CN101707942A - 产生和去除针对阴极涂层的临时性保护层的方法 - Google Patents
产生和去除针对阴极涂层的临时性保护层的方法 Download PDFInfo
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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
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Abstract
本发明涉及一种用于产生和去除针对阴极涂层的临时性保护层的方法,特别是用于制备具有优良可涂漆性的表面的硬化钢构件,其中,由可硬化钢合金制成的钢板经预氧化,在预氧化中形成厚度为100-1000nm的FeO层,并接着进行热浸涂,在热浸涂期间涂覆每面厚度为5-20μm,优选7-14μm的锌层,该热浸涂方法和锌浴中的铝含量以如下方式调节:使得在热浸涂期间抑制层中的铝含量调节为0.15-0.8g/m2,优选为0.2-0.5g/m2,接着将该钢板或由其制成的板式构件加热到高于奥氏体化温度的温度,然后以超过临界硬化速度的速度冷却,以导致硬化,其中用于热浸涂的锌浴中的亲氧元素的含量为0.10重量%-15重量%,这些元素在奥氏体化期间在阴极保护层的表面上形成由该亲氧元素的氧化物组成的薄皮,该氧化物层在硬化后通过用干冰颗粒喷射该板式构件而碎裂。
Description
本发明涉及一种用于产生和去除针对在载体金属上的阴极涂层的临时性保护层的方法。
由EP 1561542A1已知一种用于去除构件的层的方法。该层是由有机粘合剂制成并应从基材上去除而不损伤基材的层。为此在该表面上喷射干冰颗粒,以致通过干冰颗粒冲击产生的作用从材料上去除含有机粘合剂的层。通过干冰去除可避免杂质污染,并且不会损害该构件的金属基体。
由EP 1321625B1已知一种去除金属层的方法,该层体系包括金属层和由该金属层涂覆的基材,并且该去除方法是喷射法。该喷射法可以是喷砂法,这时该金属层经强烈冷却,以实现该层相对于基材的低温脆化。
由EP 1034890A2已知一种用各种喷射剂喷射的方法和设备。在此描述了用喷射剂进行磨蚀性喷射处理,该喷射剂的磨蚀作用处于在标准条件下呈流体形式存在的喷射剂的作用和在标准条件下呈固体聚集态存在的喷射剂的作用之间。其中使用由第一种喷射剂如干冰和第二种磨蚀喷射剂如砂的混合物。
由DE 19946975C1已知一种用于从基材上去除涂层的设备和方法,据信,其适合材料保护,并不仅适合去除软质涂层也适合去除硬质涂层。这时应通过致冷剂喷射进行冷处理导致涂层脆化,并接着用加工工具进行磨蚀性净化处理,与现有技术的加工工具相比,通过冷处理后可使用硬度较小的工具部件进行机械磨蚀性加工。
由DE 19942785A1已知一种用于去除固体加工残渣、表面涂层或氧化物层的方法,其中仅在存在固态加工残渣的区域需进行净化。该净化可用蒸汽喷射、干冰喷射或技术感应冲击波即所谓的激光净化器进行。该CO2净化可通过本身已知的干冰丸粒进行。
由DE 10243035B4已知一种通过加热和冷却来去除在金属件上形成的层的方法和设备。因为例如在去除金属工件上和特别是具有不平整表面的金属工件如轴构件和汽车车身构件上的氧化皮、氧化物硅酸盐(Oxydsilikat)和渣层时,在磨蚀性压缩气体喷射中的固体细粒并不是在所有情况下都能完全从金属工件上去除,用于将例如干冰细粒施加到待净化的金属工件上的压缩气体流应当经预热并处于大于该金属工件周围空气的温度和/或大于该金属工件的表面温度的温度。由此据信实现了,一方面该金属工件不会降温过于厉害,另一方面该压缩气体至少基本上不含湿汽,由此还避免形成不合意的冷凝物。该有待从该金属件表面去除的层通过具有高速冲击并由此具有磨蚀作用的干冰细粒以及通过由干冰细粒产生的表面和层的受限于局部的冷却而去除。
由本申请人的WO 2005/021822中已知,为保护阴极腐蚀保护层,在形成阴极保护层的金属中添加一定量的亲氧元素,以在用该经阴极保护的金属制备的构件硬化时起保护该阴极保护层的作用.为硬化这类构件,必需将该构件加热到超过该基底金属(在该情况下是钢)的奥氏体化温度.特别是高度可硬化的钢的情况下,该温度高于800℃.在此温度下,大部分阴极保护层经蒸发或氧化而受损,以致这种经处理过的构件在硬化后将不具有阴极保护.加入亲氧元素导致该亲氧元素由阴极保护层组合物中扩散到表面,并在表面形成非常优质的保护层.该非常优质的保护层例如可由氧化镁或氧化铝或其混合物组成.此外,由WO2005/021820还已知在辊压成型(Rollprofilieren)中应用此类方法.
本发明的目的在于提供一种方法,用此法可改进在有阴极保护层的硬化钢构件上的漆粘附性。
该目的是借助权利要求1的特征部分实现的。
有利的扩展方案列于从属权利要求中。
由本发明看出,在特定的前提下,在有优质的表面保护涂层的阴极腐蚀保护层情况下该漆粘附性不可最佳化。另一方面,也无其它方法以形成这种薄层,因为否则的话仅能对这种构件实施再镀锌,但这非常复杂和昂贵。
此外还发现,在特定情况下,适于阴极保护层的这种保护层使得难以进行针对涂漆的磷酸盐预处理。
因此,按本发明该优质保护层由一种或多种亲氧元素如此形成,以致其可再次经去除,即仅临时性存在,以在加热超过奥氏体化温度即灼烧期间确保该阴极层受保护。
根据本发明,该薄保护层由至少一种亲氧元素的氧化物如此形成,以致在该层上形成裂纹和/或缺陷。该裂纹可使由裂纹和/或缺陷所围成的氧化物鳞片经干冰喷射而脱离。
但在具有由亲氧元素氧化物制成的保护层的最新的阴极保护涂层的情况下,通常的喷砂是失效的,或者说仅可受限地使用,因为该通常的磨蚀类净化方法将清除该阴极层的大部分。此外,该喷砂对构件的尺寸精确性不利,并还需再净化。
按本发明,仅用无添加剂的干冰喷射,该干冰颗粒通过裂纹和/或缺陷进入保护层下的空隙中,并以至多800倍的体积增加进行升华。由此使由一种或多种亲氧元素的氧化物组成的潜在松脱或待松脱的颗粒与其上任选存在的氧化锌颗粒一起碎裂。由深冷的干冰颗粒产生的附加热冲击导致在由一种或多种亲氧元素的氧化物组成的层中进一步的热应力,并因此有助于所需的去除。但应避免和必须避免磨蚀性的去除,因为由此会侵蚀阴极保护层。
该合意的和对阴极腐蚀保护必需的锌或锌-铁层不会受此影响,并且也不会被去除。因此用本发明方法可选择性去除粘附性差的氧化物。与之相反,在表面上粘附性好的氧化物保留在该表面上,并对可涂漆性也无不利影响。
本发明已经证实,为了在该层上形成裂纹需一些方法步骤,这些步骤本身在该构件上产生阴极层之前早已实施。虽然在优质保护层下总是形成空隙,这归因于在辐射炉中灼烧时在阴极腐蚀保护层中所进行的铁-锌反应,而根据本发明能够发现,由一种或多种亲氧元素的氧化物组成的优质保护层的厚度和裂纹取决于该空白钢带的预处理和在热浸涂时其对锌和钢基材之间的界面动力学或界面形成的影响和取决于锌覆层。
预处理意指该空白钢带的预氧化,如在DE 10059566B3和EU-研究报告Nr.7210-PA/118中所述。这种处理是常用的,目的是使高强度的钢的性能最佳化。由此改进了锌覆层在热浸涂时的粘附特性,特别是在含有高合金成分的钢带情况下。
接着该抑制层形成对优质保护层的厚度和裂纹产生影响。通过在锌浴中加铝在连续的热浸涂时和在任选的后续热处理期间在钢基材和锌层之间产生的层称为抑制层。抑制层的目的通常是阻止铁和锌之间形成强烈的合金化或起反应。
如果形成的抑制层太厚,则在加热超过奥氏体化温度时锌与铁的反应变缓,在其上存在的和更易生长的由一种或多种亲氧元素的氧化物组成的层仅稍微或完全不会由所形成的铁-锌相而受损.因此该优质保护层的厚度仅缓慢生长,并也不导致强的裂纹形成,因为更薄的Al2O3层如薄皮一样盖在铁-锌相上。如果锌覆层选得太厚,也会产生同样效应。
下面按附图示例性说明本发明。
附图简介:
图1示出本发明的层结构,该结构可用本发明方法顺利制备;
图2示出不易净化的表面的对比图;
图3以扫描电子显微镜俯视图示出图1的易于净化表面;
图4以扫描电子显微镜照片示出图2的难于净化表面的俯视图;
图5根据图3的样品在根据本发明净化步骤后的表面;
图6示出实施净化方法后的图4表面;
图7示意性示出根据本发明的净化方法。
图1中所示的由于热处理或硬化在Al2O3保护层中产生裂纹和/或缺陷的表面是最适宜用干冰净化的。该干冰颗粒通过所形成的裂纹进入Al2O3层下的空隙中,并在其中发生前述的升华。该干冰净化是如此进行的,即该干冰颗粒不侵蚀在Al2O3层下的铁-锌层,并且甚至不破裂牢固粘附在铁-锌层上以致其对可涂漆性不产生问题的颗粒。如在图1中明显看出,满足了所需要求,按此在Al2O3层下必须存在空隙,该Al2O3层必须具有一定的厚度,此外还必须存在裂纹。此外,熔融液态锌可通过裂纹蒸发,其中与空气氧反应形成氧化锌并再冷凝在Al2O3保护层上。与此相反,在图2中看出,不仅该铁-锌层的起伏较小,而且该Al2O3层具有较大的封闭区域,该封闭区域延伸超过由该铁-锌层的起伏引发的空隙。与此相应地,在裂纹区也形成更少量的氧化锌。因为部分空隙由Al2O3层所覆盖,通过在空隙中的升华不可能导致破裂。
在图3和4中借助电子显微镜以俯视图示出在图1和2中示意性示出的状态。在该两种情况下均为1.0mm厚的板,其在辐射炉中于910℃下灼烧250秒,并接着在冷却钢板之间硬化。图4示出厚的抑制层形成和/或太厚的锌覆层情况下经硬化后的表面。因为在此情况下,该Al2O3保护层较薄,所以电子辐射能容易地穿透该层。因此在Al2O3保护层下面存在的空隙在照片中呈深色区域示出,因为这里较少来自Al2O3保护层的反射散射电子对探测器信号作出贡献。
如果氧化铝厚较厚并以较多裂纹的形式附着,则在扫描电子显微镜中看出无暗斑的连续Al2O3层。在图3中示出的情况下,该Al2O3层的厚度约为150nm-200nm。该图3所示的状态是合意的状态,而在图4中所示的不合意状态对应于图2的状态。
图5示出图3的表面,该表面经本发明净化法处理。该铁-锌相非常好地出现。不再能看到大面积的Al2O3覆层和氧化锌覆层。按本发明形成的表面可很好地经磷酸盐化后处理或以其它方法后处理,并显示出非常好的漆粘附性。
在图6中示出在实施干冰净化处理后的图4的表面。该较暗的区域表示未经去除的Al2O3和仅能得到可涂漆性差的表面。
本发明方法示于图7,其中用干冰喷枪将干冰颗粒施加到Al2O3层、到达空隙并在那里升华.通过升华时的巨大体积膨胀将Al2O3鳞片与其上粘附的氧化锌成分一起松脱,以致留下具有粗糙度的铁-锌层(见图5)。
按本发明,该预处理和热浸涂如此进行,以使在预氧化时的FeO层厚度大于100nm但小于1000nm,并优选形成抑制层,该抑制层的铝含量为0.15g/m2-0.4g/m2。在辐射炉中加热超过奥化体化温度时,导致锌-铁反应增强,该导致Al2O3保护层破裂。较高的铝含量导致图4所示状态。较低的铝含量导致不完全形成抑制层,并导致在镀锌过程中已发生的锌-铁反应。其又导致冷成型时锌会剥落。
此外,实施本发明方法的锌覆层优选在Z100-Z200即每面7-14μm是有利的。较厚覆层下会延缓锌-铁相直至表面的穿透反应,由此该Al2O3层仅稍微受损,并因此留下薄层。在较薄覆层下该阴极腐蚀保护层可能太小。
此外,最通常的方法是通过增加Al2O3保护层中裂纹和/或缺陷,以通过氧扩散从下而上生长该Al2O3保护层。较厚的Al2O3保护层由于在加热到超过奥氏体化温度时的热应力更易产生裂纹。较薄的Al2O3保护层会在加热到超过奥氏体化温度时在Al2O3保护层中形成更少的裂纹,并且少量氧扩散导致在锌-铁混合相上的薄的Al2O3-皮。
下面将用实施例说明本发明。
实施例1:
厚1.0mm的由22MnB5-钢制成的板经预氧化和在锌浴中用约0.2重量%的铝进行热浸涂。该预氧化要将FeO层厚调到大于100nm且小于1000nm。该镀锌要使锌覆层达Z200即每面14μm。该抑制层的铝含量调到0.3g/m2。接着将该板放入910℃的空气气氛的热辐射炉中4分钟。结果形成图3和5或图1的层。该层可经干冰容易地净化,并产生图5的表面,并在随后的试验中具有相应好的漆粘附性。
实施例2:
厚1.0mm的由22MnB5-钢制成的板经预氧化和在锌浴中用约0.2重量%的铝进行热浸涂。该空白钢板的预氧化要将FeO层厚调到大于100nm且小于1000nm。该镀锌要使锌覆层达Z200即每面14μm。该抑制层的铝含量调到0.8g/m2,并且灼烧条件如实施例1。结果得到含更少氧化锌的富氧化铝表面,其用干冰仅可达差的净化。结果该表面相应于图6或净化前相应于图4,在接着的涂漆试验中由于大面积的Al2O3覆层即产生差的漆粘附性。
实施例3:
相应于实施例1和2的薄钢板上形成锌覆层Z300即每面21μm以代替锌覆层Z200。该空白钢带的预氧化也要将FeO层厚调到大于100nm且小于1000nm。该抑制层的铝含量调到0.3g/m2。接着将该板放入910℃的空气气氛的热辐射炉中4分钟。结果也得到含更少氧化锌的非本发明的富氧化铝表面,其难于用干冰的净化,并且相应于图4的表面。在接着的涂漆试验中也产生差的漆粘附性。
本发明的优点是提供了一种用于产生和去除针对阴极涂层的临时性保护层的方法,用此方法成功地得到具有阴极保护层的硬化的钢构件,其中该阴极保护层在氧化前加热时和特别是生成氧化皮时保护钢,并在以简单方式对钢构件进行热处理和硬化后得到非常好的可涂漆表面。
Claims (3)
1.用于产生和去除针对阴极涂层的临时性保护层的方法,特别是用于制备具有优异可涂漆性的表面的硬化钢构件,其中,由可硬化钢合金制成的钢板经预氧化,在预氧化过程中形成厚度为100-1000nm的FeO层,并接着进行热浸涂过程,在热浸涂过程中施加每面厚度为5-20μm,优选7-14μm的锌层,其中该热浸涂过程和锌浴中的铝含量以如下方式调节:使得在热浸涂过程期间抑制层中的铝含量调节为0.15g/m2-0.8g/m2,优选为0.2g/m2-0.5g/m2,接着将该钢板或由其制成的板式构件加热到高于奥氏体化温度的温度,然后以超过临界硬化速度的速度冷却,以导致硬化,其中用于热浸涂过程的锌浴中的亲氧元素的含量为0.10重量%-15重量%,这些元素在奥氏体化期间在阴极保护层表面上形成由该亲氧元素的氧化物组成的薄皮,且在硬化后该氧化物层通过用干冰颗粒喷射该板式构件而碎裂。
2.权利要求1的方法,其特征在于,在锌浴中使用镁和/或硅和/或钛和/或钙和/或铝和/或锰和/或硼作为亲氧元素。
3.上述权利要求之一的方法,其特征在于,该亲氧元素是铝,并且该铝形成氧化铝的薄皮。
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Cited By (4)
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CN102380491A (zh) * | 2011-08-01 | 2012-03-21 | 迪普干冰制造(大连)有限公司 | 一种加热吸尘搭配干冰清洗的表面脱漆处理设备及方法 |
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Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102007061489A1 (de) * | 2007-12-20 | 2009-06-25 | Voestalpine Stahl Gmbh | Verfahren zum Herstellen von gehärteten Bauteilen aus härtbarem Stahl und härtbares Stahlband hierfür |
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EP2474649A1 (de) * | 2011-01-05 | 2012-07-11 | Voestalpine Stahl GmbH | Verfahren zur Oberflächenbehandlung eines schutzbeschichteten Substrats |
JP6509483B2 (ja) * | 2013-09-03 | 2019-05-08 | 昭和電工ガスプロダクツ株式会社 | 溶断装置 |
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EP3499548B1 (en) * | 2016-08-09 | 2024-01-31 | Sintokogio, Ltd. | Deposit removing method |
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JP6751530B2 (ja) * | 2017-03-17 | 2020-09-09 | 新東工業株式会社 | 付着物除去方法 |
US11613789B2 (en) | 2018-05-24 | 2023-03-28 | GM Global Technology Operations LLC | Method for improving both strength and ductility of a press-hardening steel |
CN112534078A (zh) | 2018-06-19 | 2021-03-19 | 通用汽车环球科技运作有限责任公司 | 具有增强的机械性质的低密度压制硬化钢 |
US11530469B2 (en) | 2019-07-02 | 2022-12-20 | GM Global Technology Operations LLC | Press hardened steel with surface layered homogenous oxide after hot forming |
EP3872229A1 (de) * | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Verfahren zum herstellen gehärteter stahlbauteile mit einer konditionierten zinklegierungskorrosionsschutzschicht |
EP3872231A1 (de) | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Verfahren zum konditionieren der oberfläche eines mit einer zinklegierungs-korrosionsschutzschicht beschichteten metallbandes |
EP3872230A1 (de) | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Verfahren zum herstellen gehärteter stahlbauteile mit einer konditionierten zinklegierungskorrosionsschutzschicht |
DE102022116082A1 (de) | 2022-06-28 | 2023-12-28 | Voestalpine Metal Forming Gmbh | Verfahren zum Konditionieren der Oberflächen von wärmebehandelten, verzinkten Stahlblechen |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU1240412A1 (ru) * | 1984-09-01 | 1986-06-30 | Ленинградское Адмиралтейское объединение | Устройство дл очистки поверхностей |
JP2782451B2 (ja) * | 1989-03-28 | 1998-07-30 | 新日本製鐵株式会社 | 高耐食性重畳めっき鋼板 |
JPH06269839A (ja) * | 1993-03-23 | 1994-09-27 | Sumitomo Metal Ind Ltd | 鋼片のスケール除去法および圧延法 |
JPH10140311A (ja) | 1996-11-14 | 1998-05-26 | Nkk Corp | 熱延鋼板の溶融めっき方法および溶融めっき設備 |
JPH1150284A (ja) * | 1997-07-31 | 1999-02-23 | Mitsubishi Heavy Ind Ltd | 鋼板の脱脂方法及び装置 |
EP1034890A3 (de) | 1999-03-05 | 2000-12-20 | Linde Gas Aktiengesellschaft | Verfahren und Vorrichtung zum Bestrahlen mit verschiedenartigen Strahlmitteln |
DE19942785A1 (de) | 1999-09-08 | 2001-03-22 | Thyssen Krupp Automotive Ag | Verfahren zum Entfernen von festen Bearbeitungsrückständen, Oberflächenbeschichtungen oder Oxidschichten |
EP1321625B1 (en) * | 2001-12-21 | 2004-09-22 | Siemens Aktiengesellschaft | Method for removing a metallic layer |
DE10243035B4 (de) | 2002-09-17 | 2006-01-05 | Daimlerchrysler Ag | Verfahren und Vorrichtung zum Entfernen von durch Erhitzung und Abkühlung auf Metallwerkstücken sich bildenden Schichten |
PL2177641T3 (pl) * | 2003-07-29 | 2013-09-30 | Voestalpine Stahl Gmbh | Blacha stalowa z ocynkowaną ogniowo warstwą ochrony przeciwkorozyjnej |
EP1561542A1 (de) * | 2004-02-03 | 2005-08-10 | Siemens Aktiengesellschaft | Verfahren zur Entfernung einer Schicht eines Bauteils |
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- 2008-01-30 WO PCT/EP2008/000721 patent/WO2008138412A1/de active Application Filing
- 2008-01-30 CN CN200880015734XA patent/CN101707942B/zh active Active
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103124802A (zh) * | 2010-08-19 | 2013-05-29 | 沃斯特阿尔派因钢铁有限责任公司 | 用于调理硬化的防腐蚀的钢板构件表面的方法 |
CN102380491A (zh) * | 2011-08-01 | 2012-03-21 | 迪普干冰制造(大连)有限公司 | 一种加热吸尘搭配干冰清洗的表面脱漆处理设备及方法 |
CN104334764A (zh) * | 2012-04-25 | 2015-02-04 | 安赛乐米塔尔研发有限公司 | 用于生产具有涂油Zn-Al-Mg涂层的金属板的方法和对应的金属板 |
CN104334764B (zh) * | 2012-04-25 | 2017-07-14 | 安赛乐米塔尔研发有限公司 | 用于生产具有涂油Zn‑Al‑Mg涂层的金属板的方法和对应的金属板 |
US10294558B2 (en) | 2012-04-25 | 2019-05-21 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having oiled Zn—Al—Mg coatings, and corresponding metal sheet |
US10865483B2 (en) | 2012-04-25 | 2020-12-15 | Arcelormittal | Metal sheet having oiled Zn—Al—Mg coatings |
CN109551372A (zh) * | 2018-11-07 | 2019-04-02 | 广州供电局有限公司 | 变电站内腐蚀钢结构件的修复方法 |
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Publication number | Publication date |
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EP2013372B1 (de) | 2012-03-14 |
JP5226067B2 (ja) | 2013-07-03 |
US9822436B2 (en) | 2017-11-21 |
ES2382496T3 (es) | 2012-06-08 |
EP2013372A1 (de) | 2009-01-14 |
KR101448188B1 (ko) | 2014-10-07 |
ATE549429T1 (de) | 2012-03-15 |
DE102007022174B3 (de) | 2008-09-18 |
KR20100017770A (ko) | 2010-02-16 |
WO2008138412A1 (de) | 2008-11-20 |
CN101707942B (zh) | 2012-08-22 |
JP2010526937A (ja) | 2010-08-05 |
US20110139308A1 (en) | 2011-06-16 |
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