CN101952477A - 用于涂覆金属带材的方法和用于实施所述方法的设备 - Google Patents
用于涂覆金属带材的方法和用于实施所述方法的设备 Download PDFInfo
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- 229910052749 magnesium Inorganic materials 0.000 claims description 21
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Abstract
本发明涉及一种用于涂覆金属带材的方法,该方法包括:在真空中将可氧化金属或可氧化金属合金的层沉积在预先涂覆有锌或锌合金的金属带材上,将涂覆的金属带材盘绕,且对卷绕的带材施加静态扩散处理以便获得具有涂层的带材,该涂层在上方部分包含由可氧化金属或可氧化金属合金在锌或锌合金层的全部或部分中扩散所形成的合金层。本发明还涉及用于实施所述方法的设备。
Description
本发明涉及用于涂覆金属带材的方法,其更特别旨在使用基于锌和可氧化的金属元素的层来涂覆钢带材,但绝不仅限于此。
用于在金属表面例如钢带材上沉积由金属层、不同金属或金属合金的若干连续层构成的金属涂层的方法是已知的。其中,可特别提及热浸镀锌,电镀和各种真空沉积方法(蒸发、磁控溅射等)。
例如出于技术或甚至经济原因,某些产品必须以若干层的形式沉积,且必须经历扩散热处理以获得具有所需性能的合金。例如,这可以是用于锌-镁涂层的情形,该涂层可有利地取代纯锌涂层或其它锌合金的涂层。
扩散热处理可证明是复杂且昂贵的。其可包括使用大量的惰性化气体以便抑制在热处理期间因高温所促进的氧化反应。此外,为了避免在沉积可氧化元素和其扩散处理之间的任何氧化风险,必须进行两种操作,在进行一种操作之后立即进行另一种,而不能将带材暴露于露天。
此外,连续的热处理生产线以与扩散所需时间不相容的速度运行。
第一解决方案在于,生产在适中温度下操作的连续处理设备,该设备的长度允许对于发生扩散所需的时间,但该设备因而是庞大且昂贵的,且常常可能没有足够的空间将其安装在已有的生产线上。因此,有试验显示,对于覆盖有1.5μm厚的镁层的锌涂层,在300℃下为完成扩散需要50秒,这表示在此温度下要对以180m/分钟运行的带材保持150m的长度。
这样尺寸的设备并非可容易接受的,而且在工业操作中,因此需要设想较高温度,使用较短的连续处理设备。因此,对于覆盖有1.5μm厚的镁层的锌涂层,将扩散时间限于约10秒是可能的,这表示在此温度下要对以180m/分钟运行的带材保持30m的长度。然而,用于这种动态扩散处理的工作窗口是很窄的,因为一旦达到350-360℃,涂层熔化,穿过共晶相,导致涂层的性能受损。因此,在高容量的生产线上操作该过程是很复杂的,在所述生产线上带材以160-180m/分钟运行。此外,涉及的能量较高,且排除了特定等级钢例如广泛用于汽车工业中的烘烤硬化等级的处理,因为它们的性能将因这样的热处理而受损。
此外,即使通过降低设备的尺寸,仍保持要进行的处理的长度使得连续处理设备必须提供带材支撑辊子或带材导向挡板,这是复杂且昂贵的,因为必须对其进行冷却和设计以便不使形成的层劣化,当带材粘附于辊子上时特别可发生该劣化。
因此,本发明的目的是通过提供一种用于制造金属带材的方法来改正现有技术的缺点,该带材覆盖有基于锌或锌合金和可氧化金属或可氧化金属合金的涂层,该方法消耗极少能量或不消耗惰性化气体,该方法易于实施,其是紧凑的且允许处理各种金属基材。
为此目的,本发明的第一目的由涂覆金属带材的方法构成,其中将可氧化金属或可氧化金属合金的层真空沉积在预涂覆有锌或锌合金的金属带材上,然后将涂覆的金属带材盘绕,且使卷绕的卷材经受静态扩散处理以便获得具有涂层的带材,该涂层在上方部分包含由可氧化金属或可氧化金属合金在锌或锌合金层的全部或部分中扩散所形成的合金层。
根据本发明的方法还可以单独或组合地包含各种任选特征:
-涂层仅包含由可氧化金属或可氧化金属合金在锌或锌合金的层中扩散所形成的合金层;
-涂层包含由锌或锌合金构成的下方层,以及由可氧化金属或可氧化金属合金扩散到锌或锌合金层的一部分所形成的合金层构成的上方层;
-通过热浸镀锌法使金属带材预涂覆有锌或锌合金;
-通过电镀法使金属带材预涂覆有锌或锌合金;
-通过真空沉积法使金属带材预涂覆有锌或锌合金;
-使金属带材预涂覆有具有0.5-15μm,优选0.5-7.5μm且更特别优选0.5-5μm厚度的锌或锌合金层;
-通过真空沉积使锌或锌合金涂覆的金属带材涂覆有镁或镁合金;
-通过真空蒸发来沉积具有0.2-5μm,优选0.2-2μm厚度的镁层;
-在静态扩散退火期间形成合金层,该合金具有任选地含有Zn11Mg2化合物的组合物Zn2Mg;
-在进行所述静态扩散处理之前使涂覆有可氧化金属或金属合金的金属带材上的涂层得到氧化;
-在低于200℃的温度下将金属带材的卷材加热4-40小时的时间;
-金属带材是钢带材且可以由烘烤硬化的钢制成。
本发明的第二目的由用于实施本发明的方法的设备构成,该设备包含:
-用于使所述金属带材镀锌的装置;其后为:
-真空沉积涂覆装置;及
-在受控气氛下工作的静态热处理装置。
根据本发明的设备还可单独或组合地包含以下变体:
-镀锌装置是热浸镀锌装置;
-镀锌装置是电镀锌装置;
-镀锌装置是真空沉积镀锌装置。
本发明的其它特征和优势将通过阅读如下以仅举例说明的方式给出的说明书而变得清楚。
根据本发明的方法更特别但非仅仅地适用于涂覆有锌或锌合金的钢带材的处理。术语“锌合金”意指包含至少50%锌且可能含有例如铝、铁、硅等的任何化合物。
可通过任何镀锌方法获得涂覆的带材,例如,无论是热浸镀锌、电镀还是真空蒸发沉积。然而,优选通过电镀或通过真空蒸发沉积所涂覆的带材,其中涂覆厚度跨钢卷材的整个表面是不变的。
优选地,涂层厚度为0.5-15μm。这是因为,低于0.5μm时,存在着带材的腐蚀防护不足的风险。根据带材的目标应用,涂层的厚度可为至多15μm,但通常其小于7.5μm,因为无需超过此厚度以具有在汽车工业中特别需要的耐腐蚀水平。
当然,根据本发明的方法可与任何其性能不易于在后续热处理期间不可逆地受损的涂覆金属基材一起使用。因此,根据本发明的方法可特别适用于在固溶体中含有大量碳的烘烤硬化的钢带材,所述碳在通过冲压或任何另外合适的方法使带材经受成形操作之前不得完全析出。根据本发明的热处理尽管其温度水平低,在这些等级中存在的固溶体中将析出少量的碳,但在扩散后的表面加工硬化(表皮光轧)处理将恢复这些等级的性能,这对于现有技术的方法将是不可能的。通过在低温下进行静态退火循环,因而能够使热处理与大多数冶金学相容。
首先,通过真空沉积法使锌或锌合金涂覆的金属带材涂覆有可氧化金属或可氧化合金的层。可特别提及磁控溅射、冷等离子体沉积和真空蒸发法,而本发明决不限于此。
使用这样的方法特别使得沉积可氧化金属或金属合金的很薄层成为可能,优选厚度为0.2-5μm。此外,这样的涂覆法允许此附加层在不加热带材的情况下得到沉积,且因此不使其经受在基材和锌层之间的任何不当扩散。
常规地,由金属卷材开始进行可氧化金属或金属合金的沉积,该金属带材在运行通过沉积腔室之前未卷绕。带材运行穿过该腔室,其中涂层得到沉积,然后离开腔室并盘绕,这也是常规的。
可氧化金属可特别由镁构成,当将镁添加到该金属带材的表面涂层中的锌时,其具有显著增强金属带材的耐腐蚀性的优势。在大多数应用中,镁层可限于2μm,这归因于这种在耐腐蚀性方面的显著改善。
在此沉积步骤后,金属带材因而覆盖有其上方为可氧化金属或合金的锌或锌合金层。由于带材是盘绕的且然后存贮而不进行惰性化,所述带材的最外表面在与空气中的氧接触时迅速氧化,因而形成氧化层。
然后,本发明人试图在未卷绕的金属卷材上进行静态退火操作,这使可氧化元素完全恰当地扩散入锌或锌合金层的上方部分成为可能。很出人意料地,氧化层决不阻碍该扩散,这不同于本领域技术人员可能预期的。
此外已证明,正是该氧化层有利于在扩散热处理期间抑制卷材的匝粘附在一起。
当然,仍可通过沉积最终保护层来防护金属带材在涂覆操作和热处理之间的传送和存贮期间免于氧化。然而,进行的实验室试验显示,该防护是非必要的。
在可能为氧化性或非氧化性气氛的气氛中,在常规箱式退火设备中进行静态退火。
特别地,本发明人显示,在氧化性气氛例如空气中的退火处理抑制了带材表面颜色出现某些不均匀性。
正如在未涂覆金属卷材的冶金学退火的情形中,必须根据金属卷材中接受的温度不均匀性来调节温度升高和降低的速率。还根据所需最大温度水平来确定要进行的热循环的其它特性,例如在升温期间的时间,均热时间和冷却的持续期。因而,图1显示了用于处理重2吨的钢卷材的实际热循环的实施例。该图显示了用于静态热处理装置的燃烧器的温度设定和控制。可见,温度升高在14小时内完成,直到达到170℃,此后停止加热且在30小时的总处理时间后逐渐使卷材冷却到55℃。
由于这种退火的持续期通常为4-40小时,达到的最大温度将通常低于200℃。这使得处理大量钢或金属级成为可能,所述钢或金属级对过大温度升高是敏感的且不能经受连续退火。这是因为,保持时间因连续退火操作期间的高运行速度而将显著更高。
在不同温度下,且以匝之间的不同拉紧水平进行静态扩散循环。在对卷材的热处理期间,这些不同的拉紧水平显示,显著高于经受的卷绕应力的标称范围且显著高于标称压力范围时,在匝之间没有粘附。
由这些静态扩散热处理得到的片材揭示了恰当的扩散产物和在涂层表面处的目标合金的形成,以及根据情况的完全或部分扩散。
示例性实施方案
实施例1
通过电镀使15吨的烘烤硬化钢带材的卷材涂覆有2.5μm的锌层,然后通过真空蒸发使该卷材涂覆有1μm的镁层。然后将该带材在露天中经历若干天而无特别防护,从而在最外表面上形成氧化镁层。
然后在160℃下将金属带材进行静态退火处理以便使镁扩散进入锌中。
在静态退火期间使用的惰性化气体是氮/氢混合物,与常规用于低碳钢退火的相同。在热处理期间没有观察到金属卷材的氧化,因为使用了非氧化性惰性气体。
图2显示了带材所经受的热循环。该图还显示了在炉内的气体温度的变化,钢卷材中不同点的温度变化,特别包括最热点和最冷点。
可见,在约14小时的时间内进行了升温。保持在160℃的均热温度持续了约2小时,其间发生了镁扩散。实际上,通过简单地将炉子关闭并将卷材留于其中来获得这种均热保持。到70℃温度的冷却持续了8小时。因而,总的循环时间为约24小时。为了开始冷却,将卷材从炉子中取出,并置于冷却罩中,从而使这些冷却条件得到控制。
因而,所有的镁均与形成第一层的锌的一部分进行了合金化,且获得了具有锌子层和Zn-Mg合金上方层的涂层。卷材的最热点和卷材的最冷点之间的温度差别代表着扩散速率差别限于几个百分点,从而对于涂层性质未产生显著改变。还可在冷却前调节温度均热时间以便允许该扩散速率成为完全均匀的,如果这证明是必要的话。
实施例2
以如同实施例1中相同的方式,通过电镀使两个与上述所用的相同的烘烤硬化钢带材的15吨卷材A和B涂覆有2.5μm的锌层,然后通过真空蒸发使所述卷材涂覆有1μm的镁层。然后将每一带材放在露天中而无任何特别防护,从而在最外表面上形成氧化镁层。
然后在160℃下,在相同的静态退火设备中,将每一金属带材依次进行静态退火处理以便使镁扩散进入锌中。这些卷材经历的热循环与实施例1中的相同,仅仅的处理区别在于为退火卷材B所选用的气氛类型。
卷材A:
在卷材A的静态退火期间使用的气体是与实施例1中所述相同的惰性氮/氢混合物。在热处理期间可观察到关于金属卷材氧化的相同效应。
此外,尽管在实施例1中金属带材的颜色在静态退火处理后是均匀的浅灰色,然而在此情形中在带材边缘出现较暗的晕圈。沿着带材轴的颜色相对于实施例1中所观察到的保持不变。电子显微镜分析显示,在浅区域中,存在于带材表面上的镁微晶具有很尖锐且良好限定的六边形几何形状。相比之下,在暗区域中,存在于带材表面上的镁微晶是变形的且具有不规则的边缘。
补充性研究没有从化学角度揭示出在浅区域和暗区域之间的任何显著区别。
因此,该稍微的颜色不均匀性很可能归因于在暗区域中的带材表面上的镁微晶的变形:这些微晶区别地散射光且产生观察到的可视效应。
由于在研究中的所有参数(钢带材、锌和镁涂层、退火的热特性和气氛)相对于实施例1中那些不变,因此证明,微晶变形的诱因归因于退火设备本身。特别地,根据进行中的生产炉期(campagnes),设备可含有不等量的污染物质,例如来自于轧制油燃烧的碳残余。此外,色彩缺陷的形状(是从边缘开始的振荡形式)使人认为,存在着由包含于退火气氛内的气态物质的匝间扩散所引起的效应。因此,在退火气氛中存在的污染剂与在带材横向(transversal)的热梯度效应结合可解释观察到的现象。
卷材B:
在卷材B的静态退火期间使用的气体是空气。在热处理期间观察到的关于金属带材氧化的效应与在卷材A和在实施例1中所观察到的那些相同。
然而,在此情形中,没有出现色彩缺陷。该带材具有均匀的浅灰色,与实施例1中的相同。此外,电子显微镜观察显示,存在于带材表面上的镁微晶具有很尖锐且良好限定的六边形几何形状,如同卷材A的浅区域。
由于在相同的退火设备中依次处理卷材A和B,后者实验的唯一独特要素是退火气氛,所有的其它参数保持不变(钢带材、锌和镁涂层、退火的热特性)。因此,在空气中进行热处理的事实具有中和热化学效应的效应,所述热化学效应造成了在卷材A上观察到的色彩缺陷的出现(消除污染物等)。
因而显示出,在工业设备上的扩散热处理的情形中,使用氧化性气氛例如空气而非惰性气体作为退火气氛的事实使中和因污染物(例如从先前设备的使用产生)存在所致的热化学效应成为可能,所述热化学效应可能导致在最终产品上出现色彩缺陷。因此,特别能够实施根据本发明的方法而无惰性化。
本发明通过沉积多层使制造包含合金的涂层成为可能,而无需投资于复杂且昂贵的运行中的扩散设备。因此,在涂覆生产线上所需的空间比对于实施生产线内退火所用的设备小约50%。因此,当生产体积是小的或当开始曲线是长且慢时,本发明特别适合于施用在已有生产线上的新产品。
相对于必须施用于连续生产线上的静态热处理,本发明使用了更长时间且在更低温度下的静态热处理。本发明允许使用紧凑工具来实施扩散。其使惰性化气体的消耗最小化或甚至得以消除,且通过降低扩散循环的温度而使每吨的能耗(以及要安装的电源)最小化,从而使处理相容于大范围的钢产品和钢号。
本发明允许使用箱式退火设备或相似的制备工具来进行对于生产目标产品所必须的合金化。通过使用已有的箱式退火工具,可降低投资成本约30%(占包括沉积和热处理的投资),且因而决定投资于且进入较短寿命或较低累积体积的新产品市场。
通过组合方法,可生产新式多层涂层。与扩散热处理组合,这些可产生对于涂覆产品提供有利的表面特性的合金。
因而,构建新的生产车间或补充已有生产车间是必要的。假使其在合金中组合了使用现有设备已沉积的金属且假使该设备在空间和容量方面是可获得的,则第二种情况对于提供新的生产是更适当的。
本发明特别旨在获得锌-镁涂层,但不限于这些涂层,其涵盖任何基于可氧化金属或可氧化合金的涂层。
Claims (18)
1.一种用于涂覆金属带材的方法,其中将可氧化金属或可氧化金属合金的层真空沉积在预涂覆有锌或锌合金的金属带材上,然后将涂覆的金属带材盘绕,且使卷绕的卷材经受静态扩散处理以便获得具有涂层的带材,该涂层在上方部分包含由可氧化金属或可氧化金属合金在锌或锌合金层的全部或部分中扩散所形成的合金层。
2.权利要求1的方法,其中在氧化性气氛中,在卷绕的卷材上进行静态扩散处理。
3.权利要求1的方法,其中在非氧化性气氛中,在卷绕的卷材上进行静态扩散处理。
4.权利要求1-3中任一项的方法,其中通过热浸镀锌法使金属带材预涂覆有锌或锌合金。
5.权利要求1-3中任一项的方法,其中通过电镀法使金属带材预涂覆有锌或锌合金。
6.权利要求1-3中任一项的方法,其中通过真空沉积法使金属带材预涂覆有锌或锌合金。
7.根据权利要求1-6中任一项的方法,其中金属带材预涂覆有厚度为0.5-15μm的锌或锌合金层。
8.根据权利要求1-7中任一项的方法,其中通过真空沉积使锌或锌合金涂覆的金属带材涂覆有镁或镁合金。
9.根据权利要求8的方法,其中通过真空沉积来沉积具有0.2-5μm厚度的镁层。
10.根据权利要求8或9的方法,其中在静态扩散退火期间形成合金层,该合金层具有任选地包含Zn11Mg2化合物的组合物Zn2Mg。
11.根据权利要求1-10中任一项的方法,其中涂覆有可氧化金属或金属合金的所述金属带材上的涂层在进行所述静态扩散处理之前在表面上得到氧化。
12.根据权利要求1-11中任一项的方法,其中通过将金属带材的所述卷材在低于200℃的温度下加热使其进行扩散热处理持续4-40小时。
13.根据权利要求1-12中任一项的方法,其中金属带材是钢带材。
14.根据权利要求13的方法,其中金属带材由烘烤硬化钢制成。
15.用于制造金属带材的设备,该金属带材通过根据权利要求1-14中任一项所述的方法得到涂覆,该设备包含:
-用于使所述裸金属带材镀锌的装置;其后为:
-真空沉积涂覆装置;及
-在受控气氛下工作的静态热处理装置。
16.根据权利要求15的设备,其中所述镀锌装置是热浸镀锌装置。
17.根据权利要求15的设备,其中所述镀锌装置是电镀锌装置。
18.根据权利要求15的设备,其中所述镀锌装置是真空沉积镀锌装置。
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CN104903493A (zh) * | 2012-12-26 | 2015-09-09 | Posco公司 | Zn-Mg合金镀层钢板及其制造方法 |
CN107354424A (zh) * | 2017-08-08 | 2017-11-17 | 常州大学 | 一种抑制高强钢钢板表面选择性氧化的蒸镀锌预处理工艺 |
CN109435362A (zh) * | 2018-09-25 | 2019-03-08 | 首钢集团有限公司 | 一种抗锈蚀冷轧钢板及其制造方法 |
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KR101867732B1 (ko) * | 2016-12-22 | 2018-06-14 | 주식회사 포스코 | 다층구조의 도금강판 및 그 제조방법 |
EP3561147A4 (en) * | 2016-12-26 | 2020-03-25 | Posco | STEEL PLATED WITH ZINC ALLOY WITH EXCELLENT WELDABILITY AND CORROSION RESISTANCE |
KR101940886B1 (ko) * | 2016-12-26 | 2019-01-21 | 주식회사 포스코 | 점용접성 및 내식성이 우수한 아연합금도금강재 |
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Cited By (7)
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CN104903493A (zh) * | 2012-12-26 | 2015-09-09 | Posco公司 | Zn-Mg合金镀层钢板及其制造方法 |
US9744743B2 (en) | 2012-12-26 | 2017-08-29 | Posco | Zn—Mg alloy plated steel sheet, and method for manufacturing same |
CN104903493B (zh) * | 2012-12-26 | 2018-04-24 | Posco公司 | Zn-Mg合金镀层钢板及其制造方法 |
CN107354424A (zh) * | 2017-08-08 | 2017-11-17 | 常州大学 | 一种抑制高强钢钢板表面选择性氧化的蒸镀锌预处理工艺 |
CN107354424B (zh) * | 2017-08-08 | 2019-10-11 | 常州大学 | 一种抑制高强钢钢板表面选择性氧化的蒸镀锌预处理工艺 |
CN109435362A (zh) * | 2018-09-25 | 2019-03-08 | 首钢集团有限公司 | 一种抗锈蚀冷轧钢板及其制造方法 |
CN109435362B (zh) * | 2018-09-25 | 2021-01-15 | 首钢集团有限公司 | 一种抗锈蚀冷轧钢板及其制造方法 |
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US20190040515A1 (en) | 2019-02-07 |
ATE513938T1 (de) | 2011-07-15 |
BRPI0908226B1 (pt) | 2019-02-05 |
WO2009118466A1 (fr) | 2009-10-01 |
CA2715174A1 (fr) | 2009-10-01 |
JP2011515574A (ja) | 2011-05-19 |
PL2098607T3 (pl) | 2011-10-31 |
UA101969C2 (ru) | 2013-05-27 |
CA2715174C (fr) | 2012-05-22 |
US20130061986A1 (en) | 2013-03-14 |
BRPI0908226A2 (pt) | 2017-10-10 |
RU2450085C1 (ru) | 2012-05-10 |
US11313023B2 (en) | 2022-04-26 |
MX2010008992A (es) | 2010-09-10 |
EP2098607B1 (fr) | 2011-06-22 |
ES2365951T3 (es) | 2011-10-13 |
KR20120126132A (ko) | 2012-11-20 |
US10072327B2 (en) | 2018-09-11 |
JP5378419B2 (ja) | 2013-12-25 |
EP2098607A1 (fr) | 2009-09-09 |
KR101249594B1 (ko) | 2013-04-01 |
KR20100126311A (ko) | 2010-12-01 |
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