IF鋼作為基材之高強度熔融鍍鋅鋼板中,無法完全防止因Si氧化物之鍍敷斑和未鍍敷、銹皮性之鍍敷斑、退火時之氮化造成加壓成形後之條紋狀缺陷,具有無法充分達成外觀品質的問題。
本發明之課題係在於解決上述先前技術之問題,提供無因Si氧化物所造成的鍍敷斑和未鍍敷、銹皮性的鍍敷斑,不會發生退火時之氮化造成加壓成形後之條紋狀缺陷,外觀優異的高強度熔融鍍鋅鋼板及其製造方法。
發明者等人為了解決上述問題,對於鋼成分及製造條件進行檢討,並且得到以下知識而達成本發明。
對於起因於Si氧化物的鍍敷斑,在添加Cu、Ni作為鋼成分以抑制扁胚加熱時之基鐵表層的Si濃化及Si氧化物生成之同時,可防止生成的Si氧化物經由粗軋製及精軋時的除銹強化而被除去。
對於銹皮性的鍍敷斑,進行粗軋製及精軋的除銹強化,更且藉由控制退火爐的氫濃度而抑制。
對於退火時之氮化所造成之加壓成形後的條紋狀缺陷,在退火爐內之氫濃度高的情形中,雖然更易發生氮化,但藉由同時添加Cu及Ni作為鋼成分,即使於氫濃度高的情形中亦可抑制表層的氮化,進一步經由熱軋的除銹強化,使得鋼板的表面狀態均勻,即使於發生若干氮化的情形中,亦可均勻發生氮化,於加壓成形後不會變成條紋狀缺陷。
解決上述課題之本發明手段為如下述。
[1] 一種外觀優異之高強度熔融鍍鋅鋼板,其特徵為,作為鋼成分,其含有以質量%計之C:0.0005~0.0040%、Si:0.1~1.0%、Mn:1.0~2.5%、P:0.01~0.20%、S:0.015%以下、Al:0.01~0.10%、N:0.0005~0.0070%、Ti:0.010~0.080%、B:0.0005~0.0020%、Cu:0.05~0.50%、Ni:0.03~0.50%,且滿足下述式(1)及式(2),殘餘部分為Fe及不可避免雜質所構成,在具有肥粒鐵單相組織之鋼板表面,具有熔融鍍鋅層或合金化熔融鍍鋅層,且具有拉伸強度(TS)為440MPa以上。
[Ti]≧(47.9/14)×[N]+(47.9/12)×[C] …(1)
[Ni]≧0.4×[Cu] …(2)
其中,[元素]為元素的含量(質量%)。
[2] 如[1]記載之高強度熔融鍍鋅鋼板,其中,作為鋼成分,進一步含有Sb:0.0030~0.0150%、Sn:0.0020~0.0150%之任一種以上。
[3] 如[1]或[2]記載之高強度熔融鍍鋅鋼板,其中,作為鋼成分,進一步含有Nb:0.01~0.08%、V:0.01~0.08%、Mo:0.01~0.10%之任一種以上,於含有Nb或V之情形為滿足下述式(3)。
[Ti]+[Nb]+[V]≦0.08 …(3)
其中,[元素]為元素之含量(質量%)。
[4] 一種肥粒鐵單相組織且拉伸強度(TS)為440MPa以上之外觀優異之高強度熔融鍍鋅鋼板之製造方法,其特徵為將[1]、[2]或[3]記載之組成所構成的鋼扁胚,於熱軋步驟中加熱至1100℃以上,進行3個軋道(pass)以上之粗軋製,且上述粗軋製之各軋道中的至少3個軋道係在軋製前實施除銹,進一步在精軋前進行衝突壓1.0MPa以上的除銹,將精軋在Ar3
點以上、950℃以下結束後,於550℃以上、680℃以下捲取,酸洗後,以50%以上、80%以下之軋縮率進行冷軋,於其後退火步驟中,於氫濃度7.0容積%以上之還原環境中以700℃以上、850℃以下均熱30秒以上後,施行熔融鍍鋅。
[5] 一種肥粒鐵單相組織且拉伸強度(TS)為440MPa以上之外觀優異之高強度合金化熔融鍍鋅鋼板之製造方法,其特徵為將[1]、[2]、或[3]記載之組成所構成的鋼扁胚,於熱軋步驟中加熱至1100℃以上,進行3個軋道以上之粗軋製,且上述粗軋製之各軋道中的至少3個軋道係在軋製前實施除銹,進一步在精軋前,進行衝突壓1.0MPa以上之除銹,將精軋在Ar3
點以上、950℃以下結束後,於550℃以上、680℃以下捲取,酸洗後,以50%以上、80%以下之軋縮率進行冷軋,於其後退火步驟中,於氫濃度7.0容積%以上之還原環境中以700℃以上、850℃以下均熱30秒以上後,施行熔融鍍鋅,並進行合金化處理。
本發明之高強度熔融鍍鋅鋼板係可取得無鍍敷斑和未鍍敷,且即使於加壓成形後亦不會發生條紋狀之表面缺陷的優異外觀。本發明之高強度熔融鍍鋅鋼板係可用於作為汽車內板和外板構件所使用的鋼板。
針對本發明之高強度熔融鍍鋅鋼板,說明鋼成分的限定理由,另外,關於鋼成分之[%]表示,只要無特別指明係意指質量%。
C愈低則愈有利於成形性,又,根據C量使得以碳化物型式固定之Ti等的合金添加量亦增加,故將上限定為0.0040%,較佳為0.0030%以下。下限愈低愈佳,但於C量極低之情形,因製鋼成本上升,故將下限定為0.0005%。
Si係有效作為固熔強化元素,可較不降低成形性地使強度上升。為了取得此效果,將下限定為0.1%。於過度添加之情形,扁胚加熱時的表面濃化或表層生成的Si氧化物顯著變多,即使添加Cu及Ni或以熱軋的除銹,亦無法充分除去Si氧化物而發生鍍敷斑和未鍍敷,因此上限定為1.0%。由外觀品質的觀點而言,較佳為0.7%以下。
Mn係有效作為固熔強化元素,為了高強度化,將下限定為1.0%。較佳為1.5%以上。於過度添加之情形,因成形性和耐二次加工脆性降低,故將上限定為2.5%。較佳為2.2%以下。
P係有效作為固熔強化元素,亦有提升r值的效果。為了取得此效果,必須添加0.01%以上。較佳為0.03%以上。於過度添加之情形,對於粒界的偏析變得顯著,使粒界脆化,且易於中央偏析,因此將上限定為0.20%。較佳為0.10%以下。
於S含量多之情形,生成許多MnS等之硫化物,且延伸突緣性所代表的局部延展性降低,故將上限定為0.015%。較佳為0.010%以下。S亦具有提高銹皮剝離性的效果,故以0.005%以上為佳。
Al在脫酸方面係為必要元素,於取得此效果上必須添加0.01%以上,但即使添加超過0.10%效果仍飽和,故將上限定為0.10%。
N與C同樣,愈低則愈有利於成形性,又,根據N量以氮化物型式固定之Ti等的合金添加量亦增加,故將上限定為0.0070%。下限愈低愈佳,但於N量極低之情形,因製鋼成本上升,故將下限定為0.0005%。
Ti:0.010~0.080%,[Ti]≧(47.9/14)×[N]+(47.9/12)×[C]
Ti係將固熔C及N以TiC、TiN型式固定俾提高成形性而添加。為了取得此效果,必須添加0.010%以上,更且,為了充分固定C及N,必須根據C及N量使添加量變化,必須滿足下述式(1)。
[Ti]≧(47.9/14)×[N]+(47.9/12)×[C] ...(1)
其中,[元素]為元素之含量(質量%)。
即使過度添加,不僅C、N的固定效果飽和,並且於退火中易引起氮化,於加壓成形後會發生條紋狀的缺陷,故將上限定為0.080%。
Cu係為取得本發明優良外觀的重要元素。於極低碳高強度鋼板中,藉由與Ni同時添加,即使在氫濃度高的環境中亦可抑制退火時的氮化,且可抑制加壓成形後發生條紋狀缺陷。認為其係藉由Cu與Ni兩者在表面上濃化,而有效抑制退火時的氮化。又,具有抑制扁胚加熱時Si在表面濃化或生成Si氧化物的效果,更且Cu亦可有效作為固熔強化元素,而為了取得此等效果,必須添加0.05%以上。過度添加之情形不僅導致成本上升,且在熱軋時於表面發生微小的破裂且表面品質降低,故將上限定為0.50%。
Ni:0.03~0.50%,[Ni]≧0.4×[Cu]
Ni係為取得本發明優良外觀的重要元素。於極低碳高強度鋼板中,藉由與Cu同時添加,即使在氫濃度高的環境中亦可抑制退火時的氮化,且可抑制加壓成形後發生條紋狀缺陷。認為其係藉由Cu與Ni兩者在表面上濃化,而有效抑制退火時的氮化。又,具有抑制扁胚加熱時Si在表面濃化或生成Si氧化物的效果,或作為固熔強化元素的效果,更且,Ni具有抑制起因於Cu之熱軋時表面的微小破裂的效果,為了取得此等效果,必須添加0.03%以上,且必須以滿足下述式(2)之方式,根據Cu添加量而變化。
[Ni]≧0.4×[Cu] ...(2)
即使添加超過0.50%此等效果仍飽和、成本上升,故將上限定為0.50%。
B具有提高耐二次加工脆性,將組織細粒化且高強度化之效果。為了取得此效果,將下限定為0.0005%。添加超過0.0020%之情形因成形性顯著降低,故以0.0020%為上限。
於上述鋼成分以外,由下列理由而言亦可添加Sb:0.0030~0.0150%、Sn:0.0020~0.0150%、Nb:0.01~008%、V:0.01~0.08%、Mo:0.01~0.10%之任一種以上。
Sb係藉由表面濃化而抑制氮化的元素,經由添加0.0030%以上,可進一步抑制因退火中之氮化而在加壓成形後發生條紋狀缺陷。即使添加0.0150%以上,不僅效果飽和且導致成本上升,故將上限定為0.0150%。
Sn亦同Sb,係藉由表面濃化而抑制氮化的元素,經由添加0.0020%以上,可進一步抑制因退火中之氮化而在加壓成形後發生條紋狀缺陷。即使添加0.0150%以上,不僅效果飽和且導致成本上升,故將上限定為0.0150%。
Nb與Ti同樣具有將固熔C、N固定且提高成形性的效果,更且藉由細粒化亦具有提高強度之效果。為了取得此效果,必須添加0.01%以上。即使過度添加,不僅此等效果飽和,且於退火中易引起氮化,於加壓成形後發生條紋狀缺陷,故將上限定為0.08%。
V與Ti同樣具有將固熔C、N固定且提高成形性的效果,更且藉由細粒化亦具有提高強度之效果。為了取得此效果,必須添加0.01%以上。即使過度添加,不僅此等效果飽和,且於退火中易引起氮化,於加壓成形後發生條紋狀缺陷,故將上限定為0.08%。
[Ti]+[Nb]+[V]≦0.08 …(3)
除了Ti尚添加Nb及V之1種以上的情形,為了抑制退火中的氮化,必須使添加量的總和以滿足上述式(3)之方式規定。其係因為若存在形成氮化物之元素,則易引起氮化。
Mo係有效作為固熔強化元素,亦具有提高耐二次加工脆性的效果。為了取得此效果,必須添加0.01%以上。即使添加0.10%以上,不僅此等效果飽和,且成本上升,故將上限定為0.10%。
其次,說明鋼板組織、拉伸強度(TS)。
本發明之高強度熔融鍍鋅鋼板的鋼板組織為肥粒鐵單相。作成肥粒鐵單相下,可取得優異的延伸度和深拉伸性等。
具有上述組成和組織的高強度熔融鍍鋅鋼板,拉伸強度(TS)為440MPa以上。若是TS為440MPa以上的高強度鋼板,則應用在先前使用270MPa級和340MPa級鋼板的構件中,可使素材薄身化,並且有助於構件的輕量化。又,若以肥粒鐵單相組織過度高強度化,則成形性顯著降低,故TS為490MPa以下為佳。上述之高強度熔融鍍鋅鋼板,於熔融鍍鋅後、合金化處理後,不會因Si氧化物而發生鍍敷斑和未鍍敷、銹皮性之鍍敷斑,具有良好的外觀,且於加壓成形後亦不會發生條紋狀之表面缺陷,取得良好的外觀。
其次說明本發明之高強度熔融鍍鋅鋼板的製造法。
本發明之高強度熔融鍍鋅鋼板,係藉由將具有上述組成的鋼扁胚以熱軋步驟加熱後,施以粗軋製、精軋,其後,以酸洗步驟除去熱軋鋼板表層的銹皮後,進行冷軋步驟、退火步驟,且於退火步驟後,施以熔融鍍鋅、以及合金化處理而製造。
鋼扁胚的製造方法並無特別限定。
將扁胚加熱後,進行粗軋製、精軋,並將軋製之鋼卷捲取。說明熱軋步驟條件的限定理由。
扁胚加熱溫度若未滿1100℃,則軋製負荷增大,且生產性降低,故定為1100℃以上。加熱溫度變成高溫,若初次銹皮增大,則銹皮易殘存,鍍敷後的外觀品質降低,故以1220℃以下為佳。
由鋼板除去初次銹皮並除去軋製中生成的2次銹皮,在防止銹皮性的表面缺陷之同時,可取得除去Si氧化物的效果,故進行3個軋道以上之粗軋製,且上述粗軋製之各軋道中之至少3個軋道係在軋製前實施除銹。進行5個軋道以上之粗軋製,且在各軋道前進行除銹為更佳。
精軋前,進行衝突壓1.0MPa以上之除銹,其後進行精軋。除去鋼板之基鐵表層的Si氧化物,為了無鍍敷斑,必須在精軋前以1.0MPa以上之衝突壓進行除銹。由進一步提高表面品質的觀點而言,衝突壓以1.5MPa以上為佳。
精軋結束溫度若未滿Ar3
點,則在熱軋鋼板中殘存加工組織,退火後的成形性降低。若超過950℃,則熱軋鋼板的組織粗大化,退火後的強度降低。因此,精軋結束溫度定為Ar3
點以上950℃以下。
於添加Ti和Nb和V之情形,形成彼等的碳化物和氮化物,將固熔C及固熔N固定,且為了提高成形性必須以550℃以上捲取。若超過680℃,則生成含有Fe和Ti等的磷化物,強度和成形性降低,故必須定為680℃以下。
熱軋步驟後,進行酸洗步驟,除去熱軋鋼板表層的銹皮。酸洗步驟並無特別限定。以常法即可。
酸洗步驟後,進行冷軋。為了使退火後之粒徑細粒化且取得指定強度上,必須使冷軋率為50%以上。更且,於要求深拉伸性之情形,冷軋率以60%以上為佳。若冷軋率超過80%,則冷軋負荷大且生產性降低,故將上限定為80%。
為了使組織再結晶,且成形性提高,使退火溫度為700℃以上且保持時間為30秒以上。退火溫度若超過850℃,則粒徑變為粗大且強度降低,故定850℃為上限。又,保持時間為長時間之情形,粒徑變為粗大且強度降低,且生產性降低,故保持時間定為300秒以下為佳。
為了將酸洗及冷軋後一部分殘存的銹皮予以完全還原,藉此不發生鍍敷斑和未鍍敷,必須使退火均熱中的氫濃度為7.0容積%以上。由防止銹皮性缺陷的觀點而言,將氫濃度定為8.0容積%以上為佳。另一方面,氫濃度愈高則退火時愈易引起氮化,故氫濃度定為15.0容積%以下為佳。
對退火後之鋼板施以熔融鍍鋅,或進一步施以合金化處理,取得本發明之高強度熔融鍍鋅鋼板。施以鍍敷時,鋅浴的浴溫定為440~480℃,鍍敷浸漬時的鋼板溫度定為鍍敷浴溫以上、鍍敷浴溫+30℃以下為佳。又,進行合金化處理之情形,以480~540℃之溫度區域保持1秒以上為佳。
其次說明本發明之實施例。將表1所示成分之鋼熔製鑄造,製造230mm厚之扁胚。將該扁胚以1200℃加熱1小時,進行熱軋時粗軋製定為7個軋道,於各粗軋製軋道前進行除銹,且合計進行7次除銹。接著在進行精軋前,將銹皮切斷器(FSB)以衝突壓1.5MPa進行除銹,並以890℃結束精軋,將厚度加工成3.2mm,冷卻至640℃,並且於同樣溫度中捲取。其次將上述製作之熱軋鋼板酸洗,並以冷軋率62.5%予以冷軋,加工成厚度1.2mm後,利用CGL,於氫濃度8.0容積%的環境中,以退火溫度820℃均熱90秒後,進行熔融鍍鋅(每單面的鍍敷附著量48g/m2
)及合金化,並進行伸長率0.7%的調質軋製,製造熔融鍍鋅鋼板。
由製造之熔融鍍鋅鋼板從軋製垂直方向採取JIS 5號拉伸試驗片,並供於拉伸試驗,以目視評估外觀品質。外觀品質係為調查有無未鍍敷和鍍敷斑,並將無未鍍敷及鍍敷斑者視為鍍敷外觀為良好(記號○),有未鍍敷斑者視為鍍敷外觀為不良(記號×)。更且,為了評估加壓成形後的外觀品質,將軋製垂直方向於長軸上切出300×700mm的長條狀樣品,並以拉伸試驗機加以10%的拉伸加工,以研磨石研磨鋼板表面並且調查有無條紋狀缺陷。無條紋狀缺陷者視為成形後之外觀為良好(記號○),有條紋狀缺陷者視為成形後之外觀為不良(記號×)。又,鋼板組織係對於軋製方向平行的板厚方向剖面進行機械研磨及腐蝕(腐蝕液:Nital)後,以光學顯微鏡觀察微細組織。另外,所得鋼板之微細組織全部為肥粒鐵單相組織。拉伸特性、鍍敷外觀及成形後的外觀評價結果示於表2。
本發明範圍內之鋼1~鋼5為TS≧440MPa之高強度,且外觀品質優異。鋼6因Si量為範圍外,故發生未鍍敷,鍍敷外觀差,更且成形後的外觀亦差。
鋼7係Cu及Ni為發明範圍外,鍍敷外觀及成形後之外觀差。又,因為無法利用Cu及Ni添加所造成的固熔強化,故強度低。鋼8、鋼9係Ni、Cu分別為發明範圍外,與鋼7同樣為外觀品質差,於提高外觀品質方面,必須同時添加Cu和Ni。鋼10係Ti量為發明範圍外,雖然鍍敷外觀為良好,但成形後發生條紋狀缺陷,且成形後的外觀差。
使用表1之鋼No.1,並以表3所示之條件製造熔融鍍鋅鋼板。另外,調質軋製的伸長率為0.7%。鋼板之拉伸特性、鍍敷外觀及成形後之外觀評價係以與上述實施例1同樣之方法進行。其評價結果示於表4。
以本發明法之製造條件所製造的鋼板A、B、C、D係TS為440MPa以上之高強度,且外觀品質優異。但是,以本發明法之製造條件範圍外所製造的鋼板則無法使拉伸特性、外觀品質兩相成立。即,鋼板E為粗軋製的去鍋垢次數為範圍外,故鍍敷外觀及成形後的外觀差。鋼板F為FSB衝突壓為範圍外,故鍍敷外觀及成形後的外觀差,捲取溫度為範圍外(低至400℃),又退火均熱時間為範圍外(短至15秒),故延伸度低。鋼板G因捲取溫度為範圍外(高至760℃),故拉伸強度低。鋼板H因加工溫度高,且為範圍外,故拉伸強度低,且氫濃度低,故鍍敷外觀及成形後的外觀差。鋼板I因氫濃度低,故鍍敷外觀及成形後的外觀差,因退火溫度低,故雖取得高強度,但延伸度低。鋼板J因FSB衝突壓為範圍外,故鍍敷外觀及成形後的外觀差,因退火溫度高,故拉伸強度低。鋼板K因冷軋率低,故拉伸強度低。
本發明之高強度熔融鍍鋅鋼板無鍍敷斑和未鍍敷,更且即使於加壓成形後亦不會發生條紋狀之表面缺陷,故適合作為汽車內板和外板的構件。本發明之高強度熔融鍍鋅鋼板之製造方法可利用作為製造上述之高強度熔融鍍鋅鋼板的方法。
Claims (4)
- 一種肥粒鐵單相組織且拉伸強度(TS)為440MPa以上之外觀優異之高強度熔融鍍鋅鋼板之製造方法,其特徵為將作為鋼成分含有以質量%計之C:0.0005~0.0040%、Si:0.1~1.0%、Mn:1.0~2.5%、P:0.01~0.20%、S:0.015%以下、Al:0.01~0.10%、N:0.0005~0.0070%、Ti:0.010~0.080%、B:0.0005~0.0020%、Cu:0.05~0.50%、Ni:0.03~0.50%,且滿足下述式(1)及式(2),殘餘部分為Fe及不可避免雜質所構成的鋼扁胚,於熱軋步驟中加熱至1100℃以上,進行3個軋道(pass)以上之粗軋製,且,上述粗軋製之各軋道中的至少3個軋道係在軋製前實施除銹,進一步在精軋前進行衝突壓1.0MPa以上的除銹,在Ar3 點以上、950℃以下結束精軋後,以550℃以上、680℃以下捲取,酸洗後,以50%以上、80%以下之軋縮率進行冷軋,其後於退火步驟中,於氫濃度7.0容積%以上之還原環境中以700℃以上、850℃以下均熱30秒以上後,施行熔融鍍鋅;[Ti]≧(47.9/14)×[N]+(47.9/12)×[C]…(1) [Ni]≧0.4×[Cu]…(2)其中,[元素]為元素的含量(質量%)。
- 如申請專利範圍第1項之高強度熔融鍍鋅鋼板之製造方法,其中,上述鋼扁胚中,作為鋼成分,進一步含有Sb:0.0030~0.0150%、Sn:0.0020~0.0150%之任一種以上。
- 如申請專利範圍第1或2項之高強度熔融鍍鋅鋼板之製造方法,其中,上述鋼扁胚中,作為鋼成分,進一步含有Nb:0.01~0.08%、V:0.01~0.08%、Mo:0.01~0.10%之任一種以上,於含有Nb或V之情形係滿足下述式(3);[Ti]+[Nb]+[V]≦0.08…(3)其中,[元素]為元素之含量(質量%)。
- 一種肥粒鐵單相組織且拉伸強度(TS)為440MPa以上之外觀優異之高強度合金化熔融鍍鋅鋼板之製造方法,其特徵為,將申請專利範圍第1、2或3項之組成所構成的鋼扁胚,於熱軋步驟中加熱至1100℃以上,進行3個軋道以上之粗軋製,且,上述粗軋製之各軋道中的至少3個軋道係在軋製前實施除銹,進一步在精軋前進行衝突壓1.0MPa以上之除銹,在Ar3 點以上、950℃以下結束精軋後,以550℃以上、680℃以下捲取,酸洗後,以50%以上、80%以下之軋縮率進行冷軋,其後於退火步驟中,於氫濃度7.0容積%以上之還原環境中以700℃以上、850℃以下均熱30秒以上後,施行熔融鍍鋅,並進行合金化處理。
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