TWI516638B - Galvanized steel sheet and manufacturing method thereof - Google Patents
Galvanized steel sheet and manufacturing method thereof Download PDFInfo
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- TWI516638B TWI516638B TW098113978A TW98113978A TWI516638B TW I516638 B TWI516638 B TW I516638B TW 098113978 A TW098113978 A TW 098113978A TW 98113978 A TW98113978 A TW 98113978A TW I516638 B TWI516638 B TW I516638B
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- steel sheet
- aqueous solution
- zinc
- galvanized steel
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 39
- 239000008397 galvanized steel Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 54
- 239000010959 steel Substances 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 28
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005246 galvanizing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 33
- 239000011701 zinc Substances 0.000 description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 28
- 229910052725 zinc Inorganic materials 0.000 description 28
- 238000000034 method Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000007747 plating Methods 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000003139 buffering effect Effects 0.000 description 7
- 239000003929 acidic solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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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
- C23C2/04—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
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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
- 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
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- General Chemical & Material Sciences (AREA)
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- Chemical Treatment Of Metals (AREA)
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Description
本發明係關於一種穩定製造衝壓成形時之滑動阻抗較小且具有優異之衝壓成形性之鍍鋅鋼板的方法及具有優異之衝壓成形性之鍍鋅鋼板。
鍍鋅鋼板以汽車車體用途為中心廣泛用於各種領域。如此用途中之鍍鋅鋼板係經由衝壓成形而供於應用。然而,鍍鋅鋼板具有衝壓成形性劣於冷軋鋼板之缺點。其原因在於:衝壓模具中鍍鋅鋼板之滑動阻抗大於冷軋鋼板。即,於模具與調整桿中之滑動阻抗較大之部分,鍍鋅鋼板難以流入衝壓模具內,容易引起鋼板之斷裂。
此處,鍍鋅鋼板中,尤其是於熔融鍍鋅處理之後經實施合金化處理之合金化熔融鍍鋅鋼板,因其焊接性及塗裝性優於未經合金化處理之熔融鍍鋅鋼板,故而更適合用作汽車車體用途。
合金化熔融鍍鋅鋼板係對鋼板實施鍍鋅之後,進行加熱處理,使鋼板中之Fe與鍍敷層中之Zn擴散而產生合金化反應,由此形成Fe-Zn合金相者。此Fe-Zn合金相通常係由Γ相、δ1相、ζ相所構成之皮膜,具有如下傾向:硬度及熔點伴隨Fe濃度下降,即按Γ相→δ1相→ζ相之順序降低。因此,由滑動性之觀點而言,高硬度、高熔點且難以引起附著的Fe濃度高之皮膜較為有效,注重衝壓成形性之合金化熔融鍍鋅鋼板係提高皮膜中之平均Fe濃度製造而成。
然而,Fe濃度較高之皮膜具有如下問題:於鍍敷-鋼板界面易於形成硬且脆之Γ相,加工時易於發生自界面剝離之現象,即所謂之粉碎。
作為解決上述問題之方法,於專利文獻1及專利文獻2中揭示有一種技術,該技術係對鍍鋅鋼板之表面實施電解處理、浸漬處理、塗佈氧化處理或加熱處理,藉此形成以ZnO為主體之氧化膜,從而提高焊接性、加工性。
然而,於將專利文獻1及2之技術適用於合金化熔融鍍鋅鋼板之情形時,由於合金化熔融鍍敷鋼板中存在Al氧化物,故導致表面反應性劣化,而且表面之凹凸較大,故而無法穩定獲得衝壓成形性之改善效果。即,因表面之反應性較低,故而即便進行電解處理、浸漬處理、塗佈氧化處理及加熱處理等,亦難以於表面形成既定之皮膜,導致膜厚於反應性較低之部分,即Al氧化物量較多之部分處減薄。又,因表面之凹凸較大,故而於衝壓成型時直接與衝壓模具接觸者為表面之凸部,而凸部中膜厚較薄之部分與模具之接觸部中之滑動阻抗變大,故無法充分獲得衝壓成形性之改善效果。
因此,於專利文獻3中揭示有一種技術,該技術係對鋼板進行熔融鍍鋅之後,藉由加熱處理進行合金化,進而實施調質軋壓之後,與具有pH緩衝作用之酸性溶液進行接觸,保持1~30秒後,進行水洗,藉此於鍍敷表層形成氧化物層。
作為同樣於未實施合金化處理之熔融鍍鋅鋼板之表面平坦部上均勻地形成氧化物層的方法,於專利文獻4中揭示有一種方法,該方法係使調質軋壓後之熔融鍍鋅鋼板與具有pH緩衝作用之酸性溶液接觸,然後,於鋼板表面形成有酸性溶液之液膜之狀態下保持既定時間之後,進行水洗、乾燥者。
專利文獻1:日本專利特開昭53-60332號公報
專利文獻2:日本專利特開平2-190483號公報
專利文獻3:日本專利特開2003-306781號公報
專利文獻4:日本專利特開2004-3004號公報
於適用上述專利文獻3及4中揭示之技術之情形時,於先前之製造條件下,可獲得良好之衝壓成形性。然而,近年來,由於生產性之提高,而期望開發一種以更短時間生成更厚之氧化膜之製造方法,於上述條件下進行時,藉由專利文獻3及4中揭示之技術,有時無法形成充分之氧化膜,從而無法獲得良好之衝壓成形性。
本發明之目的在於鑒於上述情況,而提供一種短時間亦可穩定製造具有優異之衝壓成形性之鍍鋅鋼板的製造方法及具有優異之衝壓成形性之鍍鋅鋼板。
本發明者等人為了解決上述課題,而不斷進行積極研究。其結果,獲得以下見解。
專利文獻3及4之技術中使用之酸性溶液,因促進鋅之溶解之目的,而具有pH緩衝作用。因此,認為使得pH之上升延緩,導致氧化物層之形成緩慢。而且,為了以自鍍敷皮膜溶出之鋅補充形成氧化物層之鋅,故而氧化膜之生成時間包括鋅之溶出時間。其結果,認為難以短時間內生成較厚之氧化膜。
因此,本發明者等人研究出一種技術,該技術係藉由使生成氧化膜之水溶液中預先含有鋅離子,從而省略鋅之溶出時間,可依更短時間生成氧化膜者。然而,僅藉由使水溶液中預先含有鋅離子,則無法促進氧化膜之形成。尤其是,即便使處理液中以專利文獻3及4之實施例中所示之pH2含有鋅,亦無法促進氧化膜之形成。
可認為其原因在於:於專利文獻3及4之技術中,由於鋅溶出之同時所引起之氫離子之還原,使得表面附近之pH上升而成為易於生成鋅氧化物之環境,相對於此,僅藉由使水溶液中含有鋅離子,則不會引起表面附近之pH上升,從而無法形成易於生成鋅氧化物之環境。
因此,本發明者等人研究出一種技術,該技術係使水溶液之pH為易於生成鋅氧化物之pH4~6者。而且,發現如下情形:可藉由使處理液之pH為4~6,而利用使鍍敷皮膜之鋅略微溶出所引起之表面pH之微小上升,使鋅以氫氧化物之形式生成。
本發明係基於上述見解開發而成者,其主旨如下所述。
[1]一種鍍鋅鋼板之製造方法,其係對鋼板實施鍍鋅之後,使鋼板與水溶液進行接觸處理,並於接觸處理結束之後保持1~60秒,然後進行水洗‧乾燥,藉此於鋼板表面形成氧化物層者,其特徵在於:對鋼板進行接觸處理之上述水溶液,係以鋅離子濃度為5~100g/l之範圍含有鋅離子,且pH為4~6,液體溫度為20~70℃。
[2]如上述[1]之鍍鋅鋼板之製造方法,其中,上述水溶液中含有鋅之硫酸鹽。
[3]如上述[1]或[2]之鍍鋅鋼板之製造方法,其中,與上述水溶液接觸之後形成於鋼板表面之液膜為5~30g/m2。
[4]一種鍍鋅鋼板,其特徵在於:其係藉由上述[1]至[3]中任一項之鍍鋅鋼板之製造方法而製造者,且於鋼板表面形成平均厚度10nm以上之主要含有鋅作為金屬成分之氧化物層。
再者,於本發明中,所謂鍍鋅鋼板,係指使以鋅為主成分之皮膜形成於表面之鍍敷鋼板,包括熔融鍍鋅鋼板(簡稱為GI鋼板)、合金化熔融鍍鋅鋼板(簡稱為GA鋼板)、電鍍鋅鋼板(簡稱為EG鋼板)、蒸鍍鋅鋼板或含有Fe、Al、Ni、MgCo等合金元素之合金鍍鋅鋼板等。
本發明係一種鍍鋅鋼板之製造方法,其係藉由對鋼板實施鍍鋅之後,使鋼板於水溶液中進行接觸處理,並於接觸處理結束之後保持1~60秒,然後進行水洗‧乾燥,從而於鍍鋅鋼板表面形成氧化物層時,作為上述水溶液,以鋅離子濃度為5~100g/l之範圍含有鋅離子,且pH為4~6,液體溫度為20~70℃。如此,本發明之重要之必要條件及特徵係製成含有既定濃度之鋅離子且既定pH及液體溫度的水溶液,作為對鋼板進行接觸處理之水溶液。藉此,由於確保良好之衝壓成形性故而可依短時間形成充分之氧化物層。
再者,所謂接觸處理結束後,於浸漬處理之情形係指浸漬步驟結束之後,於噴霧處理之情形係指噴霧步驟結束之後,而於輥塗之情形係指塗佈步驟結束之後。
作為對鋼板進行接觸處理之水溶液,可藉由使用含有鋅離子之水溶液,而省略鋅之溶出時間。此時,使鋅離子為5~100g/l之範圍來作為鋅離子濃度。若鋅離子濃度未達5g/l,則無法供給充分之鋅,從而無法形成氧化物層。另一方面,若超過100g/l,則所形成之氧化物層中所含之硫酸濃度會變高,此後進行之化成處理步驟中氧化物溶解時,有污染處理液之虞。
為了形成穩定之鋅化合物作為氧化物層,較佳為以硫酸鹽之形式添加鋅離子。於以硫酸鹽之形式添加鋅離子之情形時,可認為硫酸離子被吸取至所形成之氧化物層中,具有使氧化物層穩定之效果。
又,如上所述,僅藉由使處理液中預先含有鋅離子,則無法促進氧化膜之形成。因此,於本發明中,必須使pH達到易於生成鋅氧化物之pH4~6。若使處理液之pH達到4~6,則由於鍍敷皮膜之鋅略微溶出而引起之表面pH之微小上升,而鋅以氫氧化物生成。
作為該等之結果,便可省略鋅之溶出時間,且,可生成鋅氧化物。於pH超過6之情形時,水溶液中鋅離子將會沉澱(形成氫氧化物),而無法以氧化物形成於鋼板表面。又,於pH未達4之情形時,如上所述,pH上升延遲將阻礙氧化物層之形成。
使水溶液之溫度為20~70℃。因氧化物層之形成反應係於與水溶液接觸後,保持規定時間時產生,故而有效的是將保持時之鋼板溫度控制為20~70℃之範圍。若未達20℃,則氧化物層之生成反應需要長時間,導致生產性下降。另一方面,於超過70℃之情形時,反應將相對地快速進行,而相反地於鋼板表面易於產生處理不均。
專利文獻3及4中使用之水溶液之特徵為呈酸性,且具有pH緩衝作用。然而,因本發明中使用含有鋅離子之水溶液,故而即便提高水溶液之pH而使鋅不充分溶解,亦可形成充分之氧化物層。又,可認為pH上升快速有利於形成氧化物。故而,未必需要pH緩衝作用。
於本發明中,若與鋼板表面接觸之水溶液中含有鋅,則可穩定形成滑動性優異之氧化物層,故而即便水溶液中有意地含有其他金屬離子或無機化合物等作為雜質,亦不會損及本發明之效果。而且,即便N、P、B、Cl、Na、Mn、Ca、Mg、Ba、Sr、Si等進入氧化物層中,只要不損及本發明之效果,便可適用該等。
較理想的是,於使鍍鋅鋼板與包含以上元素之水溶液接觸之後,該水溶液以較薄之液膜狀存在於鋼板表面。其原因在於:若存在於鋼板表面之水溶液之量較多,則即便鋅產生溶解,水溶液之pH亦難以上升,形成氧化物層為止需要長時間。根據此觀點,較佳且有效的是將形成於鋼板表面之水溶液膜之量調整為30g/m2以下。又,為防止液膜乾燥,較佳為5g/m2以上之液膜量。根據上述觀點,較佳為,使與上述水溶液接觸之後形成於鋼板表面之液膜為5~30g/m2。再者,水溶液膜量之調整可藉由擠壓輥、去除氣體等進行。
又,於水溶液中進行浸漬之後直至水洗為止之時間(水洗為止之保持時間)設為1~60秒。若水洗為止之時間未達1秒,則形成有充分之氧化物層之前,水溶液會被沖走,故而無法獲得滑動性之提高效果。另一方面,若保持時間超過60秒,則會導致生產性下降。因本發明之目的在於可以短時間進行穩定製造,故而根據充分發揮本發明之效果之觀點,而將保持時間設為60秒以下。
根據上述觀點,於本發明之鍍敷鋼板之表面,可獲得主要含有鋅作為金屬成分且平均厚度為10nm以上之氧化物層。
再者,以鋅為主體係指含有50質量%以上之鋅作為金屬成分。
再者,所謂本發明之氧化物層,係指包含主要含有鋅作為金屬成分之氧化物及/或氫氧化物等之層。該氧化物層之平均厚度必須為10nm以上。若氧化物層之平均厚度薄到未達10nm,則降低滑動阻抗之效果將不充分。另一方面,若含有鋅作為必須成分之氧化物層之平均厚度超過100nm,則存在衝壓加工中皮膜遭破壞而使滑動阻抗上升,又,焊接性下降之傾向,故而欠佳。
再者,使鍍鋅鋼板於含有鋅之水溶液中進行接觸處理之方法,並不特別限制,存在有將鍍敷鋼板浸漬於水溶液之方法,對鍍敷鋼板噴霧水溶液之方法,經由塗佈輥將水溶液塗佈於鍍敷鋼板之方法等,較理想的是最終以較薄之液膜狀存在於鋼板表面。
又,關於製造本發明之合金化熔融鍍鋅鋼板,必須於鍍敷槽中添加Al,但並不特別限定除Al以外之添加元素成分。即,除了Al以外,即便含有或者添加Pb、Sb、Si、Sn、Mg、Mn、Ni、Ti、Li、Cu等,只要不損及本發明之效果,亦可應用。
其次,藉由實施例更詳細說明本發明。
於板厚為0.8mm之冷軋鋼板上,實施每一單面之附著量為45g/m2、Al濃度為0.20質量%之熔融鍍鋅之後,進行調質軋壓,從而製作GI鋼板。又,於板厚為0.8mm之冷軋鋼板上,藉由常法之合金化熔融鍍鋅法,形成每一單面之鍍敷附著量為45g/m2、Fe濃度為10質量%、Al濃度為0.20質量%之鍍敷皮膜,進而進行調質軋壓,製作GA鋼板。又,於板厚為0.8mm之冷軋鋼板上,藉由常法之鍍敷鋅法,製作具有每一單面之鍍敷附著量為30g/m2之鍍敷皮膜的EG鋼板。
接著,使用圖1所示之構成之處理設備,形成氧化物層。首先,將藉由上述處理獲得之GI鋼板、GA鋼板及EG鋼板等鋼板S,於溶液槽2中,浸漬於表1-1及表1-2所示之處理液成分、溫度及pH不同之水溶液中。繼而,藉由擠壓輥3來調整鋼板表面之液膜量。液膜量之調整係藉由改變擠壓輥之壓力而進行。繼而,使該等鋼板S直接穿過清洗槽5、清洗槽6,於清洗槽7中將50℃之溫水噴霧於鋼板上進行清洗,並於乾燥機8中進行乾燥,從而於鍍敷表面形成氧化物層。再者,可於溶液槽2之前方設置清洗槽1。
於溶液槽2中進行浸漬處理之水溶液,以添加鋅離子之目的,而使用添加有規定量之硫酸鋅七水合物之水溶液。再者,一部分為了進行比較,亦使用利用硫酸對含有20g/L之乙酸鈉之溶液進行pH調整後之溶液。
水洗為止之保持時間係藉由擠壓輥3來調整液膜量,直至於清洗槽7中開始清洗為止之時間,亦製成可藉由改變線速度來進行調整,並且,一部分使用擠壓輥3擠出側之淋式水洗裝置4於擠壓後立即清洗鋼板者。
其次,對如上所述製作之鋼板,判定作為汽車用外殼是否具有充分之外觀,並且作為簡單評價衝壓成形性之方法,實施摩擦係數之測定,以及以更詳細模擬實際成形性之目的實施球頭伸展試驗。再者,測定方法為如下所述。
為了對衝壓成形性進行評價,而以如下方式測定各供試材料之摩擦係數。
圖2係表示摩擦係數測定裝置之概略前視圖。如圖2所示,將取自供試材料之摩擦係數測定用樣本11固定於樣本台12,樣本台12固定於可水平移動之滑台13之上表面。於滑台13之下表面,設置有具有與此處連接之滾筒14的可上下移動之滑台支撐台15,藉由向上推動該滑台支撐台15,而將用以測定調整桿16對摩擦係數測定用樣本11之擠壓荷重N的第1荷重元17安裝於滑台支撐台15。為了測定於使上述擠壓力進行作用之狀態下使滑台13沿著軌道19水平移動之滑動阻抗力F,而將第2荷重元18安裝於滑台13之一方端部。再者,作為潤滑油,將衫村化學公司製造之衝壓用清洗油Preton R352L塗佈於摩擦係數測定用樣本11之表面進行試驗。
圖3及圖4係表示所使用之調整桿之形狀‧尺寸之概略立體圖。調整桿16之下表面以擠壓於樣本11之表面之狀態進行滑動。圖3所示之調整桿16之形狀為寬度10mm,樣本之滑動方向長度為12mm,滑動方向兩端之下部由曲率為4.5mmR之曲面構成,擠壓樣本之調整桿之下表面具有寬度為10mm且滑動方向長度為3mm之平面。圖4所示之調整桿16之形狀為寬度10mm,樣本之滑動方向長度為69mm,滑動方向兩端之下部由曲率為4.5mmR之曲面構成,擠壓樣本之調整桿之下表面具有寬度為10mm且滑動方向長度為60mm之平面。
以如下所示之兩個條件,進行摩擦係數測定試驗。
使用圖3所示之調整桿,並設定為擠壓荷重N:400kgf,樣本之牽引速度(滑台13之水平移動速度):100cm/min。
使用圖4所示之調整桿,並設定為擠壓荷重N:400kgf,樣本之牽引速度(滑台13之水平移動速度):20cm/min。
供試材料與調整桿間之摩擦係數μ利用式:μ=F/N算出。
對200×200mm尺寸之供試材料,使用150mmΦ之衝壓機,藉由液壓膨脹試驗機進行伸展成形,並測定產生斷裂時之最大成形高度。此時,以阻止材料流入為目的,而施加100Ton之壓邊力,並將潤滑油僅塗佈於衝壓機所接觸之面。所使用之潤滑油係與上述摩擦係數測定試驗相同者。
將形成有膜厚為96nm之熱氧化SiO2膜之Si晶圓用作參照物質,藉由螢光X射線分析裝置測定O‧KαX射線,藉此算出經SiO2換算之氧化層之平均厚度。分析面積為30mmΦ。
根據上述處理所獲得之試驗結果示於表1-1及表1-2。
根據表1-1及表1-2所示之試驗結果,可知悉下述事項。
(1)因No.1、No.47及No.60未利用溶液進行處理,故而於平坦部未形成有提高滑動性所必需之充分之氧化膜,故摩擦係數較高。
(2)No.2~No.4、No.48~No.50及No.61~No.63係使用具有pH緩衝作用之酸性溶液的比較例。若為30秒以上,則摩擦係數較低,最大形成高度亦變高,但10秒之處理,並不滿足充分之摩擦係數下降及最大成形高度之提高。
(3)No.5~No.7係使用具有pH緩衝作用之酸性溶液之比較例。呈現出較高之摩擦係數。
(4)No.8~No.10、No.51~No.53及No.64~No.66係雖然含有鋅離子,但其含量少於本發明範圍之比較例。若為30秒以上,則摩擦係數較低,最大形成高度亦提高,但10秒之處理,並不滿足充分之摩擦係數下降及最大成形高度之提高。
(5)No.11~No.13、No.54~No.56及No.67~No.69係以含有鋅離子之溶液進行處理的本發明例,摩擦係數下降,最大成形高度亦提高。又,No.14~No.16及No.44~No.46係於與No.11~No.13相同之處理條件下增加溶液中之鋅離子濃度的本發明例。摩擦係數低位穩定化,最大成形高度亦進一步增加。同樣地,No.57~No.59及No.70~No.72係於與No.54~No.56相同之處理條件下增加溶液中之鋅離子濃度的本發明例。摩擦係數低位穩定化,最大成形高度亦進一步增加。
(6)No.17~No.22係於鋼板表面形成溶液膜,並改變實施水洗為止之時間的示例。於未經保持便進行水洗的No.17中,摩擦係數僅略微下降,相對於此,於保持時間為1秒以上之No.18~No.22中,摩擦係數下降,伸展性亦穩定上升。
(7)No.23~No.40係改變處理液溫度之例,處理液溫度較低之No.23~No.25相比於除此以外之例,摩擦係數及最大成形高度之提高效果不充分。另一方面,No.32~No.34係處理液溫度較高之例,雖然摩擦係數或最大成形高度之增加效果充分,但可觀察到很多處理不均,作為汽車用外殼並未呈現良好之外觀。
(8)No.35~No.40係相對No.20~No.22,改變液膜形成量之本發明例。若以水洗為止之保持時間相同者進行比較,則於液膜量較多之情形時,雖然可獲得充分之摩擦係數下降及最大成形高度之提高,但相比於液膜量較少之情形,摩擦係數僅少許提高且最大成形高度亦變低。
(9)No.41~No.43係使用pH低於本發明範圍之處理液的比較例,但與No.20~No.22相比,無法確認摩擦係數之下降效果,亦未觀察到最大成形高度之提高。
圖5係使用表1-1及表1-2之No.8~No.22及No.44~No.46,表示鋅離子濃度對氧化膜厚之影響的圖。根據圖5可知,若鋅濃度為5g/l以上,則即便保持時間較短時(例如,10秒),亦可充分厚地形成氧化膜厚,解決了本發明之課題,即保持時間較短之情形時,氧化膜厚變薄。
根據本發明,即便於短時間之製造條件下,亦可穩定製造省空間、衝壓成形時之滑動阻抗小且具有優異之衝壓成形性的鍍鋅鋼板。而且,例如即便製造成形荷重較高易於產生模具擦傷之高強度鍍鋅鋼板時,衝壓成形時之滑動阻抗亦較小,亦可具有優異之衝壓成形性。因衝壓成形性優異,故而可以汽車車體用途為中心適用於廣泛領域。
1、5、6、7...清洗槽
2...溶液槽
3...擠壓輥
4...淋式水洗裝置
8...乾燥機
11...樣本
12...樣本台
13...滑台
14...滾筒
15...滑台支撐台
16...調整桿
17...第1荷重元
18...第2荷重元
19...軌道
S...鋼板
圖1係表示實施例中使用之氧化物層形成處理設備之主要部分的圖。
圖2係表示摩擦係數測定裝置之概略前視圖。
圖3係表示圖2中之調整桿形狀‧尺寸之概略立體圖。
圖4係表示圖2中之調整桿形狀‧尺寸之概略立體圖。
圖5係表示鋅離子濃度對氧化膜厚之影響的圖。
Claims (3)
- 一種鍍鋅鋼板之製造方法,其係對鋼板實施鍍鋅之後,於水溶液中進行接觸處理,並於接觸處理結束之後保持1~60秒,然後進行水洗.乾燥,藉此於鋼板表面形成氧化物層者,其特徵在於:對鍍鋅鋼板進行接觸處理之上述水溶液,以鋅離子濃度為5~100g/l之範圍含有鋅離子,且pH為4~6,液體溫度為20~70℃。
- 如申請專利範圍第1項之鍍鋅鋼板之製造方法,其中,上述水溶液中含有鋅之硫酸鹽。
- 如申請專利範圍第1或2項之鍍鋅鋼板之製造方法,其中,與上述水溶液接觸後形成於鋼板表面之液膜為5~30g/m2。
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