CN104204234B - 制造用于包装应用的回复退火的涂覆钢基材的方法及由此制备的包装钢产品 - Google Patents
制造用于包装应用的回复退火的涂覆钢基材的方法及由此制备的包装钢产品 Download PDFInfo
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- CN104204234B CN104204234B CN201380017754.1A CN201380017754A CN104204234B CN 104204234 B CN104204234 B CN 104204234B CN 201380017754 A CN201380017754 A CN 201380017754A CN 104204234 B CN104204234 B CN 104204234B
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- 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
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Abstract
本发明涉及制造用于包装应用的回复退火的涂覆钢基材的方法及由此制备的包装钢产品。
Description
本发明涉及制造用于包装应用的回复退火的涂覆钢基材的方法及由此制备的包装钢产品。
通常以厚度为0.14-0.49mm的一次或二次冷轧镀锡轧机(tin mill)产品提供包装钢。一次冷轧(SR)镀锡轧机产品是直接冷轧至最终规格然后进行再结晶退火。通过将冷轧材料连续退火或分批退火带来再结晶。在退火后,通常通过施加1-2%的厚度压下量通常将该材料平整轧制,以改进材料的性质。二次冷轧(DR)镀锡轧机产品是给予第一次冷轧以达到中间规格、再结晶退火然后给予另一次冷轧至最终规格。所得的DR产品比SR更有刚性、更坚硬并且更强,这允许消费者在它们的应用中利用更轻规格的钢。将这些未涂覆的、冷轧的、再结晶退火和任选平整轧制的SR和DR包装钢称为黑钢板。可以在通常包含多个(通常4或5个)轧制台的冷轧串联轧机中以冷轧压缩的形式给出第一次和第二次冷轧。
回复退火(RA)是制备与二次冷轧(DR)级别相当的强度水平而且具有更好的可成形性和显著的延伸率值的包装钢的成本有效的方法。在退火方法中存在三个阶段,第一阶段为回复时期,这导致金属通过晶体缺陷(其主要类型为位错)的部分移除和在变形期间引入的储存能量的降低而软化。回复时期覆盖了在出现新的无应变晶粒之前发生的所有退火现象。第二时期为再结晶,其中在具有高的储存能量的晶粒的消耗下具有大角度晶界的新晶粒成核并生长。这在根据本发明的方法和产品中是要避免的,因为其导致拉伸性质的突然且急剧的降低和延伸率值的增加。第三时期为再结晶之后的晶粒生长。
令人遗憾的是,RA的缺点在于沿着带材长度以及从带材到带材的机械性质通常是不均匀的。机械性质的这些变化是退火炉的温度的级别和/或波动的反应过于动态的结果。
本发明的一个目的是提供回复退火条件的较好控制。
本发明的另一个目的是提供具有可再现性质的回复退火的材料。
本发明的又一个目的是提供用于包装用途的更加成本有效的高强度钢,其具有耐腐蚀的外表面。
通过制造用于包装应用的回复退火的涂覆钢基材的方法达到这些目的中的一个或多个,该方法包括以下步骤:
●通过在高于或等于Ar3转变点的终轧温度下热轧来提供适于制备用于制备包装钢的低碳、超低碳或极低碳热轧带材的钢板坯或带材;
●冷轧所得的钢带材以制备一次冷轧钢基材;
●在该一次冷轧钢基材的一侧或两侧上电沉积锡层以制备涂覆锡的钢基材,其中基材的一侧或两侧上的一个或多个锡层的涂层重量为至多1000mg/m2;
●在至少513℃的温度Ta下退火该涂覆锡的钢基材持续退火时间ta:
○以将锡层转化成铁-锡合金层,其包含至少80重量%(wt.%)的FeSn(50原子%铁和50原子%锡),和
○以同时获得回复的显微组织,并且其中不发生一次冷轧基材的再结晶(即回复退火);
●在至少100℃/s和/或的冷却速率下快速冷却该退火的基材。
锡层转化成包含至少80重量%(wt.%)的FeSn(50原子%铁和50原子%锡)的铁-锡合金层意味着在基材上没有残留未合金化的锡。
本发明还体现为包装钢产品,例如罐、罐盖或罐底,其包含在一侧或两侧上提供铁-锡合金层的低碳、超低碳或极低碳钢基材,该铁-锡合金层包含至少80重量%(wt.%)的FeSn(50原子%铁和50原子%锡),其中铁-锡合金层通过如下方式制备:提供基材,在该基材的所述一侧或两侧上具有锡层,接着在至少513℃的温度Ta下的退火步骤持续退火时间ta以形成铁-锡合金层,并且其中退火步骤同时提供回复退火的基材,接着快速冷却该退火的基材。
在从属权利要求中提供了优选的实施方案。
在根据本发明的方法中,通过在高于或等于Ar3转变点的终轧温度下热轧提供了适于制备用于制备包装钢的低碳、超低碳或极低碳热轧带材的钢板坯或带材。本发明的上下文中的低碳钢具有至多0.05%的碳含量,超低碳钢具有至多0.02%的碳含量,并且极低碳具有至多0.003%的碳含量。在本发明的一个实施方案中,该钢为无晶隙钢,优选超低碳的。在这些钢中间隙元素碳和氮与元素如铌结合。
冷轧该热轧钢以制备一次冷轧(SR)钢基材。
随后在冷轧的全硬基材上沉积锡层。将该基材称为全硬基材是因为SR基材在冷轧步骤之后没有经历再结晶退火。因此该基材的显微组织仍然为严重变形的。
在镀锌后,在至少513℃的温度Ta下将涂覆锡的钢基材退火持续退后时间ta以将锡层转化成铁-锡合金层,该铁-锡合金层包含至少80重量%(wt.%)的FeSn(50原子%铁和50原子%锡),并且以同时获得回复的显微组织并且其中不发生一次冷轧基材的再结晶(即回复退火)。在这种组合的扩散/回复退火之后,将该退火的基材快速冷却。
温度Ta和退火时间ta相对高且短,因而发生扩散退火而同时回复退火该基材。由于短的退火时间,拉伸强度和屈服强度的降低仍然是有限的,但是回复效果产生了延伸率值的显著增加。非常仔细地控制该工艺参数,因为对于在扩散合金层中获得所需量的FeSn(50:50)而言扩散退火的时间-温度工艺窗口是关键的。由于正是该层提供防腐,这些参数的控制是关键的。T-t曲线的这种控制程度也确保了回复过程(其为热激活的过程)在带材的长度和宽度内并且从带材到带材是可再现的。
术语“回复的显微组织”理解为意指经热处理的冷轧显微组织,其显示最少的或不显示再结晶,将这样的最终再结晶限制于局部区域例如带材的边缘处。优选地,该显微组织是完全未再结晶的。包装钢的显微组织因此为基本上或完全未再结晶的。这种回复的显微组织提供了以强度的有限降低为代价而具有显著增加的变形能力的钢。
本发明人发现有必要在至少513℃的温度(Ta)下将涂覆锡的钢基材扩散退火以获得所需的铁-锡涂覆层。选择在扩散退火温度Ta下的扩散退火时间(ta)使得获得锡层至铁-锡层的转化。铁-锡层中主要且优选唯一的铁-锡合金组分为FeSn(即50原子%(at.%)铁和50at.%锡)。应注意扩散退火时间与温度的组合在一定程度上是可互换的。高Ta和短ta将导致与较低Ta和较长ta相同的铁-锡合金层的形成。需要513℃的最小Ta,因为在更低温度下不形成所需的(50:50)FeSn层。此外扩散退火不必在恒定温度下进行,但是温度曲线还可为使得达到峰值温度。重要的是保持513℃的最低温度持续足够长的时间以获得铁-锡扩散层中所需量的FeSn。因此扩散退火可在恒定温度Ta下发生一定的时间段,或扩散退火例如可包括Ta的峰值金属温度。在后一种情况下,扩散退火温度不是恒定的。发现优选的是使用513-645℃、优选513-625℃的扩散退火温度Ta。在更低的Ta下,回复过程进行更加缓慢。通过形成FeSn的窗口和通过变形的基材的再结晶温度来限制最高温度。
在本发明的一个实施方案中,将最高退火温度限制为625℃,并且优选将最高退火温度限制为615℃。
本发明人发现,当选择退火温度为至少550℃时,获得铁-锡合金层中的最高FeSn含量。
在一个优选的实施方案中,提供了制备用于包装的涂覆基材的方法,其中在Ta下的时间为至多4秒,优选至多2秒,并且更优选其中在Ta下不存在停留时间。在后一种情况下,通过将基材加热至Ta的峰值金属温度然后冷却该基材来发生扩散退火。在Ta下短的停留时间允许在适当修改的常规镀锡生产线中制备铁-锡合金层。这些参数的仔细控制确保了可再现的回复退火过程。
回复退火的钢的机械性质取决于该级别的组成、冷轧压下量和回复退火温度和再结晶温度之间的差异。因此,原则上可通过选择恰当的退火周期而限制储存能量的释放来控制最终的机械性质。更特别地,由相同级别制得和具有相同的加工历史(热轧、冷轧压下量)和等效的退火周期的钢片材之间,可使用下式估计储存能量的释放:
M=(Ta+273)(log ta+20)×10-3
其中Ta以℃计。具有相似的M系数的钢片材将具有相似的机械性质。通过选择对于Ta和ta的恰当值,可确定回复退火的基材和铁-锡合金层的所需性质。
在一个优选的实施方案中,铁-锡合金层包含至少85wt.%的FeSn,优选至少90wt.%,更优选至少95wt.%。FeSn层是完全覆盖基材表面的层。FeSn的分数越高,基材的防腐将越好。尽管理想地铁-锡合金层仅由FeSn组成,但是似乎难以防止非常小分数的其它化合物例如α-Sn、β-Sn、Fe3Sn或氧化物的存在。然而,已发现这些小分数的其它化合物对产品性能没有任何影响。必须注意在基材上除了FeSn层不存在其它FexSny层。在基材上也没有残留未合金化的锡。
在Ta下的时间可不超过临界时间以避免再结晶的开始。在一个优选的实施方案中,提供了制备用于包装的涂覆基材的方法,其中在Ta下的时间为至多4秒,优选至多2秒,并且更优选其中在Ta下不存在停留时间。在后一种情况下,通过将基材加热至Ta的峰值金属温度然后冷却该基材来发生扩散退火。在Ta下短的停留时间允许在适当修改的常规镀锡生产线中制备具有回复基材的铁-锡合金层,此外防止了变形基材的再结晶。
在本发明的一个实施方案中,一个或多个铁-锡合金层提供有铬金属-铬氧化物涂覆层,该涂覆层通过如共同未决申请(EP12162415.9)中描述的三价铬电镀方法来制备。
在本发明的一个实施方案中,提供了一种方法,其中在还原性气体气氛例如HNX中进行退火,同时在使用非氧化性或温和氧化性的冷却介质冷却之前将涂覆基材保持在还原性或惰性气体气氛中,从而获得坚固、稳定的表面氧化物。
在本发明的一个实施方案中,通过用水淬火实现扩散/回复退火之后的快速冷却,其中用于淬火的水具有在室温与其沸腾温度之间的温度。重要的是在冷却期间在带材宽度内保持均匀的冷却速率以消除由冷却压屈(buckling)所致带材变形的风险。这可通过经过旨在带材表面上产生均等冷却模式的(浸没)喷射***施加冷却水来实现。为了确保在喷射期间均匀的冷却速率,优选使用具有室温至60℃之间的温度的冷却水以防止水在与热钢带材接触时达到沸腾温度。后者可导致局部(不稳定)的膜沸腾效应的开始,该效应可导致在钢带材的表面内不均等的冷却速率,潜在地导致冷却压屈的形成。
在本发明的一个实施方案中,退火过程包括i)在含氢的气氛例如HNX中使用能够产生优选超过300℃/s的加热速率的加热装置,如感应加热装置,和/或ii)接着是保持在退火温度下的均热以使跨带材宽度的温度分布均匀化,和/或iii)其中优选在还原性气氛例如HNX气氛中进行冷却,和/或iv)优选经由通过使用(浸没)喷射喷嘴的水淬火进行冷却,其中用于淬火的水具有最小的溶解氧含量并且具有室温至60℃之间的温度,同时通过在淬火之前维持惰性或还原性气体气氛例如HNX气体来保持具有(一个或多个)铁-锡合金层的基材屏蔽氧。
在本发明的一个实施方案中,基材的一侧或两侧上一个或多个锡层的涂层重量为至少100和/或至多600mg/m2的基材表面。
在本发明的一个实施方案中,该钢包含(以重量%计):
●0.05%或更少的碳含量,和/或
●0.004%或更少的氮含量,和/或
●0.05%-0.5%的锰含量,和/或
●0.02%或更少的磷含量,和/或
●0.02%或更少的硅含量,和/或
●0.03%或更少的硫含量,和/或
●0.1%或更少的铝含量,和/或
●任选以下的一种或多种:0.001%-0.1%的铌含量,0.001%-0.15%的钛含量,0.001%-0.2%的钒含量,0.001%-0.1%的锆含量,和5-50ppm的硼含量,和/或
●余量为铁和不可避免的杂质。
在本发明的一个优选实施方案中,碳含量为至多0.02%,优选至多0.003%,和/或铌含量为至少0.02和/或至多0.08%,和/或锰含量为至少0.2和/或至多0.4%。优选地,铌含量为至少0.03和/或至多0.06%。
通过选择0.003或更低的碳含量和适当高的铌含量,该钢变成无晶隙的,这意味着该钢中的碳和氮变成与铌连接。这导致其性质不受时效现象所影响的钢。间隙原子例如碳和氮对钢的变形行为具有显著的影响。钢中的不连续屈服与间隙强烈有关并且可导致Lüders带,这对于表面外观是不利的,并且还可促进在成形期间的过早破裂或在变形之后的非均匀回弹。为了抵抗间隙物质的不利影响,无晶隙钢基本上没有溶质碳和氮。这些“无晶隙”钢主要依赖于碳化物、氮化物和碳硫化物的固态析出以降低间隙溶质含量。此外,通过现代炼钢技术将总碳和氮含量降低至极低的水平,通常小于0.003重量%碳和小于0.006重量%氮。
在一个实施方案中,涂覆基材还提供有有机涂层,其由热固性有机涂层或热塑性单层涂层或热塑性多层聚合物涂层组成。
在一个优选的实施方案中,热塑性聚合物涂层为包含一个或多个层的聚合物涂层体系,其包括使用热塑性树脂例如聚酯或聚烯烃,而且还可包括丙烯酸树脂、聚酰胺、聚氯乙烯、氟碳树脂、聚碳酸酯、苯乙烯型树脂、ABS树脂、氯化聚醚、离子聚合物、聚氨酯树脂和功能化聚合物。为了清楚起见:
●聚酯是由二羧酸和二醇组成的聚合物。合适的二羧酸的实例包括对苯二甲酸、间苯二甲酸、萘二羧酸和环己烷二羧酸。合适的二醇的实例包括乙二醇、丙二醇、丁二醇、己二醇、环己二醇、环己烷二甲醇、新戊二醇等。可以一起使用多于两种类型的二羧酸或二醇。
●聚烯烃包括例如乙烯、丙烯、1-丁烯、1-戊烯、1-己烯或1-辛烯的聚合物或共聚物。
●丙烯酸树脂包括例如丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯或丙烯酰胺的聚合物或共聚物。
●聚酰胺树脂包括例如所谓的尼龙6、尼龙66、尼龙46、尼龙610和尼龙11。
●聚氯乙烯包括例如具有乙烯或乙酸乙烯酯的均聚物和共聚物。
●氟碳树脂包括例如四氟聚乙烯、三氟单氯聚乙烯、六氟乙烯-丙烯树脂、聚氟乙烯和聚偏乙烯。
●例如通过马来酸酐接枝的功能化聚合物,包括例如改性聚乙烯、改性聚丙烯、改性乙烯丙烯酸酯共聚物和改性乙烯乙酸乙烯酯。
可使用两种或更多种树脂的混合物。此外,该树脂可与抗氧化剂、热稳定剂、UV吸收剂、增塑剂、颜料、成核剂、抗静电剂、脱模剂、防粘剂等混合。显示这样的热塑性聚合物涂层体系的使用在罐子制作和罐子的使用中提供了优异的性能,例如贮存寿命。
根据第二方面,提供了一种包装钢,其包含在一侧或两侧提供铁-锡合金层的低碳、超低碳或极低碳钢基材,该铁-锡合金层包含至少80重量%(wt.%)的FeSn(50原子%铁和50原子%锡),其中该铁-锡合金层通过如下方式制备:提供基材,在基材的所述一侧或两侧上具有锡层,接着在至少513℃的温度Ta下的退火步骤持续退火时间ta以形成铁-锡合金层,并且其中退火步骤同时提供了回复退火的基材,接着快速冷却该退火的基材。
由于回复退火的全硬冷轧(SR)钢基材,该钢同时提供了铁/锡合金层形式的耐腐蚀涂层和良好的强度/延伸率比。
在本发明的一个实施方案中,提供了一种包装钢产品,其中该钢基材包含(以重量%计):
○0.05%或更少的C,
○0.004%或更少的N,
○0.05%-0.5%的Mn,
○0.02%或更少的P,
○0.02%或更少的Si,
○0.03%或更少的S,
○0.1%或更少的Al,
○任选以下的一种或多种:0.001%-0.1%的Nb,0.001%-0.15%的Ti,0.001%-0.2%的V,0.001%-0.1%的Zr,5ppm-50ppm的B,
○余量为铁和不可避免的杂质;
在一个优选的实施方案中,提供了一种包装钢产品,其中:
○碳含量为至多0.02%,和/或
○铌含量为至少0.02和/或至多0.08%,优选至少0.03和/或至多0.06和/或
○锰含量为至少0.2和/或至多0.4%。
优选地,根据本发明的钢的碳含量具有至多0.003%的碳含量。
更优选地,该钢基材为无晶隙钢。
在回复退火过程之后没有预期IF钢出现带材形状问题。带材平坦度受内应力影响,而内应力又源自于因退火温度的变化所致的不均匀的显微组织。对于Nb-IF级别,机械性质的变化是缓慢的。伴随退火温度的变化,机械性质的改变相对小(例如对于50℃的温度变化为35MPa),而对于LC钢预期对于Rp和Rm的约70MPa的差异(对于回复退火的低C钢)。因而与IF级别相比制备LC钢更关键。
然而,如果带材形状或表面纹理(例如粗糙度)会需要一些小校正或者如果该产品需要在抑制屈服点的条件下提供,那么本发明还体现为一种方法,其中将涂覆和退火的基材平整轧制或使其经受张力矫平,其中基材的压下量为0.5至3%平整轧制压下量或张力矫平中等效的压下量。由于不存在游离间隙物,无晶隙钢不时效,并且因此将无晶隙钢平整轧制的唯一原因会是为了形状校正或表面纹理。还可在用热固性有机涂层或热塑性单层涂层或热塑性多层聚合物涂层涂覆基材之后进行平整轧制。平整轧制的一次冷轧基材不视为DR基材。
现在将通过以下非限制性的实施例来进一步解释本发明。
表1:以1/1000wt.%计的钢组成
C | Mn | Nb | N | Alsol | S | P | Si | Ti | |
LC | 32 | 180 | tr | 3.7 | 52 | 6 | 14 | 3 | tr |
Nb40 | 3 | 350 | 43 | 2.5 | 60 | 5 | 4 | 32 | tr |
Ti108 | 12 | 210 | tr | 3.0 | 53 | 6 | 6 | 12 | 108 |
Nb-LC | 58 | 400 | 14 | 4.0 | 63 | 6 | 7 | 34 | tr |
ULC | 2 | 270 | tr | 3.0 | 12 | 9 | 9 | 60 | tr |
tr=痕量,仅杂质
表2:在回复退火前后的机械性质
在所选择的退火时间下,回复退火窗口在再结晶开始温度和从其开始材料被视为表现为全硬的温度之间。将从其开始该钢被视为表现为全硬材料的温度估计为低于再结晶开始温度200℃。已从显微组织和机械性质的分析(其中在不同温度下处理FH试样60s)确定对于Nb40的再结晶开始温度为710℃。因此估计对于Nb40级别的回复退火范围位于710℃至510℃之间。原则上,可使用高于510℃的各温度来获得回复退火的Nb40钢。然而,获得所需的铁-锡合金层的最低温度为至少513℃。为了保持退火时间少,优选在至少550℃的温度下退火。还在625℃的最高可允许的温度下进行实验持续4s。根据上面的式子,这些条件对应于在标准连续退火生产线中在576℃下退火60s。
所使用的退火参数为:至Ta的加热速率:300℃/s,550-625℃的Ta,4-60s的ta,退火后100℃/s的冷却速率(表3)。
表3:Nb40样品的Rp、Rm和A%值(FH和100%Rex为参比值(参比))。
Nb40级别是IF级别。因此在回复退火过程之后没有预期出现带材形状问题。
Claims (25)
1.制造用于包装应用的回复退火的涂覆钢基材的方法,该方法包括以下步骤:
●通过在高于或等于Ar3转变点的终轧温度下热轧来提供适于制备用于制备包装钢的低碳、超低碳或极低碳热轧带材的钢板坯或带材;
●冷轧所得的钢带材以制备一次冷轧钢基材;
●在该一次冷轧钢基材的一侧或两侧上电沉积锡层以制备涂覆锡的钢基材,其中该基材的一侧或两侧上的一个或多个锡层的涂层重量为至多1000mg/m2;
●以超过300℃/s的加热速率加热该涂覆锡的钢基材,接着在513℃-645℃的温度Ta下退火该涂覆锡的钢基材持续退火时间ta:
○以将锡层转化成铁-锡合金层,其包含至少90重量%的FeSn,该FeSn含有50原子%铁和50原子%锡,和
○以同时获得回复的显微组织,并且其中不发生一次冷轧基材的再结晶,即回复退火;
●在至少100℃/s的冷却速率下快速冷却该退火的基材;
●其中该钢以重量%计包含:
○0.05%或更少的碳含量;
○0.004%或更少的氮含量;
○0.05%-0.5%的锰含量;
○0.02%或更少的磷含量;
○0.02%或更少的硅含量;
○0.03%或更少的硫含量;
○0.1%或更少的铝含量;
○任选以下的一种或多种:
●0.001%-0.1%的铌含量;
●0.001%-0.15%的钛含量;
●0.001%-0.2%的钒含量;
●0.001%-0.1%的锆含量;
●5-50ppm的硼含量;
○余量为铁和不可避免的杂质。
2.根据权利要求1的方法,其中铁-锡合金层包含至少95重量%的FeSn。
3.根据权利要求1的方法,其中ta为至多4s。
4.根据权利要求1-3中任一项的方法,其中在还原性气体气氛中进行退火,同时在使用非氧化性或温和氧化性的冷却介质冷却之前将涂覆基材保持在还原性或惰性气体气氛中,从而获得坚固、稳定的表面氧化物。
5.根据权利要求4的方法,其中还原性气体气氛是HNX。
6.根据权利要求1-3中任一项的方法,其中通过水淬火实现快速冷却,其中用于淬火的水具有在室温至80℃之间的温度,并且其中以这样的方式设计淬火过程使得在带材宽度内产生和保持均匀的冷却速率。
7.根据权利要求6的方法,其中用于淬火的水具有在室温至60℃之间的温度。
8.根据权利要求1-3中任一项的方法,其中退火过程包括:
●在含氢的气氛中使用能够产生超过300℃/s的加热速率的感应加热装置,和/或
●接着是保持在退火温度下的均热以使跨带材宽度的温度分布均匀化,和/或
●其中在还原性气体气氛中进行冷却,和/或
●经由通过使用喷射喷嘴的水淬火进行冷却,其中用于淬火的水具有最小的溶解氧含量和/或具有室温至60℃之间的温度,同时通过在淬火之前维持惰性或还原性气体气氛保持具有一个或多个铁-锡合金层的基材屏蔽氧。
9.根据权利要求8的方法,其中退火过程包括:
●在HNX中使用能够产生超过300℃/s的加热速率的感应加热装置。
10.根据权利要求8的方法,其中还原性气体气氛是HNX气氛。
11.根据权利要求8的方法,其中喷射喷嘴是浸没的喷射喷嘴。
12.根据权利要求1-3中任一项的方法,其中基材的一侧或两侧上一个或多个锡层的涂层重量为至少100和/或至多600mg/m2的基材表面。
13.根据权利要求1-3中任一项的方法,其中
●碳含量为至多0.02%,和/或
●铌含量为至少0.02%和/或至多0.08%,和/或
●锰含量为至少0.2%和/或至多0.4%。
14.根据权利要求13的方法,其中铌含量为至少0.03%和/或至多0.06%。
15.根据前述权利要求1-3中任一项的方法,其中涂覆基材还提供有有机涂层,其由热固性材料即漆或热塑性单层或多层聚合物涂层组成。
16.根据权利要求15的方法,其中热塑性聚合物涂层为包含包括使用热塑性树脂的一个或多个层的聚合物涂层体系。
17.根据权利要求16的方法,其中热塑性树脂选自聚酯或聚烯烃、丙烯酸树脂、聚酰胺、聚氯乙烯、氟碳树脂、聚碳酸酯、苯乙烯型树脂、ABS树脂、氯化聚醚、离子聚合物、聚氨酯树脂和功能化聚合物;和/或其共聚物;和/或其混合物。
18.根据前述权利要求1-3中任一项的方法,其中平整轧制该涂覆基材。
19.根据权利要求1-9中任一项的方法制备的包装钢产品,其包含在一侧或两侧上提供铁-锡合金层的低碳、超低碳或极低碳钢回复退火的基材,该铁-锡合金层包含至少90重量%的包含50原子%铁和50原子%锡的FeSn,其中该钢基材以重量%计包含:
○0.05%或更少的C,
○0.004%或更少的N,
○0.05%-0.5%的Mn,
○0.02%或更少的P,
○0.02%或更少的Si,
○0.03%或更少的S,
○0.1%或更少的Al,
○任选以下的一种或多种:0.001%-0.1%的Nb,0.001%-0.15%的Ti,0.001%-0.2%的V,0.001%-0.1%的Zr,5-50ppm的B,
○余量为铁和不可避免的杂质。
20.根据权利要求19的包装钢产品,其中该铁-锡合金层包含至少95重量%的FeSn。
21.根据权利要求19的包装钢产品,其中:
●碳含量为至多0.02%,和/或
●铌含量为至少0.02%和/或至多0.08%,和/或
●锰含量为至少0.2%和/或至多0.4%。
22.根据权利要求21的包装钢产品,其中:
铌含量为至少0.03%和/或至多0.06。
23.根据权利要求19或21-22中任一项的包装钢产品,其中涂覆基材还提供有有机涂层,其由热固性材料即漆或热塑性单层或多层聚合物涂层组成。
24.根据权利要求23的包装钢产品,其中热塑性聚合物涂层为包含包括使用热塑性树脂的一个或多个层的聚合物涂层体系。
25.根据权利要求24的包装钢产品,其中热塑性树脂选自聚酯或聚烯烃、丙烯酸树脂、聚酰胺、聚氯乙烯、氟碳树脂、聚碳酸酯、苯乙烯型树脂、ABS树脂、氯化聚醚、离子聚合物、氨基甲酸乙酯树脂和功能化聚合物;和/或其共聚物;和/或其混合物。
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JP5076544B2 (ja) * | 2007-02-21 | 2012-11-21 | Jfeスチール株式会社 | 缶用鋼板の製造方法 |
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WO2013144321A1 (en) | 2012-03-30 | 2013-10-03 | Tata Steel Ijmuiden Bv | A process for manufacturing a recovery annealed coated steel substrate for packaging applications and a packaging steel product produced thereby |
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