CN105358719B - 冷轧钢板、制造方法和车辆 - Google Patents

冷轧钢板、制造方法和车辆 Download PDF

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Publication number
CN105358719B
CN105358719B CN201480038015.5A CN201480038015A CN105358719B CN 105358719 B CN105358719 B CN 105358719B CN 201480038015 A CN201480038015 A CN 201480038015A CN 105358719 B CN105358719 B CN 105358719B
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cold
steel
steel sheet
rolled steel
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CN105358719A (zh
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弗兰科·迪奥弗拉特
让-米歇尔·马泰格纳
约纳什·施陶特
阿斯特丽德·佩拉德
伊恩·阿尔贝托·苏亚索-罗德里格斯
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ArcelorMittal Investigacion y Desarrollo SL
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    • 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
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • 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
    • 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
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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    • C—CHEMISTRY; METALLURGY
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    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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Abstract

本发明涉及一种经冷轧的并经热浸镀的钢板，该钢板呈现出：大于1000‑50xAl MPa的拉伸强度、大于15％的均匀延伸率以及低的密度。该钢包含：以重量百分比计，0.1％≤C≤0.5％、3.5％≤Mn≤10.0％、0％≤Al≤9.0％、Si≤5.0％、Ti≤0.2％、V≤0.2％、Nb≤0.2％、S≤0.004％、P≤0.025％、0.5％≤Si+Al≤9.0％、B≤0.0035、Cr≤1％。余量为Fe和杂质，并且显微组织包含：25％至90％的铁素体、10％至50％的奥氏体、低于5％的卡帕析出物以及低于25％的马氏体。根据本发明的钢利用完全氧化而表现出被涂覆的能力。

Description

冷轧钢板、制造方法和车辆
本发明涉及同时呈现出高机械性能、优良的成形性以及优良的接收涂层的能力的冷轧钢板。
具体地，所述钢板需要：大于或等于1000-50xAl MPa的拉伸强度TS、大于或等于15％的均匀延伸率UEI、大于或等于20％的扩孔率HE、以及允许润湿和涂层粘附的反应性表面。
此外，一些实施方案中包含大量硅或铝的所述钢板可以具有低的密度，并且与所谓的先进高强度钢(例如双相钢、多相钢、贝氏体钢或TRIP(相变诱发塑性)概念钢)相比，所述钢板轻多于10％。
具体地，在汽车工业中，不断需要轻量化同时安全性增加的车辆。因此，已经提出数个系列的钢，例如上述提供各种强度和成形性水平的钢。
首先，已经提出了具有微合金元素的钢，所述微合金元素同时通过析出以及通过晶粒尺寸的细化来实现硬化。在上述先进高强度钢之后，开发了这样的钢。
为了获得更高的拉伸强度水平，已经开发了表现出将多种性能(拉伸强度/成形性)高度有利结合的TRIP性质的钢。这些性能与这样的钢的结构相关联，所述钢由含有贝氏体和残余奥氏体的铁素体基体组成。通过添加硅或铝来使残余奥氏体稳定，这些元素阻碍了奥氏体中及贝氏体中碳化物的析出。残余奥氏体的存在给予未变形板以高延展性。
为了获得更高的拉伸强度，也就是说为了获得大于800-1000MPa的拉伸强度水平，已经开发了具有主要为贝氏体组织的多相钢。然而，对于下一代汽车部件而言，成形性和扩孔性能是不足的。
国际申请WO2009/142362公开了一种冷轧钢板和一种热浸镀锌钢板，该申请通过将用于提高残余奥氏体的稳定性以及耐延迟断裂性的合适量的Al添加至可以增加残余奥氏体的量的最佳组成中以具有在下述方面的改进：耐延迟断裂性、980MPa或更大的拉伸强度以及28％或更大的延伸率。在该现有技术的一个或更多个方面中，提供了一种高强度冷轧钢板以及一种镀锌钢板，该高强度冷轧钢板和该镀锌钢板中的每一个均由以下组成：0.05至0.3重量百分比的C、0.3至1.6重量百分比的Si、4.0至7.0重量百分比的Mn、0.5至2.0重量百分比的Al、0.01至0.1重量百分比的Cr、0.02至0.1重量百分比的Ni以及0.005至0.03重量百分比的Ti、5至30ppm的B、0.01至0.03重量百分比的Sb、0.008重量百分比或更少的S、余量为Fe和杂质。然而，这样的钢由于高含量的合金元素而难以涂覆。
国际申请WO2012/147898旨在提供一种具有优异扩孔率以及稳定的材料性能的高强度钢及其制造方法，该高强度钢板在低C钢组成中具有至少780MPa的TS以及至少22,000MPa％的TSxEL。该高强度钢具有优良的成形性和材料性能的稳定性，该高强度钢具有包含以下成分组成：以质量％计，0.03％至0.25％的C、0.4％至2.5％的Si、3.5％至10.0％的Mn、0.1％或更少的P、0.01％或更少的S、0.01％至2.5％的Al、0.008％或更少的N以及至少1.0％的Si+Al，余量为Fe和不可避免的杂质。以面积比计，该钢组织具有30％至80％的铁素体、0％至17％的马氏体，按体积比，该钢组织具有8％或更多的残余奥氏体，并且残余奥氏体的平均晶粒直径为2μm或更小。然而，这样的钢由于高含量的合金元素而难以涂覆。
最后，申请EP2383353公开了一种延伸率为断裂A80的最小4％以及拉伸强度为900MPa至1500MPa的钢。该钢包含铁、不可避免的杂质以及碳(最高0.5％)、锰(4％至12％)、硅(最高1％)、铝(最高3％)、铬(0.1％至4％)、铜(最高2％)、镍(最高2％)、氮(最高0.05％)、磷(最高0.05％)以及硫(最高0.01％)，并且可选地至多0.5％的包含钒、铌或钛的一种或更多种元素。由该钢制成的扁平轧钢产品包含30％至100％的马氏体、回火马氏体或贝氏体以及残余量的奥氏体。然而，这样的钢将表现出低的延展性水平，而导致获得的钢板的差的成形性。
本发明旨在提供一种冷轧钢板，该冷轧钢板同时表现出：
-大于或等于1000-50xAl MPa的拉伸强度TS，
-大于或等于15％的均匀延伸率UEI，
-大于或等于20％的扩孔率HE，和
-允许润湿和涂层粘附的反应性表面。
作为第一目的，本发明涉及一种冷轧钢板，其以重量百分比计包含：
0.1％≤C≤0.5％
3.5％≤Mn≤10.0％
Al≤9.0％
Si≤5.0％
0.5％≤Si+Al≤9.0％
Ti≤0.2％
V≤0.2％
Nb≤0.2％
B≤0.0035
Cr≤1％
S≤0.004％
P≤0.025％
组成的余量为铁以及由熔炼造成的不可避免的杂质，并且显微组织包含：10％至50％的奥氏体、25％至90％的铁素体、小于5％的卡帕析出物以及小于25％的马氏体，所述板从顶表面呈现出连续的下述层：
-纯金属铁的顶层，其厚度为50nm至300nm，以及
-由金属铁制成的第一下层，其还包含选自Mn、Si、Al、Cr和B的氧化物的一种或更多种析出物，该第一下层的厚度为1μm至8μm。
本发明还可以包括其他附加的特征，所述特征单独存在或彼此结合：
-根据本发明的冷轧钢板还包括第二下层，其位于第一下层之下，由铁素体构成，第二下层的厚度为10μm至50μm。
在一个优选的实施方案中，本发明包括组成如下的冷轧钢板：
-组成的锰含量为5.0％至9.0％的冷轧钢板，
-组成的碳含量为0.1％至0.3％，更优选的范围为0.15％至0.25％的冷轧钢板，
-组成的铝含量为1.5％至9％，更优选的范围为5％至8％的冷轧钢板，
-组成的硅含量等于或小于1.5％，更优选硅含量等于或小于0.3％的冷轧钢板。
在另一优选的实施方案中，根据本发明的钢包括：
-显微组织包含15％至40％的奥氏体，更优选的范围为20％至40％的奥氏体，并且最优选的范围为25％至40％的奥氏体的冷轧钢板，
-显微组织包含50％至85％的铁素体的冷轧钢板，
-显微组织包含小于15％的马氏体的冷轧钢板，该马氏体可能是经回火的，
-显微组织不含卡帕析出物的冷轧钢板。
理想地，根据本发明的冷轧钢板表现出：以MPa计大于或等于1000-50x％Al的拉伸强度TS，大于或等于15％的均匀延伸率UEI和大于或等于20％的扩孔率HE。
本发明的另一目的是一种金属涂覆钢板，其通过对根据本发明的冷轧钢板进行涂覆而获得，所述涂覆通过选自热浸镀、电沉积和真空涂覆中的工艺来完成，可能随后进行热处理。在优选的实施方案中，该金属涂覆钢板是经镀层扩散退火处理的。
可以通过任意适当的方法来制造根据本发明的经冷轧并可能经涂覆的钢板。优选的是，这样的方法与通常的连续退火作业线兼容并且对工艺参数的变化敏感度低。
本发明的另一目的在于生产冷轧钢板的工艺，该工艺包括下述步骤：
供给组成为根据本发明的热轧带钢或薄板坯，并且去除所述热轧带钢或薄板坯的氧化皮。
然后以30％至75％的冷轧率(cold rolling ratio)对热轧带钢或薄板坯进行冷轧，以获得冷轧钢板。
然后在30秒至700秒期间以至少等于1℃/s的加热速率H速率使钢板经历加热直至位于Tmin＝721-36*C-20Mn+37*Al+2*Si(以℃计)与Tmax＝690+145*C-6.7*Mn+46*Al+9*Si(以℃计)之间的退火温度T退火，随后在所述温度下进行均热，所述加热从550℃升至T退火并且所述均热的至少第一部分在氧化气氛中进行，以生产出厚度为100nm至600nm的铁氧化物顶层，然后对所述铁氧化物层进行完全还原。
这样的还原发生在均热的第二部分期间，在包含2％至35％的H2的并且露点低于-10℃的还原气氛中，以对所述铁氧化物层进行完全还原，还以大于5℃/s且小于70℃/s的冷却速率V冷却2使钢板冷却至室温。
可选地，均热的第二部分发生在露点低于-30℃的气氛中。
在另一实施方案中，以V冷却2使钢板冷却到350℃至550℃之间的温度TOA，并且保持在TOA下10秒至300秒的时间，并且然后以5℃/s至70℃/s的冷却速率V冷却3使钢板进一步冷却到室温。
在另一实施方案中，所述还原还可以发生在以大于5℃/s且小于70℃/s的冷却速率V冷却2使所述钢板冷却到室温之后，然后所述还原通过化学酸洗完成。
理想地，通过选自热浸镀、电沉积和真空涂覆中的工艺完成涂覆，可能随后进行热处理。
优选地，通过镀层扩散退火热处理完成金属涂覆。
存在不同的方法来获得热轧带钢，所述方法中之一是包括下述步骤的工艺：
-铸造组成为根据本发明的钢，以获得板坯，
-在1100℃至1300℃的温度T再加热下再加热所述板坯，
-在800℃至1250℃的温度下热轧再加热的板坯，以获得热轧带钢，
-以至少10℃/s的冷却速度V冷却1冷却热轧带钢直到低于或等于700℃的卷取温度，
-卷取处于T卷取下的冷却的热轧带钢。
在另一实施方案中，通过本身已知的被称为紧凑型带钢加工的工艺来获得热轧带钢，并且得到薄板坯，因此免除了热轧步骤。
在另一实施方案中，还使用选自在400℃至600℃、1小时至24小时的间歇式退火和在650℃至750℃、60s至180s的连续退火中的工艺对热轧带钢进行退火。
在优选的实施方案中，使用直接火焰炉(direct fire furnace)来加热，用于铁还原的气氛包含20％至35％的H2，余量为氮气和不可避免的杂质。
在优选的实施方案中，使用辐射管炉来加热，用于铁还原的气氛包含2％至8％的H2，余量为氮气以及不可避免的杂质。
可选地，在200℃至400℃的温度T回火下对经冷轧并经退火的钢进行时间t回火为200s至800s的回火。
在另一实施方案中，使经冷轧并经退火的钢经历磷酸盐转化处理。
在另一实施方案中，然后利用典型的酸洗浴(例如，甲酸、盐酸、硫酸或消除存在的表面氧化物以得到主要为金属表面的其他酸)来在现有的连续退火作业线上对在退火期间不经过还原气氛的钢进行酸洗。
本发明还涉及包括由根据本发明的钢板制成的结构部件的车辆。
通过以下段落的详细描述，本发明的其他特征和优点将显现。
借助于实施例来给出结合的图，并且所述图不应被认作对本发明范围的限制。
所述图如下：
-图1示出了在冷轧及退火之后实施例A2的显微组织。暗相为奥氏体，白相为铁素体，
-图2示出了在冷轧及退火之后实施例A2的拉伸曲线，
-图3示出了本发明之外的所制造的实施例A6的GDOS图，
-图4示出了根据本发明所制造的实施例A3的GDOS图，
-图5示出了A6实施例的3点弯曲试验的结果，
-图6示出了A3实施例的3点弯曲试验的结果，
-图7示出了A4实施例的3点弯曲试验的结果，
-图8示出了根据实施例A2的退火循环的热程(thermal path)。
-图9示出了Al对钢D(0.2C 5Mn)的拉伸强度的稳定性的影响。
根据本发明，使钢的化学组成平衡以达到性能目标。以重量百分比计给出下面的化学组成元素。
铝含量必须低于9.0％，原因是铝含量必须严格地保持小于该值以避免脆性金属间析出物。
铝的添加在许多方面引人关注，以通过增加残余奥氏体中的碳来增加残余奥氏体的稳定性。此外，发明人已示出：出乎意料的是，即使Al理应使铁素体稳定，但在本发明中，Al含量越高，在退火期间形成的奥氏体的稳定性越好。
在退火期间添加Al而提高的稳健性使得在连续退火作业线上的退火期间、奥氏体分数作为的温度的函数变化较小。
Al是最有效的元素，其能够打开连续退火的大的可行性窗口，原因是其促使了在高于非再结晶温度的退火温度T退火下充分的再结晶与奥氏体稳定化的组合。
Al还使得钢密度能够减少最高10％。此外，该元素减少了高强度钢的不利影响，例如回弹、氢脆以及刚度损失。如图9所示，Al大于1.5％，钢的稳健性得到提高，并且Δ拉伸强度等于或小于10MPa/℃的Δ退火温度。然而，这会对可以达到的拉伸强度产生影响。通过所添加Al的百分数来使拉伸强度降低50MPa。
正如铝一样，硅是用于减小钢的密度的元素。硅通过固溶体对提高强度也非常有效。然而，硅的含量限于5.0％，原因是如果超过该值，则在冷轧期间会遇到脆性问题。
根据本发明，碳含量为0.10％至0.50％。碳是伽马相形成(gamma-former)元素。碳和Mn一起促进了奥氏体的出现(onset)。碳含量低于0.10％时，难以获得大于1000-50xAlMPa的机械强度。如果碳含量大于0.50％，则冷轧的可轧制性降低并且可焊性变差。
锰必须为3.5％至10.0％。该元素也是奥氏体稳定剂，用以使显微组织中足够的奥氏体稳定化。对于显微组织，锰也具有固溶体硬化以及细化作用。对于Mn含量小于3.5％，在显微组织中的残余奥氏体的稳定性不足以实现均匀延伸率大于15％和拉伸强度大于1000-50x％Al MPa的组合。在锰的含量大于10.0％时，可焊性变差。偏析物和掺入物使损伤性能劣化。
为了获得另外的析出硬化，可以以小于0.2％的量分别地添加微合金元素例如钛、钒和铌。具体地，钛和铌用以在凝固期间控制晶粒尺寸。然而一个限制是必要的，因为超过该限制会获得饱和效应。
容许最高1％的铬。高于该限制，则可能出现不利的表面氧化物。
在硫含量大于0.004％时，由于存在过多的使延展性降低的硫化物例如MnS而使延展性降低，特别是在扩孔试验期间。
磷是使固溶体硬化但使点可焊性和热延展性降低的元素，具体是由于磷趋于在晶界处偏析或与锰一起共偏析。由于这些原因，为了获得良好的点可焊性，磷的含量必须限于0.025％，并且优选0.015％。
本发明允许的最大硼含量为0.0035％。如果大于此限制，则关于晶粒的细化预料存在饱和水平。
余量由铁和不可避免的杂质构成。
为了达到目标性能，本发明的钢板的显微组织必须包含：以表面分数计，10％至50％的奥氏体、25％至90％的铁素体、低于5％的卡帕析出物和低于25％的马氏体。
奥氏体是带来延展性的组织，其含量必须高于10％，使得本发明的钢具有均匀延伸率大于15％的足够的延展性，并且奥氏体的含量必须低于50％，原因是高于该值，机械性能平衡劣化。
本发明中的铁素体被限定为体心立方结构，该铁素体通过对在凝固期间形成的前述铁素体或者对热轧钢的贝氏体或马氏体进行退火之后的回复和再结晶而获得。铁素体的含量必须为25％至90％，以具有(1000-50x％Al)MPa的最小的拉伸强度和至少15％的均匀延伸率。
本发明中的卡帕被限定为化学计量如下的析出物：(Fe,Mn)3AlCx，其中x严格地小于1。析出物卡帕的表面密度可以达到最高5％。表面密度高于5％时，延展性降低并且不会获得大于15％的均匀延伸率。另外，可能发生卡帕不受控制地在铁素体晶界周围析出，因此提高了热轧和/或冷轧期间的作用力。优选地，卡帕析出物的表面密度应该小于2％。因为显微组织是均匀的，所以表面分数等于体积分数。
马氏体是在对不稳定的奥氏体进行均热之后的冷却期间形成的结构。马氏体的含量必须限于25％，使得扩孔率保持大于20％。在优选的实施方案中，在涂覆步骤之后或之前，根据涂层的类型来对该马氏体进行回火。
根据本发明的钢板的另一主要特征在于其反应性表面，该反应性表面可以被描述为包括连续的下述层：
-纯金属铁的顶层，其厚度为50nm至300nm，以及
-由金属铁制成的第一下层，其还包含选自Mn、Si、Al、Cr和B的氧化物的一种或更多种析出物，该第一下层的厚度为1μm至8μm。
这样的结构确保了在裸钢的磷酸盐转化处理期间的反应性、金属涂层(例如锌涂层或铝涂层)良好的润湿以及粘附性。这提高了涂料的电沉积能力。
只要获得了这样的表面，就可以采用任意适当的制造方法。
通过实施例，一个制造根据本发明的钢的方法意指铸造具有本发明的化学组成的钢。
在1100℃至1300℃之间对铸钢进行再加热。当板坯的再加热温度低于1100℃时，对于Al<4wt％，轧制负荷增加过多并且热轧过程变得困难；对于Al≥4wt％，由于在轧制过程期间的热损耗，最后一个热轧道次难以保持高于800℃。当高于1300℃时，氧化十分剧烈，这导致氧化皮损耗以及表面劣化。
然后可以在1250℃至800℃的温度下对经再加热的板坯进行热轧，最后一个热轧道次在大于或等于800℃的温度Tlp下进行。如果Tlp低于800℃，则会降低热加工性。
在至少10℃/s的冷却速度V冷却1下使钢冷却直至小于或等于700℃的卷取温度T卷取。如果冷却速度V冷却1低于10℃/s，在Al≥4wt％并且Mn≥4wt％的情况下，在铁素体与奥氏体之间的界面处出现有害卡帕析出物的析出。
T卷取必须小于或等于700℃。如果卷取温度高于700℃，则存在形成由下述组成的粗的显微组织的风险：
●当Al含量低于4wt％时，粗的铁素体和贝氏体组织
●当Al含量高于或等于4wt％Al而Mn含量高于4wt％Mn时，在铁素体与奥氏体之间的界面处的卡帕碳化物。
然后以30％至75％的冷轧率对钢进行冷轧，以获得冷轧钢。在冷轧率小于30％时，对随后退火期间的再结晶的促进不够，并且由于缺少再结晶而不会获得大于15％的均匀拉长率。在冷轧率大于75％的情况下，在冷轧期间存在边缘开裂的风险。
然后，以至少等于1℃/s的加热速率H加热加热钢直至退火温度T退火。如果加热速率小于1℃/s，则用于再结晶的力太低，阻碍了获得目标显微组织。
在加热期间，从550℃升至均热结束的T退火，钢通过氧化气氛，以主要制造厚度为100nm至600nm的铁氧化物。
●如果铁氧化物薄于100nm，则铁氧化物将消失得太早，在随后的还原退火期间允许再次对合金元素进行外部选择性氧化，妨碍了在涂覆过程期间表面的反应性。
●如果铁氧化物超过600nm，则非粘附型铁氧化物的风险通过辊印(pick-up)问题而致使炉的炉底辊的污染，并且因此由于压痕而导致表面缺陷。大于600nm的厚度还可以导致在应用还原气氛时的均热和冷却步骤期间或者在均热或冷却期间仅部分还原了铁氧化物。
如果在用于加热的熔炉中使用辐射管炉，则用于铁还原的气氛应当包含2％至8％的H2，余量为氮气和不可避免的杂质。
●如果H2含量低于2％，气氛的还原能力太低而不能完全还原铁氧化物。
●如果H2含量高于8％，还原过程完成，但是不具有经济可行性。
然后在30秒至700秒期间在Tmin℃至Tmax℃之间的温度T退火下对钢进行退火。控制退火温度是重要的工艺特征，原因是其能够控制奥氏体分数及其化学组成。退火温度应该足够高以形成在最终显微组织中需要的多于10％的残余奥氏体，并且避免析出多于5％的卡帕碳化物。退火温度不应太高，以避免形成多于50％的奥氏体并且避免当Al≥4wt％时导致拉伸强度低于1000-50xAl(％)的晶粒粗化。退火温度还应该足够高，以使得经冷轧的组织能够充分地再结晶。因为相转变取决于化学组成，所以优选的T退火被优选地限定为下述：
退火温度Tmin被限定为例如：Tmin＝721-36*C-20*Mn+37*Al+2*Si(以℃计)。低于该温度时，不会形成最小奥氏体分数。或者奥氏体的稳定性过高而使拉伸强度受限。
退火温度Tmax被限定为例如：Tmax＝690+145*C-6.7*Mn+46*Al+9*Si(以℃计)。高于Tmax时，还存在形成过多马氏体的风险，导致均匀伸长度和扩孔能力受限。
–在均热的T退火降至600℃期间，钢通过含2％至35％的H2、余量为氮气和不可避免的杂质的气氛，以减少在加热后施加露点低于铁氧化的通常低于-10℃的临界露点而形成的铁氧化物。
●如果H2含量低于2％，则气氛的还原能力太低而不能完全还原铁氧化物。
●如果H2含量高于35％，则还原过程完成，但是不具有经济可行性。
优选地，在铁还原期间的露点低于-30℃，以允许快速的还原动力学。
在优选的实施方案中，H2含量高于20％但低于35％。
–在另一实施方案中，跳过还原步骤，在完成整个退火处理之后，通过酸洗(甲酸、盐酸、硫酸)来去除铁氧化物。这是因为，如果钢不通过还原气氛，则可能发生轻度再氧化并且该层应该被去除。在本发明中：
●均热的第一部分意指加热并且最长占均热时间的90％。
●而均热的第二部分意指剩余的均热时间以及从退火温度下降到600℃的冷却。
然后以通常退火作业线的冷却速率V冷却2来对钢进行冷却，优选地，冷却速率大于5℃/s而小于70℃/s。如果冷却速率小于5℃/s，则在Al含量大于4wt％时存在形成多于5％的卡帕碳化物的风险。冷却气氛含2％至35％的H2，以避免应用露点低于铁氧化的通常低于-10℃的临界露点而形成的经还原的铁氧化物的再氧化。
–任选地，以V冷却2使钢冷却到350℃至550℃之间的温度TOA，并且保持在TOA 10秒至300秒的时间。示出了例如通过热浸过程而促进Zn涂层的这样的热处理不会影响最终的机械性能。
以通常退火工作线的冷却速率V冷却3来使钢进一步冷却至室温，优选地，该冷却速率大于5℃/s而小于70℃/s，以获得经冷轧和经退火的钢。
在另一实施方案中，在将钢保持在TOA之后，用Zn或Zn合金热浸镀钢，Zn合金意指以百分比计Zn的含量在合金中最高。
在另一实施方案中，在将钢保持在TOA之后，用Al或Al合金热浸镀钢，Al合金意指以百分比计Al的含量在合金中最高。
任选地，在200℃至400℃之间的温度T回火下对经冷轧和经退火的钢进行回火200秒至800秒的时间t回火。该处理能够对可能在均热之后的冷却期间由不稳定的奥氏体形成的马氏体进行回火。因此降低了马氏体的硬度，提高了扩孔能力。在T回火低于200℃时，回火处理不够有效。在T回火高于400℃时，强度损失变高，并且不再能够改进强度与扩孔之间的平衡。
在另一实施方案中，使经冷轧和经退火的钢经历磷酸盐转化处理。
在另一实施方案中，经冷轧和经退火的钢涂覆有Zn、Zn合金、Al或Al合金，所述Zn、Zn合金、Al或Al合金通过电沉积或真空技术施加。Zn合金和Al合金意指Zn和Al分别是涂层的主要成分。
由铸钢件开发了半成品。下面的表1中示出了以重量百分比表示的半成品的化学组成。表1中钢成分的余量由铁和由熔炼造成的不可避免的杂质组成。
表1：化学组成(wt％)
这些钢不含硼
产品已经首先被热轧。然后对经热轧的板进行冷轧和退火。在表2中示出了具有下述缩写的生产条件：
●T再加热：是再加热温度
●Tlp：是精轧温度
●V冷却1：是最后一个轧制道次之后的冷却速率
●T卷取：是卷取温度
●比率：是冷轧压下率
●H速率：是加热速率
●T退火：是退火期间的均热温度
●t退火：是退火期间的均热持续时间
●V冷却2：是均热之后的冷却速率
●tOA：是板保持在温度TOA期间的时间
●V冷却3：是低于TOA时的冷却速率
在不同的退火气氛下对产品进行退火。在表3中，给出了退火气氛，并且给出了在完成连续退火循环之后在甲酸中进行酸洗的指示。如果应用酸洗处理则为“是”，如果不应用酸洗处理则为“否”。
如果从550℃升至均热结束的T退火的退火气氛通过调节露点和氢含量来使铁氧化，则指示“氧化”被设置在列“从550℃升至均热结束的T退火的气氛”中；如果气氛使铁还原，则设置“还原”。另外，给出了退火气氛中的H2含量和露点。
如果在均热的T退火降至600℃期间的退火气氛使铁氧化物还原，则“还原”被设置在列“在均热的T退火降至600℃期间的气氛”中。如果退火气氛使铁氧化，则指示“氧化”。另外，给出了退火气氛中的H2含量和露点。
在此下述的表3中，EG代表电镀(锌)，而GI代表镀覆(锌)。
表3：在退火之后用于制造合适的反应性表面的退火条件，余量为N2
在导致差的表面反应的常规还原气氛(露点＝-40℃，5％H2)下对试样A6、B2、F2、F4和G2进行退火。这样的表面的GDOS图的特征在于Fe信号非常低而O信号高的第一区域占自由表面的大于50％。在该区域中，还检测到了Mn的富集。在该层之下，以约1％每纳米的速率，Fe信号增强而O信号减弱。该氧信号尾部是存在外部选择性氧化物层的象征，其中在测量期间氧原子被部分地溅射至并部分地注入基底。由于试样从退火模拟器被转移至GDOS分析器，所以可见一些浅表性污染。在图3中，在(A)中，由于试样从退火模拟器转移至GDOS分析器，所以可见一些浅表性污染。
表4示出了下述特征：
●铁素体：“OK”指代在经退火的板的显微组织中存在体积分数为25％至90％的铁素体。“KO”指代铁素体分数在该范围外的比较例。
●奥氏体：“OK”指代在经退火的板的显微组织中存在体积分数为10％至50％的奥氏体。“KO”指代奥氏体分数在该范围外的比较例。
●马氏体：“OK”指代在经退火的板的显微组织中存在体积分数小于25％的马氏体或者不存在马氏体。“KO”指代马氏体分数大于25％的比较例。
●K：“OK”指代在显微组织中存在表面分数小于5％的卡帕析出物或者不存在卡帕析出物。该测量利用扫描电子显微镜进行。当其表示为“KO”时，卡帕析出物的分数大于5％。
●UTS(MPa)指代通过相对于辊方向的纵向方向上的拉伸试验而测量到的拉伸强度。
●UEI(％)指代通过相对于辊方向的纵向方向上的拉伸试验而测量到的均匀延伸率。
●HE(％)指代根据标准ISO 16630 2009的扩孔率。确定扩孔率HE％的方法用于评估金属抵抗形成切边(cut-edge)的能力。该方法包括在形成孔之前测量初始直径Di，然后在形成孔之后测量最终孔径Df，最终孔径Df在当孔的边缘上观察到穿透裂纹时被确定。该方法然后使用下述公式来确定扩孔HE％的能力：
在该方法下，初始孔径为10毫米。
表4：经冷轧和经退火的板的性能
由于脆性行为，未测量B1。对于C1，显微组织(50％)的余量由贝氏体构成。C1表现出的拉伸强度为820MPa，该拉伸强度对于本发明来说太低。
表5示出了电沉积锌涂层的涂覆能力的结果。
目标表面和次表面微观结构表示为“OK”，前提是：表面由金属铁的外部层构成，其厚度为50nm至300nm，所述外部层覆盖由金属铁构成并且包含Mn、Al、Si、Cr、B和比铁更易氧化的其他元素的内部氧化物的厚度为1μm至8μm的析出物的内部层，所述层被上叠于主要由铁素体构成的厚度为10μm至50μm的脱碳层上。如果表面和次表面不同于目标表面，则显微组织被判定为不满足“KO”。
涂层质量的特征在于覆盖率和涂层粘附性。
当肉眼观察到全部覆盖时，覆盖率表示为“OK”，而如果观察到涂层缺陷例如未覆盖的区域或裸点，则覆盖率表示为“KO”。
使用具有半径为1.5mm的尖端的3mm的压头(punch)来在1mm板上进行的3点弯曲试验(180°)中对涂层粘附性进行测试。如果在贴上并撕下“思高”胶带之后观察到锌涂层没有剥落，则粘附性被判定为优异“OK”。如果观察到涂层的剥落或剥离，则粘附性被判定为不满足“KO”。
表5：经冷轧、经退火并经涂覆的板的表面性能
目标表面和次表面微观结构 覆盖率 涂层粘附性 涂层类型
A1 OK OK OK EG 本发明
A2 OK OK OK EG 本发明
A3 OK OK OK EG 本发明
A4 OK OK OK EG 本发明
A5 KO KO KO EG 参比
A6 KO KO KO EG 参比
A7 OK OK OK EG 本发明
A8 OK OK OK GI 本发明
B1 OK OK OK GI 本发明
B2 KO KO KO GI 参比
B3 OK OK OK GI 本发明
C1 OK OK OK GI 本发明
D1 OK OK OK EG 本发明
E1 OK OK OK EG 本发明
F1 OK OK OK EG 本发明
F2 KO KO KO EG 参比
F3 OK OK OK GI 本发明
F4 KO KO KO GI 参比
G1 OK OK OK EG 本发明
G2 KO KO KO EG 参比
H1 OK OK OK EG 本发明
在图5中，使用具有半径为1.5mm的尖端的3mm的压头来在1mm板上进行的3点弯曲试验(180°)中对涂层粘附性进行测试。对于钢实施例A6(在本发明之外)，观察到非粘附性的锌涂层。在(a)处，可观察到涂覆的部分，这在弯曲试验期间在低应力(solicitation)之下。在(b)处，在涂层剥落之后，可观察到钢基板；该部分在弯曲试验中在高应力之下。
板A1、A2、A3、A4、A7、A8、B1、B3、C1、D1、E1、F1、F3、G1和H1是化学组成和处理方法基于本发明的板。
对于试样A3，先在氧化气氛(露点＝+30℃)下并随后在还原气氛下进行生产。表面由第一层构成，其中，如图4所示，Fe的GDOS信号达到最大值而氧的GDOS信号达到最小值。该层(B)由金属铁构成。第二层(C)的特征在于：氧信号以约1％每100nm的慢的速率持续减小，并且与已经沉淀有Mn和Al的内部选择性氧化物处的区域对应。氧信号延伸至与厚度为4μm对应的5％的氧水平。在(A)中，由于试样从退火模拟器转移至GDOS分析器，所以可见一些浅表性污染。
对于试样A3，使用具有半径为1.5mm的尖端的3mm的压头来在1mm板上进行的3点弯曲试验(180°)中对涂层粘附性进行试验。如图6所示，对于钢实施例A3(在本发明内)，观察到非常好的粘附性的锌涂层，在(c)处，涂覆部分是可见的，这在弯曲试验期间的低应力之下。在(d)处，涂层示出了优异的粘附性，该部分在弯曲试验中的高应力之下。
如图7所示，对于A4，使用具有半径为1.5mm的尖端的3mm的压头来在1mm板上进行的3点弯曲试验(180°)中对涂层粘附性进行试验。对于钢实施例A4(在本发明内)，观察到非常好的粘附性的锌涂层。在(e)处，涂覆部分是可见的，这在弯曲试验期间的低应力之下。在(f)处，涂层示出了优异的粘附性，该部分在弯曲试验中的高应力之下。
图1示出了板A1的显微组织。图2示出了其拉伸曲线。
根据非目标的显微组织和涂覆方法，B2不是基于本发明的。B2的退火温度在目标之外。
A5在退火期间仅进行氧化的而未进行酸洗步骤，因此涂层粘附性和覆盖率差。
A6、B2、F2、F4和G2在退火期间仅进行了还原，因此，涂层粘附性和覆盖率结果差。
对于根据本发明的钢，除经由电镀(EG)或镀覆而获得的优良涂覆能力之外，拉伸强度大于1000-50xAl MPa，并且其均匀延伸率大于15％。此外，扩孔率还大于20％。
根据本发明的钢板将有利地用于在汽车工业中制造结构部件或安全部件。

Claims (26)

1.一种冷轧钢板，以重量百分比计，其包含：
0.1％≤C≤0.5％
3.5％≤Mn≤10.0％
Al≤9.0％
Si≤5.0％
0.5％≤Si+Al≤9.0％
Ti≤0.2％
V≤0.2％
Nb≤0.2％
B≤0.0035％
Cr≤1％
S≤0.004％
P≤0.025％
组成的余量为铁以及由熔炼造成的不可避免的杂质，并且显微组织包含：10％至50％的奥氏体、25％至90％的铁素体、低于5％的卡帕析出物以及低于25％的马氏体，所述板从顶表面呈现连续的以下层：
-纯金属铁的顶层，其厚度为50nm至300nm，以及
-由金属铁制成的第一下层，其还包含选自Mn、Si、Al、Cr和B的氧化物的一种或更多种析出物，所述第一下层的厚度为1μm至8μm。
2.根据权利要求1所述的冷轧钢板，还包括第二下层，其位于所述第一下层之下，由纯的铁素体构成，所述第二下层的厚度为10μm至50μm。
3.根据权利要求1或2所述的冷轧钢板，所述钢的组成的锰含量为5.0％至9.0％。
4.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的碳含量为0.1％至0.3％。
5.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的碳含量为0.15％至0.25％。
6.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的铝含量为1.5％至9％。
7.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的铝含量为5％至8％。
8.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的硅含量等于或低于1.5％。
9.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的组成的硅含量等于或低于0.3％。
10.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的显微组织包含25％至40％的奥氏体。
11.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的显微组织包含50％至85％的铁素体。
12.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的显微组织包含低于15％的马氏体。
13.根据权利要求1至2中的任一项所述的冷轧钢板，所述钢的显微组织不包含卡帕析出物。
14.根据权利要求1至2中的任一项所述的冷轧钢板，其呈现出以MPa计大于或等于1000-50x％Al的拉伸强度TS、大于或等于15％的均匀延伸率UEI以及大于或等于20％的扩孔率HE。
15.通过对根据权利要求1至14中的任一项所述的冷轧钢板进行涂覆而获得的金属涂覆钢板，通过选自热浸镀、电沉积和真空涂覆中的工艺来完成所述涂覆，任选地随后进行热处理。
16.根据权利要求15所述的金属涂覆钢板，其中所述板是经镀层扩散退火处理的。
17.一种制造根据权利要求1-9中任一项所述的冷轧钢板的方法，包括下述步骤：
-供给成分为根据权利要求1至9的热轧带钢或薄板坯，并且去除所述热轧带钢或所述薄板坯的氧化皮，
-以30％至75％的冷轧率对所述热轧带钢或所述薄板坯进行冷轧，以获得冷轧钢板，
-热处理所述钢板，在30秒至700秒期间以至少等于1℃/s的加热速率H速率使所述钢板经历加热直至位于Tmin＝721-36＊C-20＊Mn+37＊Al+2＊Si(以℃计)与Tmax＝690+145＊C-6.7＊Mn+46＊Al+9＊Si(以℃计)之间的退火温度T退火，随后在所述温度下经历均热，所述加热从550℃升至T退火，以及所述均热的至少第一部分在氧化气氛中进行，以生产厚度为100nm至600nm的铁氧化物顶层，然后对所述铁氧化物层进行完全还原。
18.根据权利要求17所述的方法，其中，所述还原发生在所述均热的第二部分期间，在包含2％至35％的H2且露点低于-10℃的还原气氛中，从而对所述铁氧化物层进行完全还原，使所述钢板以大于5℃/s且小于70℃/s的冷却速率V冷却2进一步冷却至室温。
19.根据权利要求18所述的方法，其中所述均热的所述第二部分发生在露点低于-30℃的气氛中。
20.根据权利要求17至19中的任一项所述的方法，其中：
-以V冷却2使所述钢板冷却到350℃至550℃之间的温度TOA，并且保持在TOA下10秒至300秒的时间，然后
-以5℃/s至70℃/s的冷却速率V冷却3使所述钢板进行进一步冷却至室温。
21.根据权利要求20所述的方法，其中，所述还原发生在以大于5℃/s且小于70℃/s的冷却速率V冷却2使所述钢板冷却至室温之后，并且通过化学酸洗完成。
22.通过对权利要求17至21中的任一项所述方法获得的冷轧钢板进行涂覆来制造金属涂覆钢板的方法，包括通过选自热浸镀、电沉积和真空涂覆中的工艺完成的涂覆的步骤，任选地随后进行热处理步骤。
23.根据权利要求22所述的方法，其中所述金属涂覆钢板经历镀层扩散退火热处理。
24.根据权利要求17至19，以及22至23中的任一项所述的方法，其中通过包括下述步骤的工艺来获得所述热轧钢带：
-铸造成分为根据上述权利要求的钢，以获得板坯，
-在1100℃至1300℃的温度T再加热下再加热所述板坯，
-在800℃至1250℃的温度下热轧所再加热的板坯，以获得热轧钢带，
-以至少10℃/s的冷却速度V冷却1冷却所述热轧带钢直到低于或等于700℃的卷取温度T卷取，
-卷取处于T卷取下的冷却的所述热轧钢带。
25.根据权利要求24所述的方法，其中还使用选自在400℃至600℃、1小时至24小时的间歇式退火和在650℃至750℃、60s至180s的连续退火中的工艺对所述热轧钢带进行退火。
26.包括由根据权利要求1至16中的任一项所述的钢板制成的结构部件的车辆。
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