TW201641720A - 熔融鋅系鍍敷鋼板 - Google Patents

熔融鋅系鍍敷鋼板 Download PDF

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Publication number
TW201641720A
TW201641720A TW105110549A TW105110549A TW201641720A TW 201641720 A TW201641720 A TW 201641720A TW 105110549 A TW105110549 A TW 105110549A TW 105110549 A TW105110549 A TW 105110549A TW 201641720 A TW201641720 A TW 201641720A
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Taiwan
Prior art keywords
steel sheet
oxide
less
molten zinc
plated steel
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TW105110549A
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English (en)
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TWI591207B (zh
Inventor
Koji Akioka
Yasuaki Kawamura
Akihiro Sengoku
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Nippon Steel & Sumitomo Metal Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/02—Stamping using rigid devices or tools
    • B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
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    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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    • C—CHEMISTRY; METALLURGY
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    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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  • Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Coating With Molten Metal (AREA)
  • Heat Treatment Of Articles (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

提供一可較簡便地抑制熱壓後表層上的鋅氧化物過度生成且無塗裝部之耐蝕性優異的熔融鋅系鍍敷鋼板。 本發明之熔融鋅系鍍敷鋼板具備：作為基材之基底鋼板；設置在前述基底鋼板上之熔融鋅系鍍敷層；及表面處理層，係形成於前述熔融鋅系鍍敷層之至少單面上；前述表面處理層含有以金屬換算計每單面0.1g/m2以上且1.2g/m2以下之粒狀氧化物，該粒狀氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋅之標準生成自由能(△G0Zn)且大於氧化鋁之標準生成自由能(△G0Al)，並且，前述粒狀氧化物之粒徑為3nm以上且100nm以下。

Description

熔融鋅系鍍敷鋼板 發明領域
本發明係關於一種熔融鋅系鍍敷鋼板。
發明背景
近年，為了保護環境及防止地球暖化，抑制消耗化石燃料的訴求不斷攀高，且此訴求已對各種製造業造成影響。例如，作為移動手段於日常生活及活動上不可欠缺的汽車也無例外地尋求利用車體之輕量化等來提升燃耗等。然而，就汽車而言，單僅實現車體的輕量化無法滿足於製品機能，還必須確保適當的安全性。
有許多汽車構造係藉由鐵系材料尤其是鋼板形成，減低這些鋼板重量對車體輕量化而言相當重要。然而，如上述不能單僅減輕鋼板的重量，還同時尋求確保鋼板之機械強度。此種鋼板的訴求不僅是汽車製造業，許多製造業也面臨相同情況。因此，現行係藉由提高鋼板之機械強度，針對比以往使用之鋼板更薄但又可維持或提升機械強度的鋼板進行研究開發。
一般而言，具有高機械強度的材料在彎曲加工等成形加工中有形狀凍結性降低的傾向，很難成形加工成複 雜的形狀。關於這種成形性問題的解決手段之一可列舉所謂的「熱壓法(亦稱熱印模法、熱壓製法或模具淬火法)」。熱壓方法係先將成形對象之材料加熱至高溫，並對經由加熱而軟化的鋼板施行加壓加工予以成形後再行冷卻。藉由此熱壓方法，係先將材料加熱至高溫使其軟化，因此可輕易地將對象之材料加壓加工。此外，藉由成形後的冷卻之淬火效果，可提高材料的機械強度。因此，利用熱壓方法可獲得兼具良好的形狀凍結性及高度機械強度的成形品。
然而，若對鋼板適用此種熱壓方法，鋼板在加熱至800℃以上之高溫時，鋼板表面會氧化而生成鏽皮(化合物)。因此，進行熱壓加工後需要除去該鏽皮的步驟(所謂的去鏽步驟)，會降低生產性。此外，講求耐蝕性的構件等又必須於加工後對構件表面施行防鏽處理或金屬被覆，便需要表面清潔步驟及表面處理步驟，更會降低生產性。
抑制這種生產性降低的方法可舉如事先對將進行熱壓之鋼板施行被覆的方法。鋼板上之被覆一般係使用有機系材料或無機系材料等各種材料。其中，基於其本身的防蝕性能及鋼板生產技術的觀點，在汽車鋼板等多廣泛採用對鋼板具有犧牲性防蝕作用的鋅(Zn)系鍍敷鋼板。
藉由施行鋅系金屬被覆，可防止鋼板表面上生成鏽皮，便無需去鏽等步驟，所以可提升成形品之生產性。此外，鋅系金屬被覆也有防鏽效果，所以也會提升耐蝕性。下述專利文獻1~專利文獻4中即揭示了一種將鍍敷鋼板熱壓之方法且該鍍敷鋼板係已對具有既定成分組成之鋼板施 行鋅系金屬被覆者。
下述專利文獻1~專利文獻3中，熱壓用鋼板係利用熔融鍍鋅鋼板或合金化熔融鍍鋅鋼板。於熱壓利用熔融鍍鋅鋼板或合金化熔融鍍鋅鋼板，既不會於表面形成鐵氧化物(即，鏽皮)，也可成形構造構件。此外，下述專利文獻4中揭示了一項發明，其指出若在已將鋅系鍍敷鋼板予以熱壓之熱處理鋼材表面上形成一厚厚的氧化鋅層，會對熱處理鋼材之塗膜密著性或塗裝後耐蝕性造成不良影響，因此其係對熱處理鋼材施行珠粒噴擊(shot blast)以除去氧化鋅層，或是減低氧化鋅層之厚度後再進行塗裝。
另外，下述專利文獻5及專利文獻6中揭示了一項用以改善鋅系鍍敷鋼板經過熱壓之熱處理鋼材的塗膜密著性或塗裝後耐蝕性的發明。下述專利文獻5係揭示使用表面被聚矽氧樹脂皮膜被覆之熔融鍍鋅鋼板作為熱壓用鋼板的發明，而下述專利文獻6係揭示使用經由含有磷(P)及矽(Si)之障壁層(就P係舉例磷酸鹽，就Si係舉例膠質氧化矽)被覆之熔融鍍鋅鋼板作為熱壓用鋼板的發明。
又，下述專利文獻7揭示了一技術，其係於鍍鋅層中添加比Zn更容易氧化之元素(易氧化性元素)，於熱壓時在升溫期間於鍍鋅層表層形成一該等易氧化性元素之氧化物層以防止鋅揮發。
根據下述專利文獻5~專利文獻7中揭示之發明，因鍍鋅層被前述障壁層被覆而可抑制鋅蒸發，藉此，中間塗膜或表塗塗膜可具有良好的密著性或塗裝後耐蝕性。
先前技術文獻 專利文獻
專利文獻1：日本特開2003-73774號公報
專利文獻2：日本特開2003-129209號公報
專利文獻3：日本特開2003-126921號公報
專利文獻4：日本特開2004-323897號公報
專利文獻5：日本特開2007-63578號公報
專利文獻6：日本特開2007-291508號公報
專利文獻7：日本特開2004-270029號公報
發明概要
然而，鋅系鍍敷鋼板尤其是在熔融鍍鋅鋼板或合金化熔融鍍鋅鋼板業經熱壓時，於熱壓加熱期間很難避免鋅氧化，熱壓後鍍敷層中所殘存的金屬鋅量會減少。金屬鋅量一旦減少，不僅塗裝後耐蝕性可能劣化，即使無塗裝耐蝕性也可能劣化。
另外，本發明人等在對專利文獻5所揭示之使用表面被聚矽氧樹脂皮膜被覆之熔融鍍鋅鋼板作為熱壓用鋼板而獲得的熱處理鋼材進行複試時得知，在重複乾濕環境之循環性腐蝕試驗中，塗裝後耐蝕性雖然良好，但於熱壓加熱期間鋅被過度氧化，無塗裝的耐蝕性不見得良好。因此，藉由上述專利文獻5所揭示之發明而製得的熱處理鋼材不適合直接使用在例如鋼材之接合部位或構件(例如，鋼筋 之板接合部或置物櫃內部的點熔接部附近等)上。
另一方面，如上述專利文獻7所揭示，於鍍鋅層中添加易氧化性元素可抑制鋅氧化，但在鍍浴之溫度管理及浮渣對策等操作上又需要另下番工夫。
爰此，本發明係有鑑於上述問題而實施，本發明目的在於提供一種可較簡便地抑制熱壓後表層上的鋅氧化物之過度生成且無塗裝部之耐蝕性優異的熔融鋅系鍍敷鋼板。
本發明人等針對上述目的之熱壓用鍍敷鋼板進行精闢研討並根據由該結果推衍的見解聯想到下述熔融鋅系鍍敷鋼板。
本發明主旨如下。
(1)一種熔融鋅系鍍敷鋼板，具備：作為基材之基底鋼板；設置在前述基底鋼板上之熔融鋅系鍍敷層；及表面處理層，係形成於前述熔融鋅系鍍敷層之至少單面上；前述表面處理層含以金屬換算計含有每單面0.1g/m2以上且1.2g/m2以下之粒狀氧化物，該粒狀氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋅之標準生成自由能(△G0 Zn)且大於氧化鋁之標準生成自由能(△G0 Al)，並且，前述粒狀氧化物之粒徑為3nm以上且100nm以下。
(2)如(1)記載之熔融鋅系鍍敷鋼板，其中前述表面處理層以每單面含量計，在以下所示範圍內更含有含磷化合物、 含釩化合物、含銅化合物、含鋁化合物或含鉻化合物之至少任一者。
含磷化合物：以P換算計為0.0g/m2以上且0.01g/m2以下
含釩化合物：以V換算計為0.0g/m2以上且0.01g/m2以下
含銅化合物：以Cu換算計為0.0g/m2以上且0.02g/m2以下
含鋁化合物：以Al換算計為0.0g/m2以上且0.005g/m2以下
含鉻化合物：以Cr換算計為0.0g/m2以上且0.01g/m2以下
(3)如(1)或(2)記載之熔融鋅系鍍敷鋼板，其中前述基底鋼板具有下述化學組成：以質量%計，含有：C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、Ti：0~0.1%、Cr：0~0.5%、Nb：0~0.1%、Ni：0~1.0%、及Mo：0~0.5%，且剩餘部分由Fe及雜質所構成。
(4)如(1)或(2)記載之熔融鋅系鍍敷鋼板，其中前述基底鋼板具有下述化學組成：以質量%計，含有：C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、Ti：0~0.1%、Cr：大於0%且0.5%以下、Nb：0~0.1%、Ni：0~1.0%、Mo：0~0.5%，且剩餘部分由Fe及雜質所構成，並且，滿足Mn+Cr：0.5~3.0%之關係。
(5)如(1)~(4)中任一項記載之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物為金屬氧化物。
(6)如(1)~(5)中任一項記載之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物為鈦氧化物或矽氧化物。
(7)如(1)~(6)中任一項記載之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物之粒徑為5nm以上且30nm以下。
(8)如(1)~(7)中任一項記載之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物之含量以金屬換算計為每單面0.2g/m2以上且0.8g/m2以下。
(9)如(1)~(8)中任一項記載之熔融鋅系鍍敷鋼板，其中前述表面處理層以金屬換算計更含有每單面0.05g/m2以上且0.35g/m2以下之鹼土類金屬氧化物，該鹼土類金屬氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋁之標準生成自由能(△G0 Al)。
(10)如(9)記載之熔融鋅系鍍敷鋼板，其中前述鹼土類金屬氧化物為鈣氧化物或鎂氧化物。
(11)如(9)或(10)記載之熔融鋅系鍍敷鋼板，其中前述鹼土類金屬氧化物之含量以金屬換算計為每單面0.05g/m2以上且0.2g/m2以下。
(12)如(1)~(11)中任一項記載之熔融鋅系鍍敷鋼板，其係熱壓用熔融鋅系鍍敷鋼板。
如以上說明，依據本發明可抑制熱壓中表層上的鋅氧化物生成以確保熱壓後鍍敷層中所殘存的金屬鋅量，進而無需特別提升無塗裝部之耐蝕性。
用以實施發明之形態
以下詳細說明本發明的適當實施形態。
<1.熔融鋅系鍍敷鋼板>
本發明之實施形態的熔融鋅系鍍敷鋼板於基底鋼板上具備熔融鋅系鍍敷層，更在該熔融鋅系鍍敷層上之至少單面具備以下詳述之表面處理層。該表面處理層以金屬換算計含有每單面0.1g/m2以上且1.2g/m2以下之粒狀氧化物且粒狀氧化物粒徑為3nm以上且100nm以下，該粒狀氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋅之標準生成自由能(△G0 Zn)且大於氧化鋁之標準生成自由能(△G0 Al)。具有此構成的熔融鋅系鍍敷鋼板可適用在先前所說明之熱壓法。以下針對該熔融鋅系鍍敷鋼板之構成詳細說明。
(1)基底鋼板
本實施形態之熔融鋅系鍍敷鋼板所使用的基底鋼板並無特別限定，可使用具有公知特性及化學組成的各種鋼板。鋼板之化學組成亦無特別限定，以可藉由淬火獲得高強度的化學組成為佳。例如，欲獲得拉伸強度達980MPa以上之熱處理鋼材時，可列舉基底鋼板係由具有下述化學組成之淬火用鋼所構成者：以質量%計，含有：C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、 Ti：0~0.1%、Cr：0~0.5%、Nb：0~0.1%、Ni：0~1.0%及Mo：0~0.5%，且剩餘部分由Fe及雜質所構成。
如欲獲得淬火時強度小於980MPa之較低強度的熱處理鋼材，基底鋼板之化學組成可不在上述範圍內。
從上述淬火時的淬火性觀點以及形成加熱後含在氧化鋅層中之Mn、Cr氧化物的觀點來看，適度的Mn、Cr量以Mn+Cr：0.5~3.0%為佳。更以Mn+Cr：0.7~2.5%較佳。
鋼板之化學組成中若含有Mn、Cr，熱壓後形成於表層上的氧化鋅層有一部分會成為含有Mn、Cr的複合氧化物。藉由形成該等含有Mn、Cr之複合氧化物，可提升與皮膜成分或鍍敷成分之密著性，耐模具凝著性即佳。詳細情況不明，吾等認為，與氧化鋅相較下，藉由形成該等複合氧化物，所形成之皮膜較為緻密，所以可顯現良好的耐模具凝著性。
鋼板之化學組成中含有Mn、Cr時，其含量以Mn+Cr計含有質量%計0.5%以上且3.0%以下之範圍為佳，較宜為0.7%以上且2.5%以下之範圍。Mn+Cr之含量低於0.5%時，熱壓後形成於表層之氧化鋅與含有Mn、Cr之複合氧化物的形成會不夠充分，而可能變得難以顯現較良好的耐模具凝著性。另一方面，Mn+Cr之含量超過3.0%時，在塗裝密著性方面雖然不會有問題，但有成本升高、以及點熔接部之韌性明顯降低及鍍敷濕潤性顯著劣化的情況。
(2)熔融鋅系鍍敷層
本實施形態之熔融鋅系鍍敷層並無特別限定，可使用一般周知的熔融鋅系鍍層。具體上，本實施形態之熔融鋅系鍍敷層可列舉熔融鋅鍍層、合金化熔融鋅鍍層、熔融Zn-55%Al鍍層、熔融Zn-11%Al鍍層、熔融Zn-11%Al-3%Mg鍍層、熔融Zn-7%Al-3%Mg鍍層、熔融Zn-11%Al-3%Mg-0.2%Si鍍層等。
至於，關於本發明意屬對象之熔融鋅系鍍層，就算不是以鋁(Al)作為主要成分之Zn-Al系合金鍍層，也會在鍍浴及鍍敷層中含有Al。其理由如下。即，鍍浴溫度為440~480℃左右且在該溫度區內Zn與Fe一接觸，Fe與Zn便會相繼合金化因而產生浮渣。藉由令鍍浴中含有Al，可在Fe與Zn發生反應之前先引發Fe與Al之反應，其結果可抑制浮渣之產生。基於該理由，通常會使熔融鋅鍍浴含有Al。
一般而言，針對熔融鍍鋅會在鍍浴中含有0.2~0.3%之Al且鍍敷層中含有0.2~1.0質量%之Al，就合金化熔融鍍鋅則係在鍍浴中含有0.1~0.2%之Al且鍍敷層中含有0.1~0.5質量%之Al。
鍍敷層中之Al除了在形成鍍敷皮膜時會擴散，還會在熱壓加熱時擴散而移動至鍍敷層之表層。此時，Al會比Zn優先被氧化而形成由Al2O3所構成之Al氧化膜。
本實施形態之具體的鍍敷操作係實施下述操作：將鋼板浸漬於保持有處於熔融狀態之Zn或Zn合金的鍍浴中並從該鍍浴取出鋼板。對於鋼板之鍍敷附著量的控制係藉由鋼板之取出速度或拭焊氣體(wiping gas)之流量及流速調 整等進行，該拭焊氣體係由設置在鍍浴上方之拭焊噴嘴(wiping nozzle)噴出。此外，合金化處理係於上述鍍敷處理後，以燃氣爐、感應加熱爐或將該等併用之加熱爐等額外將鍍敷後之鋼板予以加熱而進行。關於該鍍敷操作可利用卷料的連續鍍敷法或是裁切板單體的鍍敷法之任一項來進行鍍敷。
該熔融鋅系鍍敷層之厚度(即熔融鋅系鍍敷層之附著量)以每單面20g/m2~100g/m2之範圍為佳。熔融鋅系鍍敷層之厚度若每單面小於20g/m2，將無法確保熱壓後之有效Zn量，讓耐蝕性變不夠充分，故不適宜。此外，熔融鋅系鍍敷層之厚度若每單面超過100g/m2，則鍍敷層之加工性、密著性會降低，故不適宜。較適度的熔融鋅系鍍敷層厚度係每單面30g/m2~90g/m2之範圍。
(3)表面處理層
在如上述的熔融鋅系鍍敷層上更形成有含有粒狀氧化物之表面處理層，該粒狀氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋅之標準生成自由能(△G0 Zn)且大於氧化鋁之標準生成自由能(△G0 Al)。吾等認為，該氧化物係藉由鋅系鍍敷層中所含Al還原並比Zn優先被氧化而抑制氧化鋅之生成。
在此，「粒狀氧化物」並非意指像硝酸鹽或硫酸鹽、鋰鹽等化合物以溶解於處理液中之狀態存在，而是以一次粒徑達數nm以上之固體分散於處理液中之狀態存在之以氧化物為主體的物質。藉由使用這種以固體狀態分散於 處理液中且在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)小於氧化鋅(ZnO)之標準生成自由能(△G0 Zn)且大於氧化鋁(Al2O3)之標準生成自由能(△G0 Al)的粒狀氧化物，可提供尤其是塗裝無法包覆之鋼板接合部環境之耐久性優異的熱處理鋼材。至於，該粒狀氧化物在表面處理層中係以粒子狀態存在。
在此，氧化鋅(ZnO)及氧化鋁(Al2O3)在900~1300K之溫度區的標準生成自由能之具體數值可參照「腐蝕防蝕協會編：腐蝕‧防蝕指南」等公知資料集而得知。例如，氧化鋅(ZnO)在900K及1300K下的標準生成自由能(△G0 Zn)分別約-535kJ/mol、-460kJ/mol，氧化鋁(Al2O3)在900K及1300K下的標準生成自由能(△G0 Al)則分別約-945kJ/mol、-880kJ/mol。
在900~1300K之溫度區內，同一溫度下的氧化物標準生成自由能(△G0)小於ZnO之標準生成自由能(△G0 Zn)且大於Al2O3之標準生成自由能(△G0 Al)的粒狀氧化物可舉例如矽(Si)氧化物、鈦(Ti)氧化物、鉻(Cr)氧化物、釩(V)氧化物、錳(Mn)氧化物、硼(B)氧化物等。
其中，若從穩定、容易取得等觀點來看，已金屬元素之氧化物(即金屬氧化物)為宜。該金屬氧化物可列舉Si氧化物、Ti氧化物、Cr氧化物、V氧化物等。至於，像Si因結晶構造而成為半導體或金屬之元素的氧化物也含在金屬氧化物內。
在此，Cr氧化物在有鑑於近期力求環境保護思慮 的傾向之下，必定不含6價鉻，而若以不含有包含3價鉻之鉻分即無鉻為宜為出發點，滿足上述標準生成自由能之相關條件的粒狀氧化物則宜使用Si氧化物及Ti氧化物。
此外，滿足上述標準生成自由能之相關條件的粒狀氧化物之粒徑(一次粒徑)為3nm以上且100nm以下。從塗裝後耐蝕性的面向來看，氧化物粒徑愈小愈有利，不過粒徑小於3nm者不易取得，就成本面不利。此外，上述粒狀氧化物之粒徑超過500nm時，有表面積降低而使加熱時與下層鍍層之反應性降低的懸念，故不適宜。上述粒狀氧化物的較理想粒徑為5nm以上且30nm以下。
至於，如上述之粒狀氧化物粒徑(一次粒徑)可藉由公知方法測得，例如可以下述方法進行測定：製作塗裝後截面嵌入式的試樣，在多數點測得皮膜中之氧化物粒子粒徑並將所得測定結果予以平均之值視作粒徑。
本實施形態之表面處理層係由含有滿足上述標準生成自由能之相關條件之粒狀氧化物的處理液形成。於本實施形態之表面處理層以金屬換算計含有每單面0.1g/m2以上且1.2g/m2以下之滿足上述標準生成自由能之相關條件的粒狀氧化物。
該表面處理層中以金屬換算計含有每單面0.1g/m2以上且1.2g/m2以下之粒狀氧化物的熔融鋅系鍍敷鋼板在熱壓前即存在於熔融鋅鍍敷層中，且藉由熱壓時所形成的Al氧化物還原表面處理層中所含氧化物。這種氧化物被還原的金屬粒子比Zn更容易形成氧化物，所以會比Zn 優先被氧化。其結果，氧化鋅之生成即受抑制。
表面處理層中之粒狀氧化物的附著量以金屬換算計每單面少於0.1g/m2時，熱壓中抑制氧化鋅生成所需之已還原氧化物的金屬粒子會無法充分存在，進而無法抑制氧化鋅生成，無法確保充分的耐蝕性。另一方面，表面處理層中之粒狀氧化物的附著量以金屬換算計每單面超過1.2g/m2時，本實施形態之熔融鋅系鍍敷鋼板不僅成本上升，表面處理層之凝聚力也會變薄弱，熱壓後形成於表面處理層上的塗膜還容易剝離。
此表面處理層中之粒狀氧化物的附著量理想係以金屬換算計為每單面0.2g/m2以上且0.8g/m2以下。
在此，表面處理層之上述粒狀氧化物的金屬換算附著量可藉由公知方法測得，例如可將表面處理層溶解使用感應耦合電漿(Inductively Coupled Plasma：ICP)發光分光分析法等來進行測定。
含有滿足上述標準生成自由能之相關條件之粒狀氧化物的處理液可使用分散有矽或鈦、錳等之氧化物粉末的處理液。此外，預先分散之處理液較宜使用氧化鈦溶膠或氧化矽溶膠。氧化鈦溶膠之具體的販售產品可列舉TAYCA(股)製TKS(註冊商標)系列。氧化矽溶膠之具體的販售產品可列舉日產化學(股)製SNOWTEX(註冊商標)系列。
在表面處理層之形成可將上述之氧化鈦溶膠或氧化矽溶膠直接塗佈於熔融鍍鋅鋼板上，不過為了改善處理液之穩定性或表面處理層之密著性，宜作成混合有樹脂 或交聯劑之處理液後再塗佈於熔融鋅系鍍敷鋼板上。
就所述樹脂，在使用如上述之氧化鈦溶膠或氧化矽溶膠時，宜使用水溶性或水分散性之樹脂，就樹脂種類來說可列舉聚胺甲酸乙酯樹脂、聚酯樹脂、環氧樹脂、(甲基)丙烯酸樹脂、聚烯烴樹脂、酚樹脂或該等樹脂之改質體等。使用氧化鈦粉末或氧化矽粉末時，除了上述水系樹脂以外，亦可使用以各種溶劑作為溶媒之溶劑系樹脂。
就所述交聯劑，可列舉矽烷耦合劑、碳酸鋯化合物、有機鈦化合物、唑啉聚合物、水溶性環氧化合物、水溶性三聚氰胺樹脂、水分散封端異氰酸酯、水系氮化合物等。
至於，即使混合上述之樹脂或交聯劑，滿足上述標準生成自由能之相關條件的粒狀氧化物含量也如上述係設定成於表面處理層中以金屬換算計每單面0.1g/m2以上且1.2g/m2以下。
此外，本實施形態之表面處理層中更宜含有的其它成分可舉如在900~1300K之溫度區內，同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋁之標準生成自由能(△G0 Al)的廣義鹼土類金屬(即，第2族元素之鈹、鎂、鈣、鍶、鋇、鐳)之氧化物。
表面處理層中若含有上述之鹼土類金屬氧化物，熱壓時雖然係以通常的金屬氧化物狀態穩定存在，不過推測其會與熱壓之加熱時所形成的氧化鋅起反應而形成與氧化鋅之複合氧化物，進而抑制過度的鋅氧化或蒸發。可更 有效率地獲取該效果的鹼土類金屬氧化物宜使用氧化鎂或氧化鈣。
表面處理層含有氧化鎂或氧化鈣時，其含量以金屬換算計定在每單面0.05g/m2以上且0.35g/m2以下為佳，較理想係以金屬換算計為每單面0.05g/m2以上且0.2g/m2以下。氧化鎂或氧化鈣之含量以金屬換算計每單面低於0.05g/m2時，可能無法充分與氧化鋅形成複合氧化物，進而難以有效率地抑制Zn之氧化或蒸發。另一方面，氧化鎂或氧化鈣之含量以金屬換算計每單面超過0.35g/m2時，可能產生表面處理層之凝聚力降下而發生密著性的不良情況。
本實施形態之表面處理層除了上述之氧化物以外，亦可在既定含量之範圍內含有以下詳述之含P化合物、含V化合物、含Cu化合物、含Al化合物或含Cr化合物之至少任一項。
含P化合物係含有磷作為構成元素的化合物。此種含P化合物可舉如磷酸、亞磷酸、膦酸、亞膦酸(phosphonous acid)、亞膦酸(phosphinic acid)、次膦酸(phosphinous acid)、膦氧化物、膦等化合物或是以該等化合物作為陰離子之離子化合物等。該等含P化合物皆已作為試藥或製品販售流通，可輕易取得。該等含P化合物係以溶解於處理液中之狀態或以粉末分散在處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
含V化合物係含有釩作為構成元素的化合物。此種含V化合物可舉如含有五氧化釩之釩氧化物、含有偏釩酸 銨之偏釩酸系化合物、含有釩酸鈉之釩化合物及其它含V之化合物等。該等含V化合物皆已作為試藥或製品販售流通，可輕易取得。該等含V化合物係以溶解於處理液中之狀態或以粉末分散在處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以P及V換算計，在每單面0.0g/m2以上且0.01g/m2以下範圍內各含有選自上述含P化合物及含V化合物中的1種或2種以上化合物為佳。
選自上述含P化合物及含V化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物，偏佈在熔融Zn系鍍敷層與表面處理層之界面，形成含有P或V之至少任一項之凝聚力薄弱的氧化物層。選自含P化合物及含V化合物中之1種或2種以上化合物的含量以P及V換算計分別為每單面0.0g/m2以上且0.01g/m2以下之範圍，藉此，在熱壓時所形成之上述凝聚力薄弱的氧化物層厚度會變薄，而進一步提升熱壓後之熔融Zn系鍍敷層與表面處理層的密著性。
表面處理層中選自含P化合物及含V化合物中之1種或2種以上的含量在每單面超過0.01g/m2時，熱壓時所形成之凝聚力薄弱的氧化物層之厚度會變厚，令熔融Zn系鍍敷層與表面處理層之密著性降低。其結果，熱壓後之表面處理層便容易剝離，而已剝離之表面處理層可能會凝著於熱壓用模具上。從熱壓後之熔融Zn系鍍敷層與表面處理層之密著性觀點來看，表面處理層中選自含P化合物及含V化合物中之1種或2種以上化合物的含量以P及V換算計分別為 每單面0.0g/m2以上且0.003g/m2以下較佳。
含Cu化合物係含有銅作為構成元素的化合物。此種含Cu化合物可舉如金屬Cu、氧化銅、各種有機銅化合物、各種無機銅化合物及各種銅錯合物等。該等含Cu化合物皆已作為試藥或製品販售流通，可輕易取得。該等含Cu化合物係以溶解於處理液中之狀態或以粉末分散在處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以Cu換算計，在每單面0.0g/m2以上且0.02g/m2以下範圍內含有選自上述含Cu化合物中的1種或2種以上化合物為佳。
選自上述含Cu化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物，偏佈在Zn系鍍敷層與表面處理層之界面，形成含有Cu之凝聚力薄弱的氧化物層。選自含Cu化合物中之1種或2種以上化合物之含量以Cu換算計為每單面0.0g/m2以上且0.02g/m2以下之範圍，藉此，熱壓時所形成之上述凝聚力薄弱的氧化物層厚度會變薄，而進一步提升熱壓後之熔融Zn系鍍敷層與表面處理層的密著性。
表面處理層中選自含Cu化合物中之1種或2種以上之含量每單面超過0.02g/m2時，熱壓時所形成之凝聚力薄弱的氧化物層厚度會變厚，令熔融Zn系鍍敷層與表面處理層間之密著性降低。其結果，熱壓後表面處理層變容易剝離，而已剝離之表面處理層可能會凝著於熱壓用模具上。 再加上，Cu係比基底鋼板主成分之Fe更貴的元素，所以耐蝕性也有降低之傾向。若從熱壓後之熔融Zn系鍍敷層與表面處理層間之密著性觀點來看，表面處理層中選自含Cu化合物中之1種或2種以上化合物的含量以Cu換算計為每單面0.0g/m2以上且0.005g/m2以下較佳。
含Al化合物係含有鋁作為構成元素的化合物。此種含Al化合物可舉如金屬Al、氧化鋁、氫氧化鋁、以鋁離子作為陽離子的離子化合物等。該等含Al化合物皆已作為試藥或製品販售流通，可輕易取得。該等含Al化合物係以溶解於處理液中之狀態或以粉末分散在處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
本實施形態之表面處理層以Al換算計，在每單面0.0g/m2以上且0.005g/m2以下範圍內含有選自上述含Al化合物中的1種或2種以上化合物為佳。
選自上述含Al化合物中之1種或2種以上化合物在熱壓時會被氧化而成為氧化物而濃化於表面處理層表面。選自含Al化合物中之1種或2種以上化合物的含量以Al換算計為每單面0.0g/m2以上且0.005g/m2以下之範圍，藉此，在熱壓時形成於表面處理層表面之含Al之氧化物的存在比率會變小，可防止含有該等Al之氧化物凝著於熱壓用模具上。
表面處理層中選自含Al化合物中之1種或2種以上的含量每單面超過0.005g/m2時，熱壓時所形成之含Al之氧化物的存在比率會變大。該等含Al之氧化物不僅會凝著 於熱壓用模具，也會阻礙化成處理皮膜之形成，因此，熱壓時所形成之含Al之氧化物的存在比率變大會增加含Al之氧化物凝著於熱壓用模具上的情況，令操作性降低。從此操作性觀點來看，表面處理層中選自含Al化合物中之1種或2種以上化合物的含量以Al換算計為每單面0.0g/m2以上且0.002g/m2以下較佳。
含Cr化合物係含有鉻作為構成元素的化合物。此種含Cr化合物可舉如金屬Cr、具有各種價數之鉻化合物、及以具有各種價數之鉻離子作為陽離子的離子化合物等。該等含Cr化合物係以溶解於處理液中之狀態或以粉末分散在處理液中之狀態存在，在表面處理層中則以固體分散之狀態存在。
含Cr化合物因價數不同而有不同的性能及性質，6價鉻化合物中存有多種有害化合物。如先前所言及，有鑑於近期力求環境保護思慮的傾向，本實施形態之表面處理層以極力不含上述之含Cr化合物為佳，且以無鉻較佳。
基於上述觀點，本實施形態之表面處理層以Cr換算計在每單面0.0g/m2以上且0.01g/m2以下範圍內含有選自上述含Cr化合物中之1種或2種以上化合物為佳，且以不含含Cr化合物較佳。
該表面處理層之形成方法將含有滿足上述標準生成自由能之相關條件之粒狀氧化物的處理液塗佈於鍍鋅鋼板表面上並予以乾燥及燒附即可。
塗佈方法並無限定特定方法，舉例有：將基底鋼 板浸漬於處理液或對基底鋼板表面噴佈處理液後，以成為既定附著量的方式藉由輥件或氣體噴附控制附著量之方法、或是以輥塗器或棒塗器進行塗佈之方法。
此外，乾燥、燒附方法也只要是可使分散媒(主要為水)揮發的方法即可，不限於特定方法。在此，若過度以高溫加熱，有表面處理層之均一性降低的疑慮；反之，若過度以低溫加熱，則有生產性降低的疑慮。因此，為了穩定且有效率地製造具有優異特性的表面處理層，宜在80℃~150℃左右的溫度下將塗佈後之表面處理層加熱5秒~20秒左右。
又，表面處理層之形成在鍍敷鋼板製造線上以線內進行既經濟又實惠，不過亦可以其它的生產線形成，或是可實施用來進行成形的沖裁(blanking)後再予以形成。
在此，表面處理層中之上述含P化合物、含V化合物、含Cu化合物、含Al化合物、含Si化合物及含Cr化合物的含量可藉由公知方法測得，例如事先以截面能量色散型X射線(Energy Dispersive X-ray：EDX)分析等確認表面處理層中之各種化合物係在此聚焦之上述各項含有元素之化合物後，再將皮膜溶解並使用ICP(Inductively Coupled Plasma、感應耦合電漿)發光分光分析法等進行測定。
<2.關於熱壓步驟>
對先前說明之熔融鋅系鍍敷鋼板適用熱壓法時，係將熔融鋅系鍍敷鋼板加熱至既定溫度後再行加壓成形。本實施形態之熔融鋅系鍍敷鋼板在施行熱壓成形後，通常會加 熱至700~1000℃，若欲在急速冷卻後形成麻田散鐵單相或使麻田散鐵以體積率計達90%以上，令加熱溫度之下限溫度為Ac3點以上即為重要。在本發明，急速冷卻後也包含麻田散鐵/肥粒鐵之2相域的情況，因此加熱溫度以如上述定為700~1000℃為佳。
在熱壓法中有緩加熱之熱壓及急速加熱之熱壓2種方法。採用的加熱方法可列舉電爐、燃氣爐或火焰加熱、通電加熱、高頻加熱、感應加熱等，加熱時的氣體環境也無特別限制，不過就可明顯獲得本發明效果的加熱方法來說，宜採用急速加熱之通電加熱、感應加熱等。
在緩加熱之熱壓法係利用加熱爐之輻射加熱。首先，使用本實施形態之熔融鋅系鍍敷鋼板作為熱壓用鋼板並將之裝入加熱爐(燃氣爐、電爐等)。在加熱爐內將熱壓用鋼板加熱至700~1000℃，並按條件保持在該加熱溫度下(均熱)。藉此，使熔融鋅系鍍敷層中之熔融Zn與Fe結合而成為固相(Fe-Zn固溶體相)。使熔融鋅系鍍敷層中之熔融Zn與Fe結合並固相化後，再從加熱爐抽出鋼板。此外，亦可藉由均熱使熔融鋅系鍍敷層中之熔融Zn與Fe結合並以Fe-Zn固溶體相及ZnFe合金相固相化後，再從加熱爐抽出鋼板。
相對地，亦可將熔融鋅系鍍敷鋼板加熱至700~1000℃，在無保持時間或令保持時間為很短時間的情況下從加熱爐抽出鋼板。在此情況下，係在鋼板加熱至700~1000℃後，以未利用加壓成形等對鋼板賦予應力的方式冷 卻至熔融鋅系鍍敷層中之熔融Zn與Fe結合而成為固相(Fe-Zn固溶體相或ZnFe合金相)為止。具體上，係至少冷卻至鋼板溫度成為熔融鋅系鍍敷層可固相化之溫度為止。例如，在熔融鋅鍍敷層或合金化熔融鋅鍍敷層的情況下，係冷卻至鋼板溫度成為782℃以下。冷卻後，如以下說明使用模具加壓鋼板並同時進行冷卻。另一方面，加熱溫度為782℃以下時，熔融鋅系鍍敷層係維持固相狀態，因此可從加熱爐抽出鋼板後再快速進行加壓成形。
在急速加熱之熱壓也同樣地係使用本實施形態之熔融鋅系鍍敷鋼板作為熱壓用鋼板，急速加熱至700~1000℃。急速加熱例如可藉由通電加熱或感應加熱實施。此時的平均加熱速度在20℃/秒以上。在急速加熱的情況下，係在熔融鋅系鍍敷鋼板加熱至700~1000℃後，以未利用加壓成形等對鋼板賦予應力的方式冷卻至熔融鋅系鍍敷層中之熔融Zn與Fe結合而成為固相(Fe-Zn固溶體相或ZnFe合金相)為止。具體上，係至少冷卻至鋼板溫度成為熔融鋅系鍍敷層可固相化之溫度為止。例如，在熔融鋅鍍敷層或合金化熔融鋅鍍敷層的情況下，係冷卻至鋼板溫度成為782℃以下。冷卻後，如以下說明使用模具加壓鋼板並同時進行冷卻。加熱溫度為782℃以下時，熔融鋅系鍍敷層係維持固相狀態，因此可從加熱爐抽出鋼板後再快速進行加壓成形。
已抽出的鋼板係利用模具加壓。加壓鋼板時，鋼板會被模具冷卻。模具內有冷卻介質(例如水等)循環，所以模具可將鋼板除熱並冷卻。藉由以上步驟，即可利用一般 的加熱來製造熱壓鋼材。
使用具有本實施形態之表面處理層的熔融鋅系鍍敷鋼板所製出的熱壓鋼材具有優異的耐久性。
使用昔知之鍍敷鋼板來實施一般加熱之熱壓時，實施一般加熱之熱壓時鋼板會在加熱爐內均勻受熱。此時會於熱壓用鋼板之鍍敷層表層形成一氧化鋅膜，不過經由長時間之均熱加熱將形成多量的氧化鋅膜，熱壓後皮膜中所殘存的金屬鋅量便會減少。因此，若與加熱前之鍍鋅鋼材相比，可能有熱壓鋼材之無塗裝耐蝕性顯著降低的情況。
然而，本實施形態之熔融鋅系鍍敷鋼板因為表面處理層中含有滿足上述標準生成自由能之相關條件的粒狀氧化物，所以可在熱壓時抑制氧化鋅生成，確保熱壓後表層上的金屬鋅量，故而可發揮良好的無塗裝耐蝕性。
實施例
以下顯示實施例以進一步具體說明本發明實施形態之熔融鋅系鍍敷鋼板的作用效果。至於，以下所示實施例不過為本發明之熔融鋅系鍍敷鋼板的其中一例，本發明之熔融鋅系鍍敷鋼板不受下述實施例限定。
<基底鋼板>
以下，首先製造具有以下表1所示化學組成之熔鋼。然後使用所製造之各熔鋼以連續鑄造法製出鋼胚。將製得之鋼胚予以熱軋延，製造出鋼胚。接著將熱軋鋼板酸洗後，實施冷軋延，製造冷軋鋼板，藉以製作具有表1記載之化學 組成的鋼#1~#8之鋼板。如表1所示，各鋼種之鋼板板厚均為1.6mm。
[表1]
<熔融鋅系鍍敷層>
對鋼#1~#8之鋼板進行熔融鍍鋅處理，然後實施合金化處理。合金化處理中的最高溫度皆為530℃，加熱約30秒後冷卻至室溫而製出合金化熔融鍍鋅鋼板(GA)。又，使用鋼#1進行熔融鍍鋅處理且未施行合金化處理而製出熔融鍍鋅鋼板(GI)。
再來，使用熔融Zn-55%Al、熔融Zn-6%Al-3%Mg、熔融Zn-11%Al-3%Mg-0.2%Si之3種鍍浴，對鋼#1進行各種熔融鍍鋅而製造出熔融鋅系鍍敷鋼板A1~A3。
A1：熔融Zn-55%Al
A2：熔融Zn-6%Al-3%Mg
A3：熔融Zn-11%Al-3%Mg-0.2%Si
此外，對鋼#1進行電鍍鋅處理而製造出電鍍鋅鋼板(EG)。
在此，在上述熔融鋅系鍍敷鋼板中，熔融鋅系鍍敷層之附著量係定為50g/m2。
至於，關於上述熔融鍍鋅鋼板之鍍敷皮膜中的Al濃度係以下述方法求得。即，從各熔融鋅系鍍敷鋼板採取試樣。將所取得之試樣的熔融鋅系鍍敷層以10%HCl水溶液予以溶解後，利用ICP發光分光分析法分析熔融鋅系鍍敷層之組成。根據所得分析結果求出每單面之Al濃度(質量%)。所得結果係整合顯示於以下表3。
<表面處理層>
接下來，用水將氧化物及藥劑混合，以形成成為表2所 示組成及附著量之皮膜。粉末狀態的氧化物係分散在添加有樹脂之水中，並以球磨機將粉末粉碎成分散於樹脂分散溶液的程度以後作使用。以棒塗器塗佈所得處理液，並在最高到達溫度100℃下保持8秒鐘之條件下使用烘箱進行乾燥，藉以製造出熱壓用鍍敷鋼板。處理液之附著量係以表面處理層中之氧化物之金屬換算的每單面附著量成為表2所示數值的方式，藉由液體稀釋及棒塗器支數來調整。
表2中之各成分(記號)如下。
(i)氧化物等：Ti氧化物、Si氧化物
TPA：氧化鈦粉末(Ionic Liquids Technologies社製)、粒徑10~30nm(型錄值)
TPB：氧化鈦粉末(TAYCA(股)TITANIX JA-1)、粒徑180nm(型錄值)
TZ：氧化鈦溶膠(TAYCA(股)氧化鈦溶膠TKS-203)、粒徑6nm(型錄值)
SZ：氧化矽溶膠(日產化學工業(股)SNOWTEX ST-C)、粒徑10~20nm(型錄值)
MP：氧化錳(Mn3O4)粉末(IOX Co.,Ltd.製)、平均粒徑25nm(型錄值)
至於，上述5種氧化物係同一溫度下的標準生成自由能(△G0)小於ZnO之標準生成自由能(△G0 Zn)且大於Al2O3之標準生成自由能(△G0 Al)的物質。
(ii)鹼土類：鹼土類金屬氧化物
Mg：氧化Mg(高純度化學(股)氧化鎂)
Ca：氧化Ca(高純度化學(股)氧化鈣)
Sr：氧化Sr(高純度化學(股)氧化鍶)
(iii)樹脂
A：胺甲酸乙酯系樹脂乳液(第一工業製藥(股)SUPERFLEX(註冊商標)E-2000)
B：胺甲酸乙酯系樹脂乳液(第一工業製藥(股)SUPERFLEX(註冊商標)150)
C：聚酯樹脂乳液(東洋紡(股)Vylonal(註冊商標)MD1480)
(iv)交聯劑
M：三聚氰胺樹脂(Mitsui Cytec(股)Cymel(註冊商標)325)
Z：碳酸鋯銨(Kishida Chemical(股)碳酸鋯銨溶液)
S：矽烷耦合劑(日美商事(股)sila-ace S510)
(v)顏料
PZ：亞磷酸鋅(東邦顏料(股)NP-530)(含P化合物)
Al：氧化鋁溶膠(日產化學(股)AS-200)(含Al化合物)
V：釩酸鉀(一般試藥)(含V化合物)
Cr：氧化Cr(VI)(一般試藥)(含Cr化合物)
Cu：氧化銅(II)(一般試藥)(含Cu化合物)
[表2]
<熱壓步驟>
表面處理層之形成步驟後對各試驗編號的鋼板以爐加熱之加熱方式進行熱壓加熱，實施熱壓。在爐加熱係將爐內氣體環境定為910℃且空燃比定為1.1，並在鋼板溫度到達900℃後快速地從爐內取出。
熱壓加熱後進行冷卻直到鋼板溫度成為700℃。冷卻後，利用具備水冷套之平板模具夾取鋼板而製造出熱壓鋼材(鋼板)。在熱壓時冷卻速度較慢的部分也是以50℃/秒以上之冷卻速度的方式冷卻至麻田散鐵變態開始點之360℃左右，予以淬火。
<評估方法>
〔氧化鋅量之定量〕
利用化學分析之氧化鋅層的定量方法可任擇採用下述方法：以5%碘-甲醇溶液溶解鍍敷層並將所產生之殘渣溶解於鹽酸予以定量之方法、或是以重鉻酸銨水溶液溶解表面之氧化膜而予以定量之方法。在此，有溶解之溶液可使用各溶液之空白試樣，以ICP法等發光分析等予以定量。
此外，利用物理分析之氧化鋅層的定量方法可以X射線繞射求出源自ZnO的尖峰強度。此時，只要預先使用已知氧化鋅量的標準試樣製作表示氧化鋅量與源自ZnO的尖峰強度之關係的檢量線，便可藉由源自特定繞射面的尖峰強度定量已生成之氧化鋅量。
在本實施例中係利用使用Co管球之X射線繞射裝置，從ZnO之[100]面的繞射尖峰強度，按照以下式(1)算出生成氧化鋅量。
生成氧化鋅量=XZ-XZ0…式(1)
在此，上述式(1)中XZ係熱壓加熱後之ZnO[100]面的繞射尖峰強度，XZ0係熱壓加熱前之ZnO[100]面的繞射尖峰強度。將所得生成氧化鋅量與作為比較例所實施之 無表面處理層的GA及鋅系鍍敷鋼板作比較，幾乎無生成氧化鋅量者視為A，有少數生成氧化鋅量者視為B，有多數生成氧化鋅量者視為C。
〔耐蝕性試驗〕
以聚酯膠帶遮罩評估試驗片之端面及背面，並將下述循環條件的循環性腐蝕試驗實施90循環。
○循環條件
以鹽水噴霧(SST、5%NaCl、35℃氣體環境)2hr→乾燥(60℃)2hr→濕潤(50℃、98%RH)4hr為1循環進行實施。
其後，除去聚酯膠帶後以檸檬酸銨溶液溶解‧除去腐蝕生成物。將評估面劃分成8等分，並在各等分以單點測微器(pin point micrometer)測定腐蝕部之板厚，再從其與施有遮罩之無缺陷區(area free from defect)之差求出各等分中因腐蝕而減少的板厚。所得各等分之板厚減少值中算出前三項的平均值，作為各試驗片之腐蝕深度。
表3中之「耐蝕性」欄的「G」表示產生超過0.5mm之腐蝕深度。「F」表示產生0.4mm~小於0.5mm之腐蝕深度。「E」表示產生0.3mm~小於0.4mm之腐蝕深度。「D」表示產生0.2mm~小於0.3mm之腐蝕深度。「C」表示產生0.15mm~小於0.2mm之腐蝕深度。「B」表示產生0.10mm~小於0.15mm之腐蝕深度。「A」表示產生0.10mm以下之腐蝕深度。在此耐蝕性試驗中，「F」、「E」、「D」、「C」、「B」或「A」之情況係判斷為耐蝕性優異。
〔耐凝著性試驗〕
作為對於模具之凝著性的定量化指標，係使用上述平板模具，測定藉由熱壓所製得之鋼板表面的皮膜密著性而進行定量化。
具體上係針對所得鋼板表面，利用NICHIBAN製聚酯膠帶進行熱壓成形後之表層皮膜的剝離測試。此時係將剝離膠帶之剝離量當作基材的穿透程度，使用Minolta製色彩色差計CR-300以明度指數進行評估。評估方法係將明度指數L*之N=3平均值(L*ave)為55以下之情況視為「C」，表示表層皮膜之剝離大，對於模具的耐凝著性很差。此外，L*ave超過55且在60以下之情況視為「B」，L*ave超過60之情況視為「A」。關於「A」、「B」係判斷為表層皮膜之剝離有受抑制，對於模具之耐凝著性優異。
[表4]
如從上述表3明示可知，本發明之熔融鋅系鍍敷鋼板不僅可抑制熱壓後之表層上的鋅氧化物之過度生成，顯示優異的耐蝕性，亦具有優異的耐模具凝著性。
以上係就本發明的適當實施形態詳細說明，惟本發明不受該等示例限定。顯而易見地，只要係具有本發明所屬技術領域之通識人士，皆可在申請專利範圍中所記載之技術思想範疇內思及各種變更例或修正例並知悉該等亦理當歸屬本發明之技術範圍。

Claims (12)

  1. 一種熔融鋅系鍍敷鋼板，具備：作為基材之基底鋼板；設置在前述基底鋼板上之熔融鋅系鍍敷層；及表面處理層，係形成於前述熔融鋅系鍍敷層之至少單面上；前述表面處理層以金屬換算計含有每單面0.1g/m2以上且1.2g/m2以下之粒狀氧化物，該粒狀氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋅之標準生成自由能(△G0 Zn)且大於氧化鋁之標準生成自由能(△G0 Al)，並且，前述粒狀氧化物之粒徑為3nm以上且100nm以下。
  2. 如請求項1之熔融鋅系鍍敷鋼板，其中前述表面處理層以每單面含量計，在以下所示範圍內更含有含磷化合物、含釩化合物、含銅化合物、含鋁化合物或含鉻化合物之至少任一者；含磷化合物：以P換算計為0.0g/m2以上且0.01g/m2以下；含釩化合物：以V換算計為0.0g/m2以上且0.01g/m2以下；含銅化合物：以Cu換算計為0.0g/m2以上且0.02g/m2以下； 含鋁化合物：以Al換算計為0.0g/m2以上且0.005g/m2以下；含鉻化合物：以Cr換算計為0.0g/m2以上且0.01g/m2以下。
  3. 如請求項1或2之熔融鋅系鍍敷鋼板，其中前述基底鋼板具有下述化學組成：以質量%計，含有：C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、Ti：0~0.1%、Cr：0~0.5%、Nb：0~0.1%、Ni：0~1.0%、Mo：0~0.5%，且剩餘部分由Fe及雜質所構成。
  4. 如請求項1或2之熔融鋅系鍍敷鋼板，其中前述基底鋼板具有下述化學組成：以質量%計，含有： C：0.05~0.4%、Si：0.5%以下、Mn：0.5~2.5%、P：0.03%以下、S：0.01%以下、sol.Al：0.1%以下、N：0.01%以下、B：0~0.005%、Ti：0~0.1%、Cr：大於0%且0.5%以下、Nb：0~0.1%、Ni：0~1.0%、Mo：0~0.5%，且剩餘部分由Fe及雜質所構成，並且，滿足Mn+Cr：0.5~3.0%之關係。
  5. 如請求項1至4中任一項之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物為金屬氧化物。
  6. 如請求項1至5中任一項之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物為鈦氧化物或矽氧化物。
  7. 如請求項1至6中任一項之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物之粒徑為5nm以上且30nm以下。
  8. 如請求項1至7中任一項之熔融鋅系鍍敷鋼板，其中前述粒狀氧化物之含量以金屬換算計為每單面0.2g/m2以上且0.8g/m2以下。
  9. 如請求項1至8中任一項之熔融鋅系鍍敷鋼板，其中前述表面處理層以金屬換算計更含有每單面0.05g/m2以上且0.35g/m2以下之鹼土類金屬氧化物，該鹼土類金屬氧化物在900~1300K之溫度區內於同一溫度下的氧化物標準生成自由能(△G0)係小於氧化鋁之標準生成自由能(△G0 Al)。
  10. 如請求項9之熔融鋅系鍍敷鋼板，其中前述鹼土類金屬氧化物為鈣氧化物或鎂氧化物。
  11. 如請求項9或10之熔融鋅系鍍敷鋼板，其中前述鹼土類金屬氧化物之含量以金屬換算計為每單面0.05g/m2以上且0.2g/m2以下。
  12. 如請求項1至11中任一項之熔融鋅系鍍敷鋼板，其係熱壓用熔融鋅系鍍敷鋼板。
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