CN104011230A - 用于制造包装用钢的方法 - Google Patents

用于制造包装用钢的方法 Download PDF

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Publication number
CN104011230A
CN104011230A CN201280063600.1A CN201280063600A CN104011230A CN 104011230 A CN104011230 A CN 104011230A CN 201280063600 A CN201280063600 A CN 201280063600A CN 104011230 A CN104011230 A CN 104011230A
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steel
steel plate
maximum
cooling
recrystallize
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CN104011230B (zh
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阿妮卡·塞斯尼
赫尔穆特·奥伯霍费尔
马丁·施卢普
迪尔克·马图舍克
赖纳·绍尔
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ThyssenKrupp Rasselstein GmbH
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ThyssenKrupp Rasselstein GmbH
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    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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Abstract

本发明涉及一种用于制造由冷轧钢板制成的包装用钢的方法，冷轧钢板由具有小于0.1％的碳含量的非合金的或低合金的钢制成。为了提供具有良好的可变形性和高的抗腐蚀性的较高强度的、能够尽可能以节约能量的方式制造的包装用钢，根据本发明的钢板首先用金属涂层来涂覆并且随后以再结晶的方式以大于75K/s且优选大于100K/s的加热速率退火到大于700℃的温度，从而熔化金属涂层。随后，涂覆的且退火的钢板以至少100K/s的冷却速率淬火到正常温度。

Description

用于制造包装用钢的方法
技术领域
本发明涉及用于由根据权利要求1的前序部分的冷轧的钢板制造包装用钢的方法。
背景技术
从CH 469 810中已知板或带形式的薄壁的钢制品和其制造方法，该方法能够用于制造具有较高强度的白铁皮。钢制品由碳含量为0.03％的重量百分比至0.25％的重量百分比的非合金的钢制成并且具有0.2％的重量百分比至0.6％的重量百分比的锰含量以及小于0.011％的重量百分比的硅含量。该钢制品的特征在于至少部分由马氏体和铁氧体组成的微观结构并且具有至少6328kg/cm2的拉伸强度和至少1.5％的断裂延伸率。为了构成该特性，钢制品在炉中首先加热到A1点之上的温度并且随后在水池中淬火。
对用于制造包装的金属材料的特性越来越多地提出更高的要求，尤其是在其可变形性和其强度以及其抗腐蚀性方面。尽管从汽车制造中已知具有多相晶体结构的双相钢，多相晶体结构基本上由马氏体和铁氧体或贝氏体组成，并且双相钢一方面具有高的拉伸强度并且另一方面也具有高的断裂延伸率。这种具有至少580MPa屈服点(Streckgrenze)和至少10％的断裂延伸率A80的这种双相钢例如从WO 2009/021898A1中已知。由于具有高强度和良好可变形性的这种双相钢的材料特性的组合，该双相钢尤其适合于制造复杂成形的且可高负载的构件，如其例如在汽车的车身结构的范围中是必需的。
已知的双相钢的合金通常由20％至70％的马氏体份额和一些残余奥氏体以及铁氧体和/或贝氏体组成。双相钢的良好的可变形性通过相对软的铁氧体相来确保并且高的强度通过接合在铁氧体基体中的固态的马氏体和贝氏体相来产生。可变形性和强度方面的期望特征能够在双相钢中通过合金组分在宽的范围中进行控制。因此，例如能够通过添加硅，通过铁氧体或贝氏体硬化来提高强度。通过添加锰能够正面地影响马氏体形成并且能够防止出现珠光体。加入铝、钛和硼的合金能够提高强度。此外，加铝合金用于还原和用于解开可能包含在钢中的氮。为了构成多相的合金晶体结构，双相钢经受再结晶的(或奥氏体化的)热处理，在该热处理中钢带被加热到这样的温度，使得设定具有本质上铁氧体-马氏体的晶体结构构成的期望的多相的合金结构的并且随后被冷却。通常，冷轧的钢带处于经济原因以连续退火方法在退火炉中以再结晶的方式退火，其中退火炉的参数，例如通过速度、退火温度和冷却速度根据所需的晶体结构和期望的材料特性来调节。
从DE 10 2006 054 300 A1中已知较高强度的双相钢以及用于其制造的方法，其中在制造方法中，冷轧或热轧的钢带在连续退火炉中以820℃至1000℃的温度范围经由再结晶的连续退火并且退火的钢板随后从该退火温度以每秒15和30℃之间的冷却速度冷却。
为了用作为包装用钢，从汽车制造中已知的双相钢通常是不适合的，因为其尤其由于高的合金、如锰、硅、铬和铝的含量而是极其昂贵的并且因为例如为了将包装用钢应用在食品领域中而不应使用一些已知的合金，因为必须排除通过合金组成部分扩散到填充物品中而污染食品。此外，多种已知的双相钢具有下述高的强度，使得其不能够借助通常用于制造包装用钢的设备进行冷轧。
此外，包装用钢必须具有高的抗腐蚀性以及相对于酸的良好的抗性，因为由包装用钢制成的包装、例如饮料和食品罐的内含物通常是含酸的。因此，包装用钢具有金属涂层作为抗腐蚀保护层。抗腐蚀保护层的质量主要完全取决于其在钢板表面上的附着能力。为了改进涂层的抗腐蚀性和抗腐蚀保护层在钢板表面上的附着，例如在制造白铁皮时在涂覆过程之后熔化以电镀的方式施加到钢板上的锡涂层。为此，将电镀地沉积到钢带上的涂层加热到稍微超过涂覆材料的熔点之上的温度(在锡涂层中例如加热到240℃)并且随后在水池中淬火。通过加热涂层，涂层的表面获得光泽的外观并且降低涂层和钢板之间的铁锡合金层的多孔性，由此提高其抗腐蚀性并且降低其对于腐蚀性物质、例如有机酸的渗透性。
发明内容
根据上述内容，本发明基于下述目的：提供具有良好的可变形性和高的抗腐蚀性的较高强度的包装用钢和指出用于其制造的尽可能能量有效的方法。
该目的借助具有权利要求1的特征的方法以及借助具有权利要求18的特征的钢板来实现。在从属权利要求中指出方法和钢板的优选的实施例。
用于用作为包装用钢的根据本发明的钢板由非合金的或低合金的冷轧的碳含量小于0.1％的钢制成。当在下面提及钢板时，也将钢板理解为上述钢板。根据本发明的钢板除了低的碳含量之外其特征在于其他的合金组成部分的低的浓度。由根据本发明的钢板制成的钢能够为冷轧的非合金的或低合金的钢。将其中合金都不超过5％的重量百分比的平均含量的钢称作为低合金的钢。用于制造根据本发明的钢板的钢尤其具有小于0.5％的重量百分比且优选小于0.4％的重量百分比的锰含量、小于0.04％的重量百分比的硅含量、小于0.1％的重量百分比的铝含量和小于0.1％的重量百分比的铬含量。钢能够包含硼和/或铌和/或钛的合金添加物，以提高强度，其中适当地加入处于0.001-0.005％的重量百分比的范围中的硼合金以及处于0.005-0.05％的重量百分比的范围中的铌或钛合金。当然，在此优选的是：Nb的重量份额<0.03％。
钢板首先用金属的抗腐蚀保护层来涂覆。抗腐蚀保护层例如能够为由锡、锌、铝、铬或锌/镍构成的涂层。涂层适当地以电解的方式施加到钢板的一个主面或两个主面上。
为了构成多相的合金晶体结构并且为了熔化所施加的涂层，涂覆的钢板然后首先以再结晶的方式以大于75K/s的加热速率退火到大于700℃的温度，并且在再结晶方式的退火之后被淬火。淬火优选以高的冷却速率实现，以便在钢中产生硬度提高。为此，以至少100K/s的冷却速率淬火。再结晶方式的退火适当地以Al相变点之上的温度进行。通过以Tmax>Acl的最大温度以再结晶的方式进行热处理，实现钢的奥氏体化并且随后快速的冷却在钢中构成多相的晶体结构，晶体结构包括铁氧体和马氏体、贝氏体和/或残余奥氏体的晶体结构组成部分中的至少一种。如此处理的钢板具有至少500MPa的拉伸强度和大于6％的断裂延伸率。
根据本发明，抗腐蚀涂层在对涂覆的钢板进行再结晶方式的退火之后熔化，以便由此改进涂层的腐蚀抗性并且改进在钢板表面上的附着。因此为了熔化涂层，在再结晶方式的退火中涂覆的钢板至少短暂地加热到最大温度，最大温度位于涂覆材料的熔化温度之上。熔化温度例如在镀锡的钢板(白铁皮)中例如为232℃，在镀锌的钢板中例如为419℃，并且在用铝涂覆的钢板中为660℃。
借助于电磁感应对涂覆的钢板进行再结晶方式的退火证实为尤其适合于制造根据本发明的包装用钢。令人惊讶地发现：当具有小于0.1％的碳含量的冷轧的钢板首先以大于75K/s的加热速率借助于电磁感应以再结晶的方式(或者奥氏体化的方式)退火并且随后以至少100K/s的高冷却速率淬火时，能够放弃合金组成部分的加合金，合金组成部分典型地包含在双相钢中，例如加锰合金(在已知的双相钢中典型地具有0.8-2.0％的重量份额)、加硅合金(在已知的双相钢中典型地具有0.1-0.5％的重量份额)和铝合金(在已知的双相钢中典型地以至0.2％的重量份额加合金)。
感应加热对于马氏体相在感应退火的钢带中的布置和构成的令人惊讶地观察到的影响能够如下进行阐述：铁磁材料在不存在外部磁场的情况下不被磁化。然而在该物质内部中，同样存在没有外部磁场的情况下磁化至饱和的区域(白色区域)。白色区域通过布洛赫壁()分开。通过施加外部的磁场，首先适当定向的、即能量方面优选的白色区域在消耗邻近区域的条件下生长。布洛赫壁在此推移。在此电子自旋的折叠不同时进行而是自旋首先在白色区域的边界处变换其方向。在电场进一步提高时，磁化的方向旋转到该场的方向中直到磁化方向在全部区域中与外部磁场的方向一致并且达到饱和。此外已知的是，磁场能够影响位错(Versetzung)的移动而不影响外部施加的机械应力。现在看起来合理的是：布洛赫壁在其移动时携带碳原子和/或位错。由此在特定的区域中收集碳原子和/或位错，在该区域中随后在退火和淬火之后形成马氏体。
适当的是，钢板为薄钢板或极薄钢板，钢板在冷轧方法中被轧制成其最终厚度。薄钢板具有小于0.5mm的厚度。
具体实施方式
下面根据一个实施例详细阐述本发明：
为了制造根据本发明的钢板以作为包装用钢的实施例而应用以连铸制成的且热轧的以及缠绕到线圈上的钢带由具有下述成分的钢：
-C：最大0.1％；
-N：最大0.02％；
-Mn：最大0.5％，优选小于0.4％；
-Si：最大0.04％，优选小于0.02％；
-Al：最大0.1％，优选小于0.05％；
-Cr：最大0.1％，优选小于0.05％；
-P：最大0.03％，
-Cu：最大0.1％，
-Ni：最大0.1％，
-Sn：最大0.04％，
-Mo：最大0.04％，
-V：最大0.04％；
-Ti：最大0.05％，优选小于0.02％；
-Nb：最大0.05％，优选小于0.02％；
-B：最大0.005％
-和其他的合金组成部分，包括杂质：最大0.05％；
-剩余为铁。
该钢板首先在50％至96％的厚度减小的情况下被冷轧至大约0.5mm范围中的最终厚度并且随后以电解的方式在带镀锡设备中设有锡涂层。在涂覆过程之后，涂覆的钢板在感应炉中通过感应加热以再结晶的方式退火。在此，例如对于20×30的试样大小而言，在f＝200kHz的情况下应用具有50kW功率的感应线圈。在图1中示出退火曲线。如能够从图1的退火曲线中得出：钢带在典型为大约0.5s和10s之间的极其短的加热时间tA之内加热到A1温度(T(A1)≈725℃)之上的最大温度Tmax上。最大温度适当地位于铁磁的相过渡(Tf≈770℃)的相过渡温度Tf之下。然后，钢带的温度在大约1秒的退火时间段tG之上保持在大于A1温度之上的温度值上。在该退火时间段tG期间，钢带稍微地从其例如750℃的最大温度冷却到A1温度(大约725℃)上。此后，借助于例如能够通过水冷或气冷或通过用惰性气体进行的喷射冷却产生的流体冷却将钢带在大约0.25秒的冷却区间之内冷却到室温(大约23℃)。在冷却之后，如果需要的话还能够进行涂覆的钢带的矫直。
如此处理的钢带随后在其强度和其断裂延伸率方面进行研究。通过比较试验能够示出：在全部情况下，断裂延伸率高于6％并且通常高于10％并且拉伸强度最小为500MPa并且在许多情况下甚至证实拉伸强度位于600至800MPa的范围中。
通过根据克雷姆(Klemm)的色彩沉积刻蚀(Farbniederschlagaetzung)能够证实：根据本发明处理的钢板具有合金晶体结构，合金晶体结构具有铁氧体作为软相和马氏体以及可能的贝氏体和/或残余奥氏体作为硬相。在图2中示出借助根据克雷姆的色彩沉积刻蚀的横磨削中的晶体结构，其中在那示出为白色的区域示出马氏体相并且示出为蓝色或棕色的区域示出铁氧体相。从中示出较高强度的相(马氏体/贝氏体)的行状的布置。
通过比较试验能够测定：当再结晶方式的退火中的加热速率位于200K/s和1200K/s之间时且当再结晶方式退火的钢带随后以大于100K/s的冷却速率冷却时，实现关于可变形性的强度方面最佳的结果。在仪器方面适当的是，在此冷却速率为350K/s和1000K/s之间，因为因此能够放弃仪器方面耗费的水冷或油冷装置并且能够借助于冷却气体、例如空气进行冷却。当然，在应用具有大于1000K/s的冷却速率的水冷装置的情况下实现在材料特性方面最佳的结果。当然，过高的冷却速率在淬火期间隐含钢带的破裂危险和变形。
因为在再结晶方式退火时涂覆的钢带被加热到(锡)涂覆的熔点之上的温度，所以抗腐蚀涂层在退火期间熔化。这引起涂层的抗腐蚀和抗酸性的改进并且引起涂层改进地附着在钢板表面上。在此，改进的附着通过构成薄的(与涂层的厚度相比)和钢板表面和涂层之间的极其厚的合金层来引起，合金层由钢的铁原子和涂覆材料的原子(因此例如为锡)构成。根据方法参数，能够实现合金层的厚度，该厚度相应于小于0.5g/m2或者甚至小于0.3g/m2的合金层涂层。通过涂层在再结晶方式的退火中熔化还降低涂层的多孔性进而提高抗腐蚀和抗酸性。同时，涂层的熔化引起涂层的表面光泽度的改进，因为涂层的原始粗糙的表面通过熔化和快速淬火来变得光泽。
其示出，在涂覆的钢板在水池中淬火之后，在涂层的表面上构成厚的氧化层。为了移除该不期望的氧化层，涂覆的钢板在淬火期间或之后适当地用弱酸、例如15％的盐酸来处理。然而，为此也能够应用其他的酸并且以不同的浓度应用。尤其有效的是，应用冷的酸池作为淬火液体，酸池包含酸。然后，通过酸处理进行氧化层的移除并且同时通过将涂覆的钢板浸入酸池中进行淬火。
根据本发明制造的钢板突出地适合于用作为包装用钢。因此，例如能够由根据本发明的钢板制成罐头或饮料罐，罐头或饮料罐满足对于包装的抗腐蚀和抗酸性的尤其在食品领域中所需要的高的要求。
相对于从汽车制造中已知的双相钢，根据本发明的用于作为包装用钢的钢板的特征尤其在与显著更低的制造成本和下述优点：能够应用具有低的合金浓度和少量的合金组成部分的钢，由此能够避免所包装的食品的污染。在强度和可变形性方面，根据本发明的钢板与从汽车制造中已知的双相钢类似。冷轧钢的轧制的晶体结构通过再结晶方式的退火转换成多相的晶体结构，多相的晶体结构具有高的强度和良好的断裂延伸率。在此，再结晶的退火—与例如在已知的镀锡方法中不同—首先在用金属涂层对钢板涂覆之后才进行。因为根据本发明同时借助再结晶方式的退火熔化金属涂层，所以也在腐蚀和酸抗性方面和表面光泽度方面提高抗腐蚀涂层的质量。因此，根据本发明的方法是极其能量有效的，因为同时在唯一的方法步骤中进行钢中的晶体结构转化和涂层的熔化(再结晶方式的退火与随后的淬火)。因此，钢板的再结晶的退火能够(在涂覆之后)在涂覆设备中并且不如在现有技术中那样通常(在涂覆之前)在涂覆设备之外在分开的退火步骤中进行。这实现快捷的过程控制并且显著地降低设备方面的耗费。在根据本发明的方法中在涂覆过程之前不需要钢板的再结晶方式的热处理。

Claims (20)

1.一种用于制造由冷轧钢板制成的包装用钢的方法，所述冷轧钢板由具有小于0.1％碳含量的非合金的或低合金的钢制成，其特征在于，所述钢板首先用金属涂层来涂覆并且随后以再结晶的方式在大于75K/s且优选大于100K/s的加热速率的情况下退火到大于600℃的温度并且优选大于700℃的温度，从而使得所述金属涂层熔化，并且随后使涂覆的且退火的所述钢板淬火。
2.根据权利要求中1所述的方法，其特征在于，涂覆的所述钢板在以再结晶的方式进行所述退火之后以至少100K/s的且优选大约500K/s的冷却速率进行淬火，由此在所述钢中构成多相的晶体结构，所述晶体结构包括铁氧体，以及马氏体、贝氏体和/或残余奥氏体的晶体结构组成部分中的至少一种。
3.根据权利要求中2所述的方法，其特征在于，涂覆的所述钢板在以再结晶的方式进行所述退火之后以大于700K/s并且优选至少1000K/s的冷却速率淬火。
4.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢具有
-小于0.4％的重量百分比的锰含量，
-小于0.04％的重量百分比的硅含量，
-小于0.1％的重量百分比的铝含量，
-以及小于0.1％的重量百分比的铬含量。
5.根据权利要求2所述的方法，其特征在于，至大于80％并且优选至至少95％的多相的所述晶体结构由铁氧体、马氏体、贝氏体和/或残余奥氏体的所述晶体结构组成部分构成。
6.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢板由低合金的钢制成，所述低合金的钢包含硼和/或铌和/或钛。
7.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢板为冷轧的薄钢板或极薄钢板。
8.根据前述权利要求中的任一项所述的方法，其特征在于，借助于电磁感应实现以再结晶的方式进行的所述退火。
9.根据前述权利要求中的任一项所述的方法，其特征在于，涂覆的所述钢板在以再结晶方式进行所述退火时加热到所应用的所述钢的Al相变点之上的温度。
10.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢板在以再结晶方式进行所述退火和所述冷却之后具有至少500MPa、优选大于650MPa的抗拉强度和大于5％、优选大于10％的断裂延伸率。
11.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢板由具有下述用于合金组成部分的重量份额的上限的低合金的钢制成：
-N：最大0.02％，
-Mn：最大0.4％，
-Si：最大0.04％，
-Al：最大0.1％，
-Cr：最大0.1％，
-P：最大0.03％，
-Cu：最大0.1％，
-Ni：最大0.1％，
-Sn：最大0.04％，
-Mo：最大0.04％，
-V：最大0.04％；
-Ti：最大0.05％，优选小于0.02％；
-Nb：最大0.05％，优选小于0.02％；
-B：最大0.005％
-和其他的合金组成部分，包括杂质：最大0.05％。
12.根据前述权利要求中的任一项所述的方法，其特征在于，所述钢板在以再结晶方式进行所述退火之后借助于冷却液体或借助于用惰性气体进行喷射冷却在100K/s和1200K/s之间的冷却速率下并且优选以750K/s和1000K/s之间的冷却速率进行冷却。
13.根据前述权利要求中的任一项所述的方法，其特征在于，以再结晶的方式进行的所述退火在0.5至1.5秒的、优选大约1秒的时间区间内实现，其中将所述钢板在此加热到至少700℃的温度并且优选加热到至少720℃的温度。
14.根据前述权利要求中的任一项所述的方法，其特征在于，所述金属涂层为由锡、锌、铝或铬构成的抗腐蚀保护层。
15.根据前述权利要求中的任一项所述的方法，其特征在于，所述金属涂层以电解的方式涂覆到所述钢板上。
16.根据前述权利要求中的任一项所述的方法，其特征在于，在所述冷却期间或在所述冷却之后用酸处理所述钢板的、以所述金属涂层所涂覆的表面。
17.根据权利要求16所述的方法，其特征在于，所述钢板的涂覆的所述表面的所述冷却和所述处理通过使涂覆的所述钢板浸入到冷却的酸池中来实现。
18.一种钢板，其由非合金的或低合金的且冷轧的、具有小于0.1％的碳含量的钢制成，其中所述钢板在至少一个表面上具有金属涂层并且为了构成多相的晶体结构且为了熔化所述金属涂层而首先以再结晶的方式在至少75K/s且优选大于100K/s的加热速率下退火到大于600℃的温度并且优选至少700℃的温度，并且在以再结晶的方式进行的所述退火之后被淬火。
19.根据权利要求18所述的钢板，由非合金的或低合金的且冷轧的钢制成，所述钢具有
-小于0.1％的碳含量，
-小于0.4％的重量百分比的锰含量，
-小于0.04％的重量百分比的硅含量，
-小于0.1％的重量百分比的铝含量，
-和小于0.1％的重量百分比的铬含量，
其中所述钢板具有多相的晶体结构，所述晶体结构包括铁氧体，以及马氏体、贝氏体和/或残余奥氏体的晶体结构组成部分中的至少一种。
20.一种将使根据权利要求18或19所述的钢板作为包装用钢的应用，尤其用于制造食品、饮料和其他填充物质、如化学或生物产品的罐以及用于制造气溶胶罐和封盖。
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DE102011056847B4 (de) 2014-04-10
BR112014014176B1 (pt) 2018-12-26
CN104011230B (zh) 2016-08-24
EP2794936A1 (de) 2014-10-29
US20150017469A1 (en) 2015-01-15
EP2794936B1 (de) 2016-12-28
ES2617233T3 (es) 2017-06-15
ES2613886T3 (es) 2017-05-26
ES2613886T5 (es) 2020-03-30
BR112014014788A2 (pt) 2017-06-13
RU2014128999A (ru) 2016-02-20
JP5855761B2 (ja) 2016-02-09
EP2794936B2 (de) 2019-10-02
JP2015508449A (ja) 2015-03-19
BR112014014176A2 (pt) 2017-06-13
BR112014014788B1 (pt) 2019-03-26
US20150010779A1 (en) 2015-01-08
DE102011056847A1 (de) 2013-06-27
EP2794937A1 (de) 2014-10-29
CA2857987C (en) 2016-09-20
EP2794937B1 (de) 2017-01-18
PL2794936T3 (pl) 2017-06-30
RU2586196C2 (ru) 2016-06-10
AU2012359105A1 (en) 2014-07-10
JP2015507086A (ja) 2015-03-05
CA2857987A1 (en) 2013-06-27
WO2013092170A1 (de) 2013-06-27
PT2794936T (pt) 2017-03-31
AU2012359105B2 (en) 2015-11-05
RS55574B1 (sr) 2017-05-31

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