TWI551435B - 鋼材及其製造方法 - Google Patents

鋼材及其製造方法 Download PDF

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Publication number
TWI551435B
TWI551435B TW103115972A TW103115972A TWI551435B TW I551435 B TWI551435 B TW I551435B TW 103115972 A TW103115972 A TW 103115972A TW 103115972 A TW103115972 A TW 103115972A TW I551435 B TWI551435 B TW I551435B
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Taiwan
Prior art keywords
plating layer
zinc
steel material
material according
alloy
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TW103115972A
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English (en)
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TW201542350A (zh
Inventor
林招松
陳宗榮
吳駿泓
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國立臺灣大學
中國鋼鐵股份有限公司
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Priority to TW103115972A priority Critical patent/TWI551435B/zh
Priority to US14/703,895 priority patent/US9486984B2/en
Publication of TW201542350A publication Critical patent/TW201542350A/zh
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Publication of TWI551435B publication Critical patent/TWI551435B/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • 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
    • 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
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/04—Decarburising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • 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
    • 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
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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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
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
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    • 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
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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
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    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • 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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Description

鋼材及其製造方法
本發明是有關於一種鋼材及其製造方法，且特別是有關於一種表面上有鋅合金鍍層的鋼材及其製造方法。
鋼鐵材料是當前最常被使用的工業材料之一。為了改善鋼鐵工件的耐腐蝕性，一種已知方法是在鐵基材的表面上形成一層鍍層，例如以電鍍法或熱浸鍍法形成一層金屬鋅。金屬鋅鍍層的防蝕原理有二，第一是透過包覆鐵基材，隔絕它和環境的接觸，藉此防蝕；第二是透過所謂的「犧牲陽極保護法」來達到防蝕效果。具體而言，即是將還原性較強的金屬作為保護電極，與被保護的金屬相連，以構成原電池(primary cell)。還原性較強的金屬作為陽極，將發生氧化反應而消耗，被保護的金屬作為陰極，從而得以避免腐蝕。
然而，如果表面有金屬鋅鍍層的鋼材後續要接受熱沖壓處理，熱沖壓之預熱步驟的高溫會讓金屬鋅大量氧化，使能提供保護效果的有效的金屬鋅含量減少；同時，該高溫也可能讓鋅熔化，使液態鋅滲入鐵的晶界中，在沖壓時造成沿晶破壞，這就是所謂的液態金屬誘發脆化現象(liquid metal induced embrittlement,LMIE)。基於此，對於鋼鐵材料的表面鍍層，仍有進一步研究的必要。
本發明提供一種鋼材及其製造方法，該鋼材的表面配置有特殊鍍層，能提供犧牲陽極保護的效果；此外，該鍍層的熱穩定性高，可防止LMIE現象的發生。
本發明的鋼材包括鐵基材、配置在該鐵基材上的第一鍍層以及配置在該第一鍍層上的第二鍍層，其中該第一鍍層包括鋅合金，而該第二鍍層主要由鉻和碳所組成。
在一種實施方式中，該鋅合金為鋅鎳合金、鋅鈷合金或其組合。
在一種實施方式中，該鋅合金為鋅鎳合金，且其中鎳的比例介於16到30原子%之間。
在一種實施方式中，該鋅合金為鋅鎳合金，且其中鎳的比例約為20原子%。
在一種實施方式中，該鋅合金的還原電位比該鐵基材的還原電位低至少100mV。
在一種實施方式中，該鋅合金的熔點高於該鐵基材的沃斯田鐵化溫度。
在一種實施方式中，該第一鍍層和該第二鍍層的厚度分別為2μm到100μm和0.1μm到10μm，較佳是分別為2μm到10μm和0.5μm到5μm。
在一種實施方式中，該第二鍍層中碳的含量大於10原子%。
本發明的鋼材的製造方法包括在鐵基材的表面依序形成第一鍍層和第二鍍層，其中該第一鍍層包括鋅合金，而該第二鍍層主要由鉻和碳 所組成。
在一種實施方式中，前述製造方法更包括在該第二鍍層上形成表層，其中該表層包括ZnCr2O4。
在一種實施方式中，該表層更包括ZnO和Cr2O3。
在一種實施方式中，前述製造方法更包括進行加熱步驟，以移除該第二鍍層中的碳。
在一種實施方式中，前述製造方法更包括進行加熱步驟，以氧化該第二鍍層表面的鉻並移除該第二鍍層中的碳。
在一種實施方式中，該加熱步驟同時使該第一鍍層中的鋅擴散至該第二鍍層的表面。
在一種實施方式中，該加熱步驟同時使擴散至該第二鍍層的該表面的鋅被氧化。
基於上述，本發明提供了一種鋼材及其製造方法，特徵是在鐵基材上形成由含鋅合金的第一鍍層和含鉻和碳的第二鍍層組成的複合鍍層。具有複合鍍層的鐵基材可以減緩鋅合金在熱處理期間的氧化，讓第一鍍層在高溫處理後仍舊保有對鐵基材的保護能力。
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例作詳細說明如下。
100‧‧‧鐵基材
102‧‧‧第一鍍層
104‧‧‧第二鍍層
104a‧‧‧表面
106‧‧‧表層
114‧‧‧空缺
圖1到圖3是根據本發明的第一實施方式所繪示的鋼材的製造流程。
圖4是實施例1的鋼材樣本的掃描式電子顯微鏡(SEM)照片。
圖5、圖6和圖7分別呈現實施例1到實施例3之樣本的XPS鍵結能分析圖譜。
圖8、圖9、圖10和圖11分別顯示比較例1和實施例1到3的樣本的表面元素分析結果。
圖12和圖13分別呈現實施例1到3的樣本在熱處理前和熱處理後的X光繞射圖譜。
圖14呈現三種不同的鋼材的高溫拉伸試驗結果。
以下將參照隨附圖式更全面地描述本發明的示範性實施方式；然而，本發明可按不同的形式體現，且不侷限於本文闡述的實施方式。為了進行清楚的說明，圖式所示的結構，尺寸可能有所誇大；亦即，圖式不一定是按比例繪製的。也應理解的是，當某一特徵被稱為在另一特徵或基板「上」時，可能是直接位於另一特徵或基板上，也可能存在中介層；對其他空間相對用語(如「下方」、「左側」、「旁」等)和描述特徵間關係的用語(如「連接」、「覆蓋」等)也應作如此理解。
在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，記載了某一特定數值範圍，等同於揭露了該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。例如，記載「尺寸為10~100μm」的範圍，就等同於揭露了「尺寸為20μm~50μm」的範圍，無論說明書中是否列舉其他數值。
本發明的第一實施方式涉及一種鋼材的製造方法，以下將參照圖 1到圖3說明之。
參照圖1，首先，提供鐵基材100。鐵基材100可以是一般的鋼鐵材料，例如熱軋鋼板(hot-rolled steel sheet)或冷軋鋼板(cold-rolled steel sheet)。其組成除了鐵以外，還可能含有其他雜質，例如含量為0.15到0.5質量%的碳、含量為0.05到2.0質量%的矽、含量為0.5到3質量%的錳、含量為0.1質量%以下的磷、含量為0.05質量%以下的硫、含量為0.1質量%以下的鋁或含量為0.1質量%以下的氮。鐵基材100的主要成份例如為肥粒鐵(ferrite)或肥粒鐵和波來鐵(pearlite)。
參照圖2，接著，在鐵基材100的表面依序形成第一鍍層102和第二鍍層104。第一鍍層102含有鋅合金，其例如是鋅鎳合金、鋅鈷合金或其組合。由於第一鍍層102和鐵基材100直接接觸，且其還原電位又比鐵基材100更低，因此可以作為「犧牲陽極」，防止鐵基材100的腐蝕。就此而言，該鋅合金的還原電位較佳是比鐵基材100的還原電位低至少100mV，較佳是低至少200mV。再者，和習知的金屬鋅鍍層相比較，由於第一鍍層102的材料是鋅合金，其熔點得以大幅提高，在熱沖壓製程期間不易熔化，因此可避免LMIE現象的產生。就此而言，該鋅合金的熔點較佳是高於鐵基材100的沃斯田鐵化溫度(隨材料的不同而變，通常在750℃到950℃之間)。
進而言之，以鋅合金為鋅鎳合金為例，若鎳的含量愈高，則鋅鎳合金的熔點愈高，熱穩定性愈佳；但與此同時，鋅的擴散能力也受到限制(關於鋅的擴散的影響，請參照0032段以下的說明)，且鋅鎳合金的還原電位的絕對值下降。將這些因素納入考量，在鋅鎳合金中，鎳的比例以介於16到30原子%之間較佳，以約20原子%(亦即，鋅和鎳的比例接近介金屬化合物Ni5Zn21)更佳。需要注意的是，在本文中使用「約」來對數值 加以修飾時，申請人希望涵蓋的，是所屬技術領域中具有通常知識者所理解的必然存在的誤差範圍。如果沒有特別限定，使用「約」就表示容許至少5%的誤差範圍。
至於第一鍍層102的形成方法，並沒有特別限制，只要是本技術領域中習知的可以形成鋅合金的方法均可使用，例如物理氣相沈積製程、化學氣相沈積製程或電鍍製程。此外，第一鍍層102的厚度可以介於2μm到100μm之間。
第二鍍層104主要由鉻和碳所組成，因此亦可將第二鍍層104稱之為鉻碳層(chromium-carbon layer)。具體而言，第二鍍層104的主成分是鉻，其所佔比例應大於50原子%，例如70原子%至75原子%。鉻可形成晶體結構，至於碳，則是作為雜質存在於鉻晶體中。在「鐵基材100/第一鍍層102/第二鍍層104」之整體經歷熱處理時，第二鍍層104的存在有助於減緩第一鍍層102的鋅合金的氧化，讓第一鍍層102可以在熱處理之後繼續發揮它「犧牲陽極」的作用。再者，在熱處理期間，第二鍍層104的元素還可以和第一鍍層102的元素產生交互作用，以進一步保護第一鍍層102，其原理在下文將參照圖3說明之。
第二鍍層104的形成方法沒有特別限制，舉例來說，可透過電鍍製程來形成；此時，第二鍍層104中的碳可能來自於電鍍液中的有機添加劑，如pH調節劑等，其含量以大於10原子%較佳(原因請參見0032段)。此外，第二鍍層104的厚度可為1μm到10μm。
參照圖3，接著，在第二鍍層104上形成表層106。詳言之，表層106是透過對圖2所示的結構進行熱處理，使第一鍍層102和第二鍍層104中的元素擴散、氧化而形成的。此處所謂「熱處理」，可以指鋼鐵材料在熱沖壓製程期間的預熱處理，亦即，熱處理的溫度大約等於鐵基材100 的沃斯田鐵化溫度，這通常介於750℃到950℃之間。在此熱處理期間，第二鍍層104中的碳首先會被氧化成氣體而逸散，從而在第二鍍層104中留下一些空缺(vacancies)114。而第一鍍層中的鋅在高溫環境下會開始往外擴散，空缺114的存在對於鋅擴散到第二鍍層104的表面104a有所助益。由於空缺114的數量由第二鍍層104中碳的含量決定，因此，要讓足夠量的鋅擴散到表面104a，碳的含量不可太低，例如，可大於或等於10原子%。
擴散至表面104a處的鋅可能氧化而形成氧化鋅(ZnO)；同時，第二鍍層104所含的鉻亦可能在高溫環境下氧化，形成氧化鉻(Cr2O3)。ZnO和Cr2O3可以續而在高溫環境下反應，形成具有尖晶石(spinel)結構的ZnCr2O4。因此，總括來說，表層106的組成成分包括ZnO、Cr2O3和ZnCr2O4，且這些物種的含量分布可能有一定趨勢，例如，ZnO的量由外而內遞減，而Cr2O3的量由外而內遞增。
值得注意的是，在ZnCr2O4的尖晶石結構中，氧離子構成面心立方堆積(FCC)的晶格結構，而鋅離子和鉻離子分別佔據此晶格中的部分四面體位置和八面體位置，其結果是構成一種非常緻密的結構。這可以在相當程度上阻絕環境中的氧氣通過表層106，因此可以進一步避免第一鍍層102所含的鋅被氧化。
綜上所述，本發明提供了一種鋼材的製造方法，包括在鐵基材上形成由含鋅合金的第一鍍層和含鉻和碳的第二鍍層組成的複合鍍層(請注意，這種鐵基材和複合鍍層的組合亦屬本發明的具體實施方式之一，亦即，本發明不僅涉及鋼材的製造方法，也涉及一種具有特殊鍍層的鋼材)。具有複合鍍層的鐵基材在經過熱沖壓處理時，在其表面會形成一層含有ZnCr2O4的表層，ZnCr2O4的結構緻密，可以減緩鋅合金的氧化，讓第一鍍層在高溫處理後仍舊保有對鐵基材的保護能力。
〈實施例〉
下文將列舉實施例以更具體地描述本發明。雖然描述了以下實驗，但是在不逾越本發明範疇之前提下，可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應根據下文所述的實驗對本發明作出限制性的解釋。
鋼材的製備-
實施例1：在一鋼板上以電鍍法形成一層鋅鎳合金(鎳的含量約16原子%)，接著，同樣以電鍍法形成一層鉻碳層(碳含量約為12原子%)，以完成實施例1的鋼材樣本。其中，該鋼板是一般商業化低碳鋼，組成成分除了鐵以外，還包括0.04重量%的C、0.002重量%的Si、0.18重量%的Mn、0.014重量%的P和0.015重量%的S。鋼板的電鍍面積約為6.5cm×2cm。鋅鎳合金的電鍍是採用定電流密度(4A/dm2)電鍍的方式，電解液為0.55M的ZnCl2溶液、0.45M的NiCl2 6H2O溶液、4.49M的NH4Cl溶液和0.32M的H3BO3溶液的混合物，其pH值為4.06。電鍍溫度為35℃。該層鋅鎳合金的厚度約為3-4μm。鉻碳層的電鍍是採用脈衝電流電鍍(電流密度20A/dm2，持續9毫秒，間隔1毫秒)的方式，電解液為0.39M的CrCl3 6H2O溶液、3.72M的NH4COOH溶液、0.81M的KCl溶液、0.084M的KBr溶液和0.01M的C12H25OSO3Na溶液的混合物，其pH值為4.48。電鍍溫度為35℃。該層鉻碳層的厚度約為1μm。圖4顯示實施例1的樣本剖面的SEM照片。
實施例2和3：以類似實施例1的方式形成實施例2和3的鋼材樣本，其區別在於，在實施例2和3中，鋅鎳合金的鎳含量分別為約19原子%和約30原子%(分別是在45℃和55℃的電鍍溫度下製成的)。
比較例1：以類似實施例1的方式形成比較例1的鋼材樣本，其區別 在於，在比較例1中，鉻碳層的碳含量是5原子%。
對比較例1和實施例1到3的樣本分別進行熱處理(溫度850℃，時間5分鐘)，並透過XPS光電子能譜儀(X-ray Photoelectron Spectroscopy)別對這四種樣本進行表面元素分析，所得的結果呈現在圖5到圖11。
圖5、圖6和圖7分別呈現實施例1到實施例3之樣本的XPS鍵結能分析圖譜。其中，左上圖顯示的是三維圖形；右上、左下、右下依序顯示左上圖的第2、第5和第8條曲線，其蝕刻時間由短而長，意味著所示意的位置由靠近表面處逐漸進入樣本內部。參照圖5可知，在樣本的表面處偵測不到電鍍Cr層的訊號；隨著深度逐漸加深，電鍍Cr層的訊號開始出現，而ZnCr2O4的訊號則逐漸變弱(含量逐漸變少)。
根據如圖5到圖7的此類分析，可繪出各個樣本中各元素隨著深度而變的分布曲線，所得的結果呈現在圖8到圖11。
比較圖8和圖9可知，在鉻碳層的碳含量較低(5原子%)時，其表面處的Zn量也非常低，因此，可能不足以在表面形成ZnCr2O4的尖晶石結構。相對地，在鉻碳層的碳含量較高(12原子%)時，Zn的量在接近樣本表面處明顯提高，表示在此情況下Zn較容易擴散到樣本表面，有助於ZnCr2O4的形成。此外，根據實驗結果，發明人還發現，實施例1的樣本表面經熱處理後會形成較緻密的氧化物，而比較例1的樣本表面則是生成島狀不緻密的氧化物。其原因可能是碳空缺的減少阻礙了鋅在鉻碳層中的擴散，導致樣品表面沒有足夠的氧化鋅，所以不能形成ZnCr2O4尖晶石結構。
再者，比較圖9、圖10和圖11可以看出，隨著鋅鎳合金鍍層中鎳含量提高(從16原子%逐步提高到30原子%)，鍍層的熔點跟著上升，使得擴散到表面的鋅含量逐漸降低，這可能會使形成的尖晶石結構隨之變薄。
發明人也另以X光分析技術，證實了實施例1到3的樣本在經歷熱處理後，確實有ZnCr2O4的生成。請參照圖12和圖13，其分別顯示實施例1到3的樣本在熱處理前和熱處理後的X光繞射圖譜。從這些圖式中可以看出，所有的實施例樣本在熱處理之後都出現了ZnO和ZnCr2O4的繞射峰。
最後，圖14呈現了三種不同高溫拉伸試驗(900℃，拉伸速度0.13S-1)的結果，其分別是對沒有鍍層的鋼材(商業化低碳鋼，成分與實施例1的鋼板相同)、電鍍鋅的鋼材和電鍍鋅鎳合金(16at% Ni)的鋼材所進行的。 從圖14可以看出，對鋼材施予鍍層時，鋼材的強度無可避免地會稍微下降，但是，由於鋅鎳合金的熔點(熱穩定性)遠高於金屬鋅，不易發生LMIE現象，因此具有鋅鎳合金鍍層的鋼材，其機械性質遠優於具有金屬鋅鍍層的鋼材。
雖然已以實施例對本發明作說明如上，然而，其並非用以限定本發明。任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍的前提內，當可作些許的更動與潤飾。故本申請案的保護範圍當以後附的申請專利範圍所界定者為準。
100‧‧‧鐵基材
102‧‧‧第一鍍層
104‧‧‧第二鍍層

Claims (15)

  1. 一種鋼材，包括鐵基材、配置在該鐵基材上的第一鍍層以及配置在該第一鍍層上的第二鍍層，其中該第一鍍層包括鋅合金，而該第二鍍層主要由鉻和碳所組成。
  2. 如申請專利範圍第1項所述的鋼材，其中該鋅合金為鋅鎳合金、鋅鈷合金或其組合。
  3. 如申請專利範圍第1項所述的鋼材，其中該鋅合金為鋅鎳合金，且其中鎳的比例介於16到30原子%之間。
  4. 如申請專利範圍第1項所述的鋼材，其中該鋅合金為鋅鎳合金，且其中鎳的比例約為20原子%。
  5. 如申請專利範圍第1項所述的鋼材，其中該鋅合金的還原電位比該鐵基材的還原電位低至少100mV。
  6. 如申請專利範圍第1項所述的鋼材，其中該鋅合金的熔點高於該鐵基材的沃斯田鐵化溫度。
  7. 如申請專利範圍第1項所述的鋼材，其中該第一鍍層和該第二鍍層的厚度分別為2μm到100μm和0.1μm到10μm。
  8. 如申請專利範圍第1項所述的鋼材，其中該第二鍍層中碳的含量大於10原子%。
  9. 一種鋼材的製造方法，包括在鐵基材的表面依序形成第一鍍層和第二鍍層，其中該第一鍍層包括鋅合金，而該第二鍍層主要由鉻和碳所組成。
  10. 如申請專利範圍第9項所述的鋼材的製造方法，更包括在該第二鍍層上形成表層，其中該表層包括ZnCr2O4。
  11. 如申請專利範圍第10項所述的鋼材的製造方法，其中該表層更包括ZnO和Cr2O3。
  12. 如申請專利範圍第9項所述的鋼材的製造方法，更包括進行加熱步驟，以移除該第二鍍層中的碳。
  13. 如申請專利範圍第9項所述的鋼材的製造方法，更包括進行加熱步驟，以氧化該第二鍍層表面的鉻並移除該第二鍍層中的碳。
  14. 如申請專利範圍第13項所述的鋼材的製造方法，其中該加熱步驟同時使該第一鍍層中的鋅擴散至該第二鍍層的表面。
  15. 如申請專利範圍第14項所述的鋼材的製造方法，其中該加熱步驟同時使擴散至該第二鍍層的該表面的鋅被氧化。
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