TW201309847A - 鍍鋅系鋼板 - Google Patents
鍍鋅系鋼板 Download PDFInfo
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- TW201309847A TW201309847A TW101134656A TW101134656A TW201309847A TW 201309847 A TW201309847 A TW 201309847A TW 101134656 A TW101134656 A TW 101134656A TW 101134656 A TW101134656 A TW 101134656A TW 201309847 A TW201309847 A TW 201309847A
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- steel sheet
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- galvanized steel
- oxide layer
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 50
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 239000011701 zinc Substances 0.000 title abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052725 zinc Inorganic materials 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 title abstract description 3
- 239000002184 metal Substances 0.000 title abstract description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 46
- 239000008397 galvanized steel Substances 0.000 claims description 46
- 238000007747 plating Methods 0.000 claims description 34
- 239000010410 layer Substances 0.000 description 37
- 239000010408 film Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000011324 bead Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005275 alloying Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000013585 weight reducing agent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910007542 Zn OH Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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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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- 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
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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
- 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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- A61F13/511—Topsheet, i.e. the permeable cover or layer facing the skin
- A61F13/513—Topsheet, i.e. the permeable cover or layer facing the skin characterised by its function or properties, e.g. stretchability, breathability, rewet, visual effect; having areas of different permeability
- A61F13/51305—Topsheet, i.e. the permeable cover or layer facing the skin characterised by its function or properties, e.g. stretchability, breathability, rewet, visual effect; having areas of different permeability having areas of different permeability
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
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Abstract
本發明係提供衝壓成形時的滑動性優異之鍍鋅系鋼板。在鍍敷表面上形成具有結晶性3Zn(OH)2‧ZnSO4‧xH2O的氧化物層,且該氧化物層厚度為10nm以上。結晶性氧化物層係3Zn(OH)2‧ZnSO4‧3~5H2O。
Description
本發明係關於在衝壓成形中的滑動性優異之鍍鋅系鋼板。
鍍鋅系鋼板係以汽車車體用途為中心廣泛地被應用於廣泛領域中,在此類用途中,將經施行衝壓成形而使用。但是,相較於冷軋鋼板,鍍鋅系鋼板潛在有衝壓成形性差的缺點。此現象係因為在衝壓模處的表面處理鋼板之滑動阻力大於冷軋鋼板的緣故。亦即,在模具與壓條之滑動阻力較大之部分,表面處理鋼板不易輸送入衝壓模中,容易發生鋼板斷裂情況。
近年,在汽車車體輕量化之目的下,對高張力鋼板的需求正增加中,但相較於軟鋼板,高張力鋼板因為衝壓成形性較差,因而在模具與壓條處之滑動阻力較大部分處,容易發生鋼板斷裂情況。
在此,因為合金化熔融鍍鋅鋼板相較於鍍鋅鋼板,其熔接性及塗裝性均較優異,因而更適合作為汽車車體用。
合金化熔融鍍鋅鋼板係在對鋼板施行鍍鋅之後,再施行加熱處理,藉由產生使鋼板中的Fe、與鍍敷層中的Zn進行擴散的合金化反應,形成Fe-Zn合金相。該Fe-Zn合金相通常係由Γ相、δ1相、ζ相構成的皮膜,隨Fe濃度的降低,即依照Γ相→δ1相→ζ相的順序,而有硬度及熔點降低的傾
向。因而,由滑動性的觀點而言,高硬度、高熔點、不易發生膠著情況的高Fe濃度皮膜將屬有效,重視衝壓成形性的合金化熔融鍍鋅鋼板係可提高皮膜中的平均Fe濃度進行製造。
然而,高Fe濃度的皮膜係有在鍍敷-鋼板界面處容易形成硬且脆的Γ相,且加工時容易發生從界面剝落現象,即所謂「粉化(powdering)」的問題。因而,如專利文獻1所示,為求兼顧滑動性與抗粉化性,而有採行對上層利用電鍍等手法賦予第二層之硬質Fe系合金的方法。但是,當使用該方法進行製造時,有成本提高的問題。
提升鍍鋅系鋼板使用時之衝壓成形性的方法,除此之外,尚廣泛採用塗佈高黏度潤滑油的方法。但是,該方法中,因為潤滑油的高黏性,導致在塗裝步驟中因脫脂不良而發生塗裝缺陷。此外,因衝壓成形時的缺油,導致發生衝壓性能不安定等問題。所以,合金化熔融鍍鋅鋼板本身係強烈渴望衝壓成形性之改善。
解決上述問題的方法,在專利文獻2及專利文獻3中揭示有:藉由對鍍鋅系鋼板表面施行電解處理、浸漬處理、塗佈氧化處理、或加熱處理,形成以ZnO為主體的氧化膜,俾提升熔接性、或加工性的技術。
專利文獻4揭示有:在鍍鋅系鋼板表面上,藉由將鍍敷鋼板浸漬於含磷酸鈉5~60g/L的pH2~6水溶液中、或施行電
解處理、或塗佈上述水溶液,形成以P氧化物為主體的氧化膜,俾提升衝壓成形性及化成處理性的技術。
專利文獻5揭示有:在鍍鋅系鋼板表面上,藉由電解處理、浸漬處理、塗佈處理、塗佈氧化處理、或加熱處理,而生成Ni氧化物,俾提升衝壓成形性及化成處理性的技術。
專利文獻6揭示有:藉由使合金化熔融鍍鋅鋼板接觸至酸性溶液,而在鋼板表面上形成以Zn為主體的氧化物,俾抑制鍍敷層與衝壓模的膠著,而提升滑動性的技術。
專利文獻1:日本專利特開平1-319661號公報專利文獻2:日本專利特開昭53-60332號公報專利文獻3:日本專利特開平2-190483號公報專利文獻4:日本專利特開平4-88196號公報專利文獻5:日本專利特開平3-191093號公報專利文獻6:日本專利特開2003-306781號公報
上述專利文獻中,特別係專利文獻6之在鋼板表面上形成以Zn為主體的氧化物、而改善衝壓成形性的技術,相較於專利文獻5之使用Ni等的技術,因為其使用以原本在鍍敷鋼板中便含有的Zn為主體,因而由製造成本、環境負荷等方面較有利,但當使用於難成形零件等的情況,係需要高度的衝壓成形性,並需要進一步改善滑動特性。
本發明之目的在於提供針對藉由在鋼板表面上形成以Zn
為主體的氧化物,而改善衝壓成形性的技術,進一步在衝壓成形時具優異滑動性的鍍鋅系鋼板。
本發明者等針對合金化熔融鍍敷鋼板的滑動性施行調查,結果獲得以下的發現。合金化熔融鍍鋅鋼板表面的平坦部係相較於周圍而依凸部形式存在。在衝壓成形時之所以實際會接觸到衝壓模,係因為該平坦部成為主體,因而若該平坦部存在具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層,發現可防止鍍敷層與模具間的膠著。再者,不僅侷限於合金化熔融鍍鋅鋼板,即使未施行合金化處理的熔融鍍鋅鋼板、電鍍鋅鋼板,若鍍敷表面存在有具結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層,發現則可防止鍍敷層與模具間的膠著。
本發明係根據以上的發現而完成,主旨如下述:
(1)一種鍍鋅系鋼板,係在鍍敷表面上形成具有結晶性3Zn(OH)2‧ZnSO4‧xH2O的氧化物層,且該氧化物層厚度為10nm以上。
(2)如(1)之鍍鋅系鋼板,其中,結晶性氧化物層係3Zn(OH)2‧ZnSO4‧3~5H2O。
本發明的鍍鋅系鋼板係可獲得衝壓成形時的滑動阻力較小、安定且優異的衝壓成形性。
應用本發明之一形態的合金化熔融鍍敷鋼板,係利用合金
化處理時的鋼板-鍍敷界面之反應性之差,而在表面上存在凹凸。然而,若利用諸如調質軋延等方法將表層施行平坦化,鍍敷表面的凹凸便被緩和。所以,在衝壓成形時,可減輕模具用於將鍍敷表面的凸部押潰而需要的力,可提升滑動特性。
因為合金化熔融鍍鋅鋼板表面的平坦部,係屬於在衝壓成形時模具所直接接觸的部分,因而防止與模具間發生膠著的硬質且高熔點物質之存在,對滑動性的提升將屬重要。此外,相較於合金化熔融鍍鋅鋼板,即使是表面凹凸較少的熔融鍍鋅鋼板、電鍍鋅鋼板,表面當然屬於在衝壓成形時直接接觸到模具的部分,而表層上存在有硬質且高熔點物質者,對滑動性的提升而言將屬重要。
由此觀點而言,在表層上形成氧化物層者,對滑動特性的提升將屬有效,尤其是具有結晶性3Zn(OH)2‧ZnSO4‧xH2O的氧化物層將屬非常有效,特別係具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層將更為有效。
此處,在氧化物層中是否存在有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O,係使用薄膜X射線繞射法施行氧化物層的X射線繞射圖譜測定,並與ICDD卡的標準圖譜進行比對而調查。結果,在繞射角度(2θ)為約8°至約12°間,確認到來自氧化物的尖峰,該等尖峰被鑑定屬於結晶水分別為3、4、5的3Zn(OH)2‧ZnSO4‧3H2O(ICDD卡:39-689)、3Zn(OH)2
‧ZnSO4‧4H2O(ICDD卡:44-673)、3Zn(OH)2‧ZnSO4‧5H2O(ICDD卡:39-688)。
再者,藉由將鍍敷表層的氧化物層厚度設定為10nm以上,可獲得顯示良好滑動性的鍍鋅系鋼板,而若將厚度設為20nm以上則更具效果。其理由係在將模具與被加工物間之接觸面積加大的衝壓成形加工中,即使表層的氧化物層遭受磨損其仍殘存,而不會有造成滑動性降低的情況發生。另一方面,厚度的上限並無特別的限制,但若超過200nm,即使屬於具有Zn-OH鍵的氧化物層,仍因化成處理液而造成蝕刻速度降低,難以形成緻密且均勻的化成皮膜,因而最好設定在200nm以下。
作為在鍍鋅系鋼板的表面上形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O之氧化物層的方法,最有效者係利用水溶液進行反應的方法。其中,藉由在鋼板表面上形成含有Zn離子與硫酸根離子之溶液液膜,並放置既定時間,便可在表面上形成前述具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層。當使用僅含Zn離子的溶液時,則不會形成結晶性3Zn(OH)2‧ZnSO4‧3~5H2O,但是含有Zn離子及硫酸根離子的溶液,係隨硫酸根離子濃度的提高,而有促進結晶性3Zn(OH)2‧ZnSO4‧3~5H2O形成的傾向。此外,Zn離子及硫酸根離子的濃度越高,亦有所形成之氧化膜的厚度越厚之傾向。
表面上已形成氧化物層的鍍鋅系鋼板之鍍敷附著量,較佳係每單面為20~150g/m2範圍內。其理由係若未滿20g/m2,則附著量變少,因而原本作為防鏽鋼板功能變差,反之,若超過150g/m2,雖防鏽性足夠,但有因加工導致鍍敷層剝離的問題。特別係合金化熔融鍍鋅鋼板,當為了能滿足合金化熔融鍍鋅鋼板特徵的熔接性與塗裝性,而施行合金化處理時,在鍍敷-鋼板界面處無法避免Γ相的形成,導致粉化等鍍敷剝離。
合金化熔融鍍鋅鋼板係鍍敷皮膜中的Fe濃度為6~14質量%範圍內。其理由係若Fe濃度未滿6質量%,則呈於表面殘留純Zn相(η相)的狀態,無法滿足前述熔接性及塗裝性等,反之,若超過14質量%,則在鍍敷-鋼板界面上形成厚Γ相,導致鍍敷密接性變差。為了控制成此種Fe濃度,係使鍍浴中適量含有Al者將屬重要,Al濃度必需為0.05~0.40質量%範圍內。
熔融鍍鋅鋼板係為了使鍍敷-鋼板界面處不生成較厚的合金層,重要的是在鍍浴中適量含有Al,Al濃度必需為0.15~0.40質量%範圍內。
鍍敷表面的平坦部面積率最好設為20~80%。若未滿20%,則於平坦部以外的部分(凹部)與模具間之接觸面積變大,實際接觸到模具的面積中,可確實控制氧化物厚度的平坦部面積率變小,因而導致衝壓成形性的改善效果變小。此
外,除平坦部以外的部分,係在衝壓成形時具有保持衝壓油的功用。所以,若除平坦部以外的部分之面積率未滿20%(若平坦部面積率超過80%),則在衝壓成形時容易發生缺油情況,衝壓成形性的改善效果變小。
當製造本發明的合金化熔融鍍鋅鋼板或熔融鍍鋅鋼板之際,必需在鍍敷浴中添加Al,但除Al以外的添加元素成分則無特別的限制。即,除Al之外,即使含有或添加Pb、Sb、Si、Sn、Mg、Mn、Ni、Ti、Li、Cu等,仍不致損及本發明的效果。
當製造本發明的電鍍鋅鋼板之際,鍍敷浴若含有鋅作為主體即可,在不損及本發明效果之前提下,尚可含有其他的金屬、氧化物等。
本發明的鍍鋅系鋼板係若使用高張力鋼板作為底層鋼板,可獲得輕量化等效果,因而較佳。例如考量汽車車體輕量化的方法,藉由使用高張力鋼板,可在維持車體碰撞性能之情況下,達到素材重量減輕(板厚減少)效果。然而,一般隨著拉伸強度的增加,而有衝壓成形性降低的傾向,高張力鋼板的衝壓成形性差劣亦可想而知。本發明者等為了改善高張力鋼板的衝壓成形性,經深入鑽研的結果發現,藉由在表層上形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層,可特別提升高張力鋼板的衝壓成形性,就目前為止因成形性而難以適用高強度鋼板的用途,將轉為可適用高強度鋼
板,並可獲得達成上述輕量化效果。在此,所使用的鋼板種類並無特別的限制,為了獲得充分的輕量化效果,最好使用拉伸強度:340MPa以上的高張力鋼板。
其次,針對本發明利用實施例進行更詳細的說明。
在板厚0.8mm冷軋鋼板上,依照常法的合金化熔融鍍鋅法,形成鍍敷附著量60g/m2、Fe濃度:10質量%、Al濃度:0.20質量%的鍍敷皮膜,再施行調質軋延。另外,此時的平坦部面積率雖依照採取位置而多少有所偏差,但全部均涵括於40~60%範圍內。
將該合金化熔融鍍鋅鋼板浸漬於經添加硫酸鋅七水合物的水溶液中,經利用橡膠製輥將表面液膜量控制為10g/m2之後,直接放置於大氣中,經10~60秒後,再實施水洗、乾燥的氧化處理。其中一部分,為了作為比較,亦使用經添加硝酸鋅六水合物的水溶液、或含有醋酸鈉及硫酸亞鐵的酸性溶液。處理時所使用溶液的溫度全部均設定為35℃。
再者,準備板厚0.8mm的下述熔融鍍鋅鋼板與電鍍鋅鋼板。熔融鍍鋅鋼板係依照常法的熔融鍍鋅方法,形成鍍敷附著量70g/m2的鍍敷皮膜,再施行調質軋延。電鍍鋅鋼板係依照常法的電鍍鋅方法形成鍍敷附著量50g/m2的鍍敷皮膜。
將該熔融鍍鋅鋼板與電鍍鋅鋼板,浸漬於經添加硫酸鋅七水合物的水溶液中,利用橡膠製輥將表面的液膜量控制為10g/m2之後,直接放置於大氣中,經10~60秒後,實施水洗、乾燥的氧化處理。處理時所使用之溶液的溫度全部均設定為35℃。
經氧化處理過的鍍敷鋼板之摩擦係數測定、氧化膜厚的測定、及3Zn(OH)2‧ZnSO4‧3~5H2O的分析,係依如下述實施。為了比較,對於未實施氧化處理者亦進行同樣的調查。
(1)衝壓成形性評估試驗(摩擦係數測定試驗)
為了施行衝壓成形性的評估,依下述測定各供試材的摩擦係數。圖1所示係摩擦係數測定裝置的概略正視圖。如該圖所示,將從供試材所採取的摩擦係數測定用試料1固定於試料台2上,而試料台2固定於可進行水平移動的滑動機台3上面。在滑動機台3的下面設有具備與該滑動機台3接觸的輥4、且可上下移動的滑動機台支撐台5,在該滑動機台支撐台5上安裝著第1測力器7,該第1測力器7係用於測定當將滑動機台支撐台5往上推時,壓條6對摩擦係數測定用試料1的押抵荷重N。在滑動機台3之一端部安裝著第2測力器8,該第2測力器8係用於測定當在作用上述押抵力的狀態下,用於使滑動機台3朝水平方向移動的滑動阻力F。另外,潤滑油係使用杉村化學公司製衝壓用洗淨油Preton(註冊商標)R352L,並塗佈於試料1的表面上再施行
試驗。
圖2係所使用之壓條的形狀‧尺寸之概略立體圖。在壓條6下面押抵於試料1表面的狀態下進行滑動。圖2所示壓條6的形狀係由寬10mm、試料滑動方向的長度12mm、滑動方向二端的下端為曲率4.5mmR的曲面所構成,押抵著試料的壓條下面係具有寬10mm、滑動方向的長度3mm之平面。
摩擦係數測定試驗係依照如下示2條件實施。
[條件1]
使用圖2所示壓條,設定為押抵荷重N:400kgf、試料的抽伸速度(滑動機台3的水平移動速度):100cm/min。
[條件2]
使用圖2所示壓條,設定為押抵荷重N:400kgf、試料的抽伸速度(滑動機台3的水平移動速度):20cm/min。
供試材與壓條間的摩擦係數μ係依式:μ=F/N計算出。
(2)氧化物層厚度的測定
氧化物層厚度的測定係使用螢光X射線分析裝置。測定時的管球電壓及電流係設定為30kV及100mA,分光結晶係設定為TAP,並檢測出O-Kα射線。在施行O-Kα射線測定之際,除該尖峰位置之外,亦測定背景位置的強度,便可計算出O-Kα射線的真正強度。另外,尖峰位置及背景位置的積分時間分別設為20秒。
再者,在試料平台上,與該等一連串試料一起安裝矽晶圓
(其係形成有經劈裂為適當大小且膜厚96nm、54nm及24nm的氧化矽皮膜),而亦可從該等氧化矽皮膜計算出O-Kα射線強度。使用該等數據製作氧化膜厚度與O-Kα射線強度的檢量線,將供試材的氧化物層厚度依氧化矽皮膜換算而算出氧化膜厚度。
(3)結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的存在確認
依照薄膜X射線繞射法確認結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的存在。使用Cu-Kα射線,將入射角度設為0.5°,並利用薄膜法施行X射線繞射圖形的測定。在繞射角度(2θ)為約8°至約12°間,發現3Zn(OH)2‧ZnSO4‧3~5H2O的各結晶結構所對應之繞射尖峰。
在合金化熔融鍍鋅鋼板的情況,從該繞射尖峰、與在約42°所出現之鐵鋅合金層的繞射尖峰間之強度比,可確認結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的存在。以經扣掉各自背景的尖峰強度計,當尖峰強度比(3Zn(OH)2‧ZnSO4‧3~5H2O的尖峰強度)/(鐵鋅合金層的尖峰強度)達0.020以上時,則判斷其形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的皮膜。
在熔融鍍鋅鋼板、電鍍鋅鋼板的情況,從在繞射角度(2θ)約8°至約12°之間3Zn(OH)2‧ZnSO4‧3~5H2O的各結晶結構所對應之繞射尖峰、與在約36°所出現之鋅的η層繞射尖峰強度比,可確認到結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的
存在。以扣掉各自背景的尖峰強度計,當尖峰強度比,(3Zn(OH)2‧ZnSO4‧3~5H2O的尖峰強度)/(鋅的η層尖峰強度)達0.020以上時,可判斷其形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的皮膜。
繞射角度(2θ)約8°至約12°間的尖峰,判斷係來自結晶水分別為3、4、5的3Zn(OH)2‧ZnSO4‧3H2O(ICDD卡:39-689)、3Zn(OH)2‧ZnSO4‧4H2O(ICDD卡:44-673)、3Zn(OH)2‧ZnSO4‧5H2O(ICDD卡:39-688)之尖峰。合金化熔融鍍鋅鋼板的氧化處理條件、與所獲得之結果,如表1所示。熔融鍍鋅鋼板、電鍍鋅鋼板的氧化處理條件、與所獲得之結果,如表2所示。
由表1及表2得知以下事項。
未施行氧化處理的No.1、No.17、No.21,係氧化物層厚度未滿10nm,在平坦部並未形成足以提升滑動性的氧化膜,摩擦係數較高。
No.2~7、No.18~20、No.22~24係尖峰強度比達0.020以上,形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層,且其厚度達10nm以上,因而摩擦係數非常低且安定,可發現充分的滑動性提升。
No.8~16係雖平坦部形成有厚度10nm以上的氧化物層,但因為尖峰強度比未滿0.020,因而並無法認定為有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的形成,摩擦係數呈較高值,並未發現有充分的滑動性提升效果。
使用鋼板強度程度不同的板厚1.2mm合金化熔融鍍鋅鋼板,浸漬於經添加硫酸鋅七水合物(濃度20g/L)的水溶液(pH5.5、溫度35℃)中,利用橡膠製輥將表面的液膜量控制為10g/m2之後,直接放置於大氣中,經10~60秒後,再實施水洗、乾燥的氧化處理。合金化熔融鍍鋅係依照常法的合金化處理形成鍍敷附著量45~50g/m2、Fe含有率:10~11質量%的鍍敷皮膜,並依平坦部面積率在40~60%範圍內之方式施行調質軋延。
經氧化處理過的合金化熔融鍍鋅鋼板之氧化膜厚測定、及
3Zn(OH)2‧ZnSO4‧3~5H2O的分析,係依照實施例1所記載的方法實施。此外,實施母材鋼板的機械特性測定、衝壓成形性的評估。衝壓成形性係利用摩擦係數測定試驗與鼓脹成形試驗施行評估。為了比較,針對未實施氧化處理者亦進行相同的調查。
(1)機械特性的測定
使用將軋延方向的90°方向設為長邊方向(拉伸方向)之JIS Z2201的5號試驗片,根據JIS Z2241施行拉伸試驗並評估。
(2)衝壓成形性評估試驗(摩擦係數測定試驗)
依照實施例1所記載的方法,依照下述條件3施行各供試材的摩擦係數測定。
[條件3]
使用圖3所示壓條,並設定為押抵荷重N:400kgf、試料的抽伸速度(滑動機台3的水平移動速度):20cm/min。供試材與壓條間的摩擦係數μ係依式:μ=F/N計算出。
(3)衝壓成形性評估試驗(鼓脹成形試驗)
對200mm×200mm供試材,使用ψ 150mm衝孔(衝模徑:ψ 153mm)施行球頭鼓脹試驗,並測定當供試材出現斷裂時的最大成形高度。此時,在抑制供試材之流入之目的下,而施加100ton的皺摺壓制力,在供試材上將塗佈著作為潤滑油之杉村化學公司製衝壓用洗淨油Preton(註冊商
標)R352L。
氧化處理條件、與所獲得之結果,如表3所示。
由表3可得知以下事項。
未施行氧化處理者(比較例:No.2、No.4、No.6、No.8、No.10、No.12、No.14),係氧化物層的厚度未滿10nm,並未形成為足以提升滑動性的氧化膜,且摩擦係數較高。
經施行氧化處理者(發明例:No.1、No.3、No.5、No.7、No.9、No.11、No.13),其尖峰強度比達0.020以上,形成具有結晶性3Zn(OH)2‧ZnSO4‧3~5H2O的氧化物層,且厚度達10nm以上,因而摩擦係數非常低且安定,可發現充分地提升滑動性。
當將鋼板強度程度相同的鋼板進行比較時(No.1與No.2、No.3與No.4、No.5與No.6、No.7與No.8、No.9與No.10、No.11與No.12、No.13與No.14),相較於未施行氧化處理者(比較例),經施行氧化處理(發明例)者的成形度較高,可發現充分的衝壓成形性提升。
本發明的鍍鋅系鋼板因為滑動性優異,因而具有優異的衝壓成形性,可適用於以汽車車體用途為中心的廣泛領域中。
1‧‧‧摩擦係數測定用試料
2‧‧‧試料台
3‧‧‧滑動機台
4‧‧‧輥
5‧‧‧滑動機台支撐台
6‧‧‧壓條
7‧‧‧第1測力器
8‧‧‧第2測力器
9‧‧‧滑軌
F‧‧‧滑動阻力
N‧‧‧押抵荷重
圖1為摩擦係數測定裝置的概略正視圖。
圖2為圖1中的壓條形狀‧尺寸之概略立體圖。
圖3為圖1中的壓條形狀‧尺寸之概略立體圖。
1‧‧‧摩擦係數測定用試料
2‧‧‧試料台
3‧‧‧滑動機台
4‧‧‧輥
5‧‧‧滑動機台支撐台
6‧‧‧壓條
7‧‧‧第1測力器
8‧‧‧第2測力器
9‧‧‧滑軌
F‧‧‧滑動阻力
N‧‧‧押抵荷重
Claims (4)
- 一種熔融鍍鋅鋼板,係在鍍敷表面上形成具有結晶性3Zn(OH)2‧ZnSO4‧xH2O的氧化物層,該氧化物層厚度為10nm以上。
- 如申請專利範圍第1項之熔融鍍鋅鋼板,其中,結晶性氧化物層係3Zn(OH)2‧ZnSO4‧3~5H2O。
- 一種電鍍鋅鋼板,係在鍍敷表面上形成具有結晶性3Zn(OH)2‧ZnSO4‧xH2O的氧化物層,該氧化物層厚度為10nm以上。
- 如申請專利範圍第3項之電鍍鋅鋼板,其中,結晶性氧化物層係3Zn(OH)2‧ZnSO4‧3~5H2O。
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CA2784174A1 (en) | 2009-03-12 |
TWI398550B (zh) | 2013-06-11 |
JP2012087417A (ja) | 2012-05-10 |
JP2009079291A (ja) | 2009-04-16 |
KR101266713B1 (ko) | 2013-05-28 |
EP2186925B1 (en) | 2018-08-01 |
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JP5239570B2 (ja) | 2013-07-17 |
US8623514B2 (en) | 2014-01-07 |
CN102321885A (zh) | 2012-01-18 |
JP5522185B2 (ja) | 2014-06-18 |
USRE45821E1 (en) | 2015-12-22 |
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US20120082845A1 (en) | 2012-04-05 |
US20100255341A1 (en) | 2010-10-07 |
CA2784174C (en) | 2013-07-30 |
TW200925320A (en) | 2009-06-16 |
CN101784699A (zh) | 2010-07-21 |
WO2009031699A1 (ja) | 2009-03-12 |
CA2696567A1 (en) | 2009-03-12 |
TWI480423B (zh) | 2015-04-11 |
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