TW201511933A - 具優異塗裝後耐蝕性之Ａｌ系合金鍍敷鋼材 - Google Patents
具優異塗裝後耐蝕性之Ａｌ系合金鍍敷鋼材 Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 84
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 84
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 59
- 239000010959 steel Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000005260 corrosion Methods 0.000 title claims description 45
- 230000007797 corrosion Effects 0.000 title claims description 41
- 238000000576 coating method Methods 0.000 title claims description 38
- 239000011248 coating agent Substances 0.000 title claims description 37
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract 5
- 239000010410 layer Substances 0.000 claims abstract description 139
- 238000007747 plating Methods 0.000 claims abstract description 94
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 230000003746 surface roughness Effects 0.000 claims description 21
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910001676 gahnite Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
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- 230000000052 comparative effect Effects 0.000 description 3
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- 230000001965 increasing effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明之Al系合金鍍敷鋼材係由鋼材及形成於前述鋼材表面上之覆蓋層所構成；前述覆蓋層以質量%計含有10%以上且50%以下之Fe，及3%以上且15%以下之Si，並且為包含下述而成者：形成於前述鋼材表面上之Al系合金鍍敷層；形成於前述Al合金鍍敷層的表面上之含ZnO之層；及，ZnAl2O4層，係形成於前述Al合金鍍敷層與前述含有ZnO之層之間，且厚度為0.05μm以上且2μm以下。
Description
本發明有關於一種具優異塗裝後耐蝕性之Al系合金鍍敷鋼材。
各種防銹材料已廣泛使用於環境負荷減少及壽命週期成本之降低，進而確保安全性等方面至各種範疇。使用例則自電子零件等小型零件至家電產品、汽車、土木材料，進而擴大至基礎設施等大型結構物。
防銹材料之一種即為鍍敷鋼材，其中較常用鍍Zn鋼材。常用鍍Zn鋼材之較重要理由乃其較為廉價且對於基體金屬具有犠牲防蝕作用、在大氣環境中之Zn本身之腐蝕速度較慢。鍍Zn鋼材以外之其它鍍敷鋼材則有諸如鍍Al鋼材。但，鍍Al鋼材具有因存在Al鍍敷層表面上之氧化覆膜而不具備對基體金屬之犠牲防蝕性，且因Al鍍敷層表面上存在之氧化覆膜而使化學轉化性不足且塗裝後耐蝕性不佳之問題。另一方面，Al本身之腐蝕速度較Zn慢，故若可藉Al鍍敷層確保犠牲防蝕性及塗裝後耐蝕性，則推論用途可
望擴大。
因此，已提案有Al鍍敷層之耐蝕性改善技術。舉例言之，日本專利特開2003-34845號公報(專利文獻1)中，已揭示於Al鍍敷層中含有0.5~10%之Mg，即可生成足量之化學轉化膜而提昇塗裝後耐蝕性。然而，將Mg等活性元素添加於Al鍍敷層中，將增加Al鍍敷層本身之活性度，反而將使裸耐蝕性(未塗裝時之耐蝕性)劣化。
另，日本專利特開2007-302982號公報(專利文獻2)中，則揭示對Al鍍敷層表面附加Zn或其化合物等，而改善塗裝後耐蝕性之技術。然而，Zn或Zn化合物與鍍敷層之密著性不足，故塗裝後耐蝕性之提昇效果尚嫌不足。
專利文獻1：日本專利特開2003-34845號公報
專利文獻2：日本專利特開2007-302982號公報
本發明有鑑於上述問題，目的在提供一種具備犠牲防蝕性，且塗裝後耐蝕性較習知之鍍Al鋼材更為優異之Al系合金鍍敷鋼材。
本發明人等人為克服上述問題而致力檢討之結果，發現了於Al系合金鍍敷層表面上設置含有ZnO之層，
並於Al系合金鍍敷層中含有Fe及Si，進而於含有ZnO之層與Al系合金鍍敷層之間形成由Zn及Al所構成之複合氧化層，即可實現具有犠牲防蝕效果，且塗裝後耐蝕性較習知之Al系鍍敷鋼材更為優異之Al系合金鍍敷鋼材。本發明之要點則如下所述。
(1)本發明係一種具優異塗裝後耐蝕性之Al系合金鍍敷鋼材，係由鋼材及形成於前述鋼材表面上之覆蓋層所構成；該鋼材之特徵在於：前述覆蓋層以質量%計含有10%以上且50%以下之Fe，及3%以上且15%以下之Si，並且為包含下述而成者：形成於前述鋼材表面上的Al系合金鍍敷層；形成於前述Al合金鍍敷層的表面上之含有ZnO之層；及，ZnAl2O4層，係形成於前述Al合金鍍敷層與前述含有ZnO之層之間，且厚度為0.05μm以上且2μm以下。
(2)如項1之具優異塗裝後耐蝕性之Al系合金鍍敷鋼材，其特徵在於前述覆蓋層之表面粗度Ra在1μm以上且5μm以下之範圍內。
如上所述，依據本發明之Al系合金鍍敷鋼材，可具備犠牲防蝕性，並較習知之鍍Al鋼材更為大幅提昇塗裝後耐蝕性。因此，可適用於家電產品、汽車、土木材料，進而亦可適用於諸如基礎設施等大型結構物，故對產業上之助益極大。
以下，詳細說明本發明之實施形態。本實施形態之Al系合金鍍敷鋼材由鋼材及該鋼材表面上形成之覆蓋層所構成。覆蓋層構成包含：形成於鋼材表面上之Al系合金鍍敷層，形成於Al合金鍍敷層表面上之含有ZnO之層，形成於Al合金鍍敷層與含有ZnO之層之間的ZnAl2O4層。實施形態及實施例之說明中，將含有ZnO之層稱為「ZnO含有層」。
Al系合金鍍敷層中須含有Fe。Fe具有可對Al系合金鍍敷層本身賦予犠牲防蝕性之效果，以及增加Al系合金鍍敷層之表面粗度以表現固著效果而提昇塗裝後耐蝕性之效果。Al系合金鍍敷層中之Fe之含有率依質量%而須為10%以上、50%以下。Fe之含量若低於10%，則犠牲防蝕性之賦予效果及Al系合金鍍敷層之表面粗度增大之效果不佳，故不適用。且，Fe之含量若超過50%，則Al系合金鍍敷層本身將易於破碎且鍍敷密著性不佳，故不適用。
又，Al系合金鍍敷層中，除Fe以外，就更為提高鍍敷密著性之觀點而言，依質量%而須在3%以上且15%以下之範圍內含有Si。使Al系合金鍍敷層中含有Si，即可抑制Fe-Al合金層之成長，並提昇鍍敷密著性。另，Si含量若低於3%，其效果不佳，若超過15%則反而將使鍍敷密著性劣化。
又，Al系合金鍍敷層之表面粗度Ra宜為1μm以上、
5μm以下。表面粗度Ra乃JIS B 0601所規定之表面性質參數。表面粗度Ra若低於1μm，將因固著效果不足而使塗裝後耐蝕性劣化。表面粗度Ra若超過5μm，則凹凸將過大而成為導致塗膜厚度差異之主要因素，反而將使耐蝕性劣化。另，本實施形態之Al系合金鍍敷鋼材中，Al系合金鍍敷層之表面粗度Ra將反映於覆蓋層之表面粗度。因此，覆蓋層之表面粗度Ra將在1μm以上且5μm以下之範圍內。
又，覆蓋層上，於Al系合金鍍敷層之正上方，即，於ZnO含有層與Al系合金鍍敷層之間須設有ZnAl2O4層。ZnAl2O4層具有可強化Al系合金鍍敷層及鋼材與ZnO含有層之密著性，並提昇塗裝後耐蝕性之效果。ZnAl2O4層之厚度須為0.05μm以上且2μm以下。厚度若低於0.05μm，則提高密著性而提昇塗裝後耐蝕性之效果將不足。且，厚度若超過2μm，ZnAl2O4層本身將易於破碎而容易剝離。另，在裁切本實施形態之Al系合金鍍敷層之任意截面後，加以嵌入樹脂中再加以研磨，並以掃描式電子顯微鏡觀察其任意截面，即可測定ZnAl2O4層之厚度。
Al系合金鍍敷鋼材之最外層上，須設有ZnO含有層。ZnO含有層具有賦予化學轉化性之效果，並為本實施形態之Al系合金鍍敷鋼材之耐蝕性提昇所需之ZnAl2O4層之形成所需之Zn供給來源。ZnO含有層之量雖未特別加以規定，但ZnO含有層之Zn量若低於0.4g/m2，則難以形成足量之ZnAl2O4層。反之，Zn量若超過5g/m2，則與Al系合金鍍敷層之密著性將劣化而容易脫落或導致熔接性劣化。因
此，ZnO含有層之量宜為可使Zn量為0.4g/m2以上且5g/m2以下之量。
就作為Al系合金鍍敷鋼材之基材之鋼材之成分及形態等完全未加以限制。成分亦可為軟質鋼材或含有Si或Mn等強化元素之鋼材。且，形態亦可為薄板、厚板、鋼管、型鋼或模製品。
以下，說明本實施形態之具優異塗裝後耐蝕性之Al系合金鍍敷鋼材之製造方法。
本實施形態之Al系合金鍍敷鋼材之製造方法包含以下步驟：於鋼材上形成Al系合金鍍敷層之步驟；於Al系合金鍍敷層表面(正上方)上形成ZnO含有層之步驟；及，於Al系合金鍍敷層與ZnO含有層之間形成ZnAl2O4層之步驟。以下，即說明各步驟。
(Al系合金鍍敷層之形成步驟)
Al系合金鍍敷層之形成方法可應用迄今所使用之熱浸鍍等。且，熱浸鍍之方式亦可為氧化還原平衡法、總還原法、內部氧化法、助熔劑法、預鍍法等之任一種。欲使Al系合金鍍敷層中含有Fe時，亦可預先於含Si之Al系合金鍍浴中混入Fe，或在進行含Si之Al系合金鍍敷後，再加熱鋼材而使鋼材中所含之Fe擴散至Al系合金鍍敷層中。Al系合金鍍敷層之附著量宜為各單面30g/m2以上且200g/m2以下。附著量若低於30g/m2，則耐蝕性將略微劣化，若超過200g/m2則可能發生鍍層剝離。
欲使Al系合金鍍敷層之表面粗度Ra為1μm以上
且5μm以下，可就已形成有Al系合金鍍敷層之鋼材依昇溫速度1℃/秒以上且低於50℃/秒之條件而在600℃以上且1000℃以下之領域中予以加熱至850℃以上且1000℃以下為止。且，亦可控制Al系合金鍍敷層之形成前之鋼材表面之表面粗度Ra，而使Al系合金鍍敷層之表面粗度Ra為1μm以上且5μm以下。但，控制鋼材表面之表面粗度Ra之方法可能隨鍍敷附著量之不同而改變Al系合金鍍敷層之表面粗度Ra。因此，宜採用藉加熱而控制Al系合金鍍敷層之表面粗度Ra之方法。一如前述，表面粗度Ra乃JIS B 0601所規定之表面性質參數。且，表面粗度Ra之測定及評價方法並無特別之規定，可採用迄今已普遍採用之方法，舉例言之，可採用JIS B 0633所規定之方法。
又，控制表面粗度Ra之加熱處理時，亦可同時對Al系合金鍍敷層進行Fe之擴散。
(ZnO含有層之形成步驟)
ZnO含有層之形成方法可列舉諸如於含有ZnO之懸濁液中混合預定之有機性黏結劑而調製塗布液，再於Al系合金鍍敷層表面上塗布該塗布液之方法。含有ZnO之懸濁液則可使用於水等分散介質中分散有ZnO粉體而成者。且，預定之有機性黏結劑可例舉聚胺甲酸酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、矽烷耦合劑。進而，有機系黏結劑成分中亦可含有氧化矽。該等有機系黏結劑宜為水溶性而可與ZnO懸濁液混合。可將如上而製得之塗布液塗布於Al系合金鍍敷層表面上，並使其乾燥。
又，其它方法亦可採用藉粉末塗裝法塗布含有ZnO粉體及預定之有機系黏結劑等之固形物之粉體之方法。
上述有機系黏結劑成分之含量宜依照相對於ZnO之質量比而總計為5~30%左右。黏結劑成分之含量依質量比而低於5%時，黏結劑效果將不足，而導致塗膜易於剝落。為安定獲致黏結劑效果，使黏結劑成分之質量比為10%以上則更佳。另，黏結劑成分之含量之質量比若超過30%，則加熱時將明顯產生氣味，故不適用。
(ZnAl2O4層之形成步驟)
欲於ZnO含有層與Al系合金鍍敷層之間形成ZnAl2O4層時，首先，預先於Al系合金鍍敷層表面上形成ZnO含有層。然後，於大氣環境下，在600℃以下之範圍內依超過25℃/秒且100℃/秒以下之昇溫速度進行加熱，並在超過600℃、1000℃以下之範圍內依1℃/秒以上且低於50℃/秒之昇溫速度進行加熱，並在最終溫度為850℃以上且1000℃以下之範圍內進行加熱。即，以600℃為界，而改變昇溫速度。然後，進行依氣冷或氣冷以上之速度冷卻之步驟。
如上所述，以600℃為界，其以下之溫度範圍內之昇溫速度與超過該溫度之溫度範圍內之昇溫速度不同。藉上述步驟，可使ZnO與Al系合金鍍敷層中之Al反應，而於Al系合金鍍敷層中之Al與ZnO含有層之間形成ZnAl2O4層。進而，依據上述步驟，所形成之ZnAl2O4層之厚度可為目標之0.05μm以上且2μm以下。另，藉上述步驟而可形成
預定厚度之ZnAl2O4層之原因雖未確定，但可推論其原因如下。即，在600℃以下之範圍內，昇溫速度若低於25℃/秒以下，則Al系合金鍍敷層本身將過度氧化，昇溫速度若超過100℃/秒，則有機黏結劑將燃燒不全而殘留於Al系合金鍍敷層之表面上。因此，其後之加熱所致與ZnO之反應將不充分而無法充分生成ZnAl2O4層。另，在超過600℃之範圍內，昇溫速度若低於1℃/秒，將過度生成ZnAl2O4層而易於破碎並容易剝離，若為50℃/秒以上，則無法充分生成ZnAl2O4層而導致耐蝕性劣化。如上所述，以600℃為昇溫速度之變更點之原因可推論乃因ZnAl2O4層之形成受到600℃以下之Al系合金鍍敷層之表面狀態之影響，以及超過600℃則與ZnAl2O4層之形成特別顯著有關之故。且，可推論乃因在600℃時改變昇溫速度，即可於已適度生成之Al系合金鍍敷層表面上生成微細之裂隙，並促進ZnAl2O4層之形成之故。另，本實施形態中，在600℃以下之範圍與超過600℃且1000℃以下之範圍內，昇溫速度重複了超過25℃/秒且低於50℃秒之範圍。但，依照該重複之範圍之昇溫速度而加熱時，昇溫速度亦在600℃以下之範圍及超過600℃且1000℃以下之範圍內改變。此時，宜將超過600℃且1000℃以下之範圍之昇溫速度設成低於600℃以下之範圍之昇溫速度。且，上述加熱處理亦可兼用作為用於控制Al系合金鍍敷層之表面粗度Ra之加熱處理，以及用於對Al系合金鍍敷層擴散Fe之加熱處理。
另，ZnO含有層之形成前，宜於大氣中加熱處理
Al系合金鍍敷層而預先使其氧化。上述之加熱處理可應用諸如於大氣環境下在300~600℃範圍內預先加熱30秒至10分鐘之處理。預先進行上述之加熱處理，即可於Al系合金鍍敷層表面上形成足量之Al2O3薄膜，且更易進行Al2O3層+ZnO含有層→ZnAl2O4之反應。上述加熱處理亦可兼用作為用於控制Al系合金鍍敷層之表面粗度Ra之加熱處理，以及用於對Al系合金鍍敷層擴散Fe之加熱處理。
如以上之說明，依據本實施形態之Al系合金鍍敷鋼材，可藉Zn之犠牲防蝕效果而較習知之鍍Al鋼材更為大幅提昇塗裝後耐蝕性。且，設有ZnAl2O4層，而可提高加工性。
以下，詳細說明本發明之實施例。
首先，對具有表1所示成分之板厚1.2mm之冷軋鋼材藉熱浸鍍法而形成Al系合金鍍敷層。表1為顯示冷軋鋼材之Fe以外之成分之質量%之表格。熱浸鍍則藉無氧化加熱爐-還原爐型態之作業線而進行。其次，鍍敷後則藉氣體抹拭法(gas wiping)將鍍敷附著量調整為各單面40g/m2。然後，加以冷卻而進行無鋅花處理。鍍浴組成為Al-10%Si，鍍浴之溫度為660℃。
於如上而製成之Al系合金鍍敷層表面上，藉輥塗機塗布ZnO之懸濁液與胺甲酸乙酯系樹脂所構成之黏結劑混合而成之塗布液，在約80℃下進行加熱乾燥。另，胺甲酸乙酯系樹脂相對於ZnO之質量比為20%。上述塗布液之塗布量則為可使Zn量為1.0g/m2之量。然後，於大氣環境下依表2所示之條件進行加熱、氣冷，而於Al系合金鍍敷層中擴散Fe，並於ZnO含有層與Al系合金鍍敷層之間形成ZnAl2O4層。然後，依照以下之方法，評價塗裝後耐蝕性與加工性作為Al系合金鍍敷鋼材之特性之例。
(塗裝後耐蝕性)
將製成之Al系合金鍍敷鋼材分割成70×150mm之大小而作成試樣。其次，就作成之試樣進行鹼脫脂後，藉Parubondo SX35(NIHON PARKERIZING出品)而依廠商配方進行化學轉化，進而依15μm之厚度實施陰極電沈積(POWERNIX 110：NIPPONPAINT出品)，並實施了橫切。然後，依據日本自動車技術會(JASO)規定之M610法就上述試樣進行了300周程之試驗。塗裝後耐蝕性則基於以下指標而加以評價。1代表不合格，2及3代表合格。
(塗膜膨脹)
1：超過0.5mm。
2：0.2~0.5mm。
3：低於0.2mm。
(加工性)
將製成之Al系合金鍍敷鋼材分割成30×70mm之大小，
並依彎曲半徑1mm進行90度折彎試驗。然後，施予回彎，並對彎曲部貼附膠帶，進而測定剝除後鍍層剝離寬度。加工性則基於以下之指標而加以評價。1代表不合格，2及3代表合格。
(鍍層或塗膜剝離寬度)
1：超過5.0mm。
2：2.0~5.0mm。
3：低於2.0mm。
結果顯示於表2。結果，本發明之範圍內之實施例之加工性及塗裝後耐蝕性均良好，但本發明之範圍外之比較例之加工性或塗裝後耐蝕性則不佳。
如No.30、31之比較例所示，超過600℃且1000℃以下之昇溫速度若未在1℃/sec以上且低於50℃/sec之範圍內，塗裝後耐蝕性較低。且，如No.28、29之比較例所示，600℃以下之昇溫速度若非超過25℃/秒且100℃/秒以下，則塗裝後耐蝕性較低。又，No.32為昇溫速度不變而加熱後之結果，塗裝後耐蝕性則不佳。推論乃因其等之鍍敷後加熱條件均在本發明之範圍外，而無法於ZnO含有層與Al系合金鍍敷層之間形成厚度為0.05μm以上且2μm以下之ZnAl2O4層之故。
以上，已就本發明之較佳實施形態及實施例加以說明，但本發明不受限於該等實施形態，而可於本發明要點之範圍內進行各種變形及變更實施。
如上所述，依據本發明之Al系合金鍍敷鋼材，可較習知之鍍Al鋼材更為大幅提昇塗裝後耐蝕性，故可適用於家電產品、汽車、土木材料，進而亦可適用於諸如基礎設施等大型結構物，故對產業上之助益極大。
Claims (2)
- 一種具優異塗裝後耐蝕性之Al系合金鍍敷鋼材，係由鋼材及形成於前述鋼材表面上之覆蓋層所構成；該鋼材之特徵在於：前述覆蓋層以質量%計含有10%以上且50%以下之Fe，及3%以上且15%以下之Si，並且為包含下述而成者：形成於前述鋼材表面上的Al系合金鍍敷層；形成於前述Al合金鍍敷層之表面上的含有ZnO之層；及ZnAl2O4層，係形成於前述Al合金鍍敷層與前述含有ZnO之層之間，且厚度為0.05μm以上且2μm以下。
- 如請求項1之具優異塗裝後耐蝕性之Al系合金鍍敷鋼材，其中前述覆蓋層之表面粗度Ra在1μm以上且5μm以下之範圍內。
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| KR102193650B1 (ko) * | 2019-06-11 | 2020-12-21 | 충남대학교산학협력단 | 아연 알루미네이트 박막의 소수성 표면개질 방법 |
| KR102311502B1 (ko) * | 2019-12-20 | 2021-10-13 | 주식회사 포스코 | 가공성 및 내식성이 우수한 알루미늄계 합금 도금강판 및 이의 제조방법 |
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Family Cites Families (16)
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| JPS6047347B2 (ja) * | 1979-09-10 | 1985-10-21 | マツダ株式会社 | 耐剥離性を有するアルミナ被膜の形成方法 |
| JP2648679B2 (ja) * | 1992-10-20 | 1997-09-03 | 新日本製鐵株式会社 | 耐食性と加工性に優れた塗装アルミメッキ鋼板の製造法 |
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| JP4023710B2 (ja) | 2001-06-25 | 2007-12-19 | 新日本製鐵株式会社 | 耐食性，耐熱性に優れたホットプレス用アルミ系めっき鋼板およびそれを使用した自動車用部材 |
| AU2002309283B2 (en) | 2001-06-15 | 2005-04-14 | Nippon Steel Corporation | High-strength Alloyed Aluminum-system Plated Steel Sheet and High-strength Automotive Part Excellent in Heat Resistance and After-painting Corrosion Resistance |
| JP5005254B2 (ja) | 2006-05-15 | 2012-08-22 | 新日本製鐵株式会社 | 昇温特性、加工性、および塗装後耐食性に優れたホットプレス用Ａｌめっき鋼材 |
| JP5476676B2 (ja) | 2008-04-22 | 2014-04-23 | 新日鐵住金株式会社 | ホットプレス部材及びその製造方法 |
| CN104149411B (zh) | 2008-04-22 | 2017-08-08 | 新日铁住金株式会社 | 镀敷钢板及镀敷钢板的热压方法 |
| CA2729942C (en) | 2008-07-11 | 2013-08-06 | Nippon Steel Corporation | Aluminum plated steel sheet for rapid heating hot-stamping, production method of the same and rapid heating hot-stamping method by using this steel sheet |
| US9037279B2 (en) * | 2009-09-09 | 2015-05-19 | Taiwan Semiconductor Manufacturing Company, Ltd. | Clustering for prediction models in process control and for optimal dispatching |
| JP5573195B2 (ja) * | 2010-01-25 | 2014-08-20 | 新日鐵住金株式会社 | 昇温特性に優れた熱間プレス用Ａｌめっき鋼板及びその製造方法 |
| JP5263258B2 (ja) * | 2010-10-25 | 2013-08-14 | 新日鐵住金株式会社 | 高強度自動車部品の製造方法および高強度部品 |
| WO2012137687A1 (ja) * | 2011-04-01 | 2012-10-11 | 新日本製鐵株式会社 | 塗装後耐食性に優れたホットスタンプ成形された高強度部品およびその製造方法 |
| MX369572B (es) | 2012-04-18 | 2019-11-13 | Nippon Steel Corp Star | Laminas de acero enchapadas con aluminio, metodo para formar por prensado en caliente las laminas de acero enchapadas con aluminio, y partes automotrices. |
| JP5692152B2 (ja) | 2012-04-25 | 2015-04-01 | 新日鐵住金株式会社 | 熱間プレス用Ａｌ系めっき鋼板とその熱間プレス方法及び高強度自動車部品 |
| JP5692148B2 (ja) * | 2012-04-18 | 2015-04-01 | 新日鐵住金株式会社 | 熱間プレス用Ａｌ系めっき鋼板及びその熱間プレス方法 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI664299B (zh) * | 2017-03-27 | 2019-07-01 | 日商新日鐵住金股份有限公司 | Al系鍍敷鋼板 |
| TWI664301B (zh) * | 2017-06-02 | 2019-07-01 | Nippon Steel & Sumitomo Metal Corporation | 熱壓印構件 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112015026525A2 (pt) | 2017-07-25 |
| MX2015014709A (es) | 2016-03-07 |
| KR20150133851A (ko) | 2015-11-30 |
| PL3000916T3 (pl) | 2020-06-01 |
| CN105189818A (zh) | 2015-12-23 |
| EP3000916A1 (en) | 2016-03-30 |
| US10174413B2 (en) | 2019-01-08 |
| RU2015144335A (ru) | 2017-06-13 |
| CA2909300A1 (en) | 2014-11-13 |
| MY174906A (en) | 2020-05-21 |
| JP6044711B2 (ja) | 2016-12-14 |
| BR112015026525B1 (pt) | 2021-08-31 |
| EP3000916A4 (en) | 2017-02-22 |
| JPWO2014181653A1 (ja) | 2017-02-23 |
| CA2909300C (en) | 2018-07-31 |
| EP3000916B1 (en) | 2019-12-11 |
| US20160068942A1 (en) | 2016-03-10 |
| ES2768627T3 (es) | 2020-06-23 |
| KR101734745B1 (ko) | 2017-05-11 |
| TWI519410B (zh) | 2016-02-01 |
| WO2014181653A1 (ja) | 2014-11-13 |
| CN105189818B (zh) | 2017-09-12 |
| RU2646655C2 (ru) | 2018-03-06 |
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