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CN1761772A - 控制金属涂覆带中表面缺陷的方法 - Google Patents

控制金属涂覆带中表面缺陷的方法 Download PDF

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CN1761772A
CN1761772A CNA2004800075534A CN200480007553A CN1761772A CN 1761772 A CN1761772 A CN 1761772A CN A2004800075534 A CNA2004800075534 A CN A2004800075534A CN 200480007553 A CN200480007553 A CN 200480007553A CN 1761772 A CN1761772 A CN 1761772A
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calcium
aluminium
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zinc
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CN100557064C (zh
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韦恩·伦肖
刘启阳
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BHP Steel JLA Pty Ltd
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    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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Abstract

一种控制在以铝－锌－硅合金涂覆的钢带上的″粗糙涂层″和″针孔未涂覆″表面缺陷的方法。该合金具有50－60重量％Al、37－46重量％Zn和1.2－2.3重量％Si。该方法包括在热处理炉(5)中对钢带进行热处理，随后将该带在熔融浴(6)中进行热浸涂覆，并从而在钢带上形成合金涂层。该方法的特征在于将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm。

Description

控制金属涂覆带中表面缺陷的方法
本发明涉及控制在具有耐蚀金属涂层的钢带中的在此所述的表面缺陷，该耐蚀金属涂层是通过将该带在涂层金属的熔融浴中进行热浸涂覆而形成在带上。
本发明特别但不排它地涉及金属涂覆钢带，其可冷成型(例如通过辊轧成型)为最终用途制品(例如屋顶制品(roofing product))。
本发明特别但不排它地涉及具有铝-锌-硅合金涂层的金属涂覆钢带，其可冷成型(例如通过辊轧成型)为最终用途制品(例如屋顶制品)。本申请人对铝-锌-硅合金涂覆的钢带特别感兴趣，该钢带以注册商标ZINCALUME在澳大利亚进行销售并以注册商标GALVALUME在其他国家进行销售。
本发明还特别但不排它地涉及具有带有小海绵尺寸(sponge size)的铝-锌-硅合金涂层的金属涂覆钢带，即涂层具有小于0.5mm级的平均亮金属片(spangle)尺寸。由于亮金属片图样的出现掩盖了缺陷，因而具有较大亮金属片尺寸的涂覆的钢带制品不易于显示出通常的小缺陷。
在这里术语″铝-锌-硅合金″理解为是指包括下列重量百分数范围的元素铝、锌和硅的合金：
铝：50-60
锌：37-46
硅：1.2-2.3
在这里术语″铝-锌-硅″合金也理解为是指可含或不含其它元素的合金，这些元素举例例如铁、钒、铬、和镁中的任意一种或多种。
在常规热浸金属涂层法中，钢带通常经过一个或多个热处理炉，然后进入并通过保持在涂布罐中的熔融涂层金属(例如铝-锌-硅合金)浴。可对这些炉进行排列，以使带水平穿过各炉。还可对这些炉进行排列，以使带垂直穿过各炉并环绕通过一系列上和下导辊。在涂布罐中，通过使用加热感应器，涂层金属通常保持熔融。带通常经过输出端部分离开热处理炉，该输出端部分为浸在浴中的延长的炉出口斜槽或喷嘴(snout)的形式。在浴中，带环绕通过一个或多个导辊(sink roll)并从该浴中向上取出。在离开涂布浴后，带通过涂层厚度控制站(例如气刀或气体擦拭(wiping)站)，带的涂覆表面在该处受到擦拭气体的喷射以控制涂层厚度。然后将涂覆带通过冷却部分并对其进行强制冷却。随后通过将涂覆带相继通过表皮光轧部分(也称为硬化冷轧部分)和张力平整部分，对该冷却的带进行任选地调节。将经调节的带在卷绕站进行卷绕。
本发明特别但不排它地涉及使在用铝-锌-硅合金热浸涂覆的钢带上存在的具体表面缺陷最小化。
本申请人将该具体的表面缺陷描述为″粗糙涂层″和″针孔未涂覆″缺陷。典型地，″粗糙涂层″缺陷是在带的1mm长度上的涂层中具有厚度变化为10微米厚-40微米厚的显著变化的区域。典型的，″针孔未涂覆″缺陷是未涂覆的极小区域(直径＜0.5mm)。
一般来说，本发明提供一种控制在以铝-锌-硅合金涂覆的钢带上的上述类型表面缺陷的方法，其包括下列步骤：将钢带相继通过热处理炉和熔融的铝-锌-硅合金浴，和：
(a)在热处理炉中对钢带进行热处理；和
(b)将该带在熔融浴中进行热浸涂覆，并从而在钢带上形成合金涂层；和
该方法的特征在于将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm。
本发明基于本申请人进行的工作的结果，该结果证明分别或组合使用的锶和钙充分降低上述形成在钢带上的表面缺陷的数量，其中钢带在铝-锌-硅合金的熔融浴中进行热浸涂覆。
本申请人观察到″粗糙涂层″和″针孔未涂覆″表面缺陷总是与其中金属涂层未与钢带进行合金的小区域有关。
虽然不希望受下列说明束缚，本申请人相信在带表面上的氧化物是导致铝-锌-硅合金涂层与钢带在小区域上缺乏合金化的一个因素。本申请人还相信氧化物的一个主要来源是熔融浴的表面。该表面氧化物是由熔融浴中的金属形成的固体氧化物，是熔融浴金属和水蒸气在熔融浴上方的喷嘴中进行反应的结果。在铝-锌-硅合金的熔融浴中，除了铝、锌、和硅外，熔融浴还含有包括镁在内的较少量的其它金属。本申请人相信当带通过氧化层以进入熔融浴时，带上吸收表面氧化物。本申请人已证明锶和钙使浴表面上形成的氧化物的量最小并猜想这些元素可减少能够被带吸收的氧化物的量。本申请人还猜想，锶和钙可选择地或组合地改变表面氧化物的性质并，例如，提高氧化物的强度，从而有较少的可能使氧化物离开浴表面并被带吸附。
上述方法的特征在于在涂层铝-锌-硅合金中蓄意(deliberate)包含元素锶和/或钙。在本发明中，认为这些元素是有益的。
铝-锌-硅合金可包括其它元素。
然而，优选铝-锌-硅合金不含有元素钒和/或铬作为蓄意的合金元素-与以痕量存在相反，例如由于熔融浴中的污染。
在其中熔融浴中含有锶且不含有钙的情况下，优选该方法包括将熔融浴中的锶浓度控制在2-4ppm的范围内。
更优选锶浓度为3ppm。
在其中熔融浴中含有钙且不含有锶的情况下，优选该方法包括将熔融浴中的钙浓度控制在4-8ppm的范围内。
更优选钙浓度为6ppm。
在其中熔融浴中含有锶和钙的情况下，优选该方法包括将熔融浴中的锶和钙的浓度控制为至少4ppm。
优选该方法包括将熔融浴中的锶和钙的浓度控制在2-12ppm的范围内。
优选该方法包括将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为不大于150ppm。
更优选该方法包括将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为不大于50ppm。
本申请人发现对熔融浴中锶和钙的浓度进行控制对含有镁的铝-锌-硅合金具有特别有利的效果。
优选铝-锌-硅合金具有小于1％的镁浓度。
更优选铝-锌-硅合金具有小于50ppm的镁浓度。
可通过任何适宜的方法控制熔融浴中(i)锶或(ii)钙或(iii)锶和钙的浓度。
本申请人优选的一个选择是限定铝中的锶和/或钙的最小浓度，供给该铝以形成用于熔融浴的铝-锌-硅合金。
另一个选择(虽然不是唯一的其它选择)是周期性地以保持浓度在所需浓度所需要的锶和/或钙的量给予(dose)熔融浴。
本发明对于″最小亮金属片″带是特别有利的。
在这里术语″最小亮金属片″带理解为是指在基本穿过带的表面的亮金属片的主要尺寸上，具有小于0.5mm，优选小于0.2mm的亮金属片的金属涂覆带。
标准亮金属片带掩盖了表面缺陷。最小亮金属片带没有掩盖表面缺陷。
可通过任何适宜的方法步骤形成最小亮金属片带，例如Bethlehem SteelCorporation的国际申请PCT/US00/23164(WO01/27343)中所描述的。通过交叉引用在此引入该国际申请说明书中的公开内容。
本发明对于不具有掩盖表面缺陷的表面外观(例如亮金属片带)且未通过重的表皮光轧对该带进行调节以掩盖表面缺陷的钢带，是特别有利的。这种非-重表皮光轧带的实例为经调节使带中具有不大于100MPa残余应力的钢带-如举例来说在本申请人的澳大利亚完整申请43836/01中所描述的。通过交叉引用在此引入该澳大利亚完整申请中的公开内容。
炉可为任何适宜的炉，例如卧式炉或竖式炉。
优选炉具有延伸进浴中的延长的炉出口斜槽或喷嘴。
根据本发明，还提供了以通过上述方法制造的铝-锌-硅合金涂覆的钢带。
参考下列附图，通过实例对本发明作进一步描述：
图1为根据本发明的方法，用于生产以铝-锌-硅合金涂覆的钢带的连续生产线的一个实施方式的示意图
图2为评价在5个月内含有铝-锌-硅合金的熔融浴中锶浓度的曲线图，该熔融浴形成本申请人在Westernport，Victoria的工厂的本申请人的钢带涂布线的一部分；且
图3为在图2曲线图所涵盖的部分时间范围内，通过经过熔融浴将钢带热浸涂覆形成的铝-锌-硅合金涂层中的上述表面缺陷的频率的曲线图。
参考图1，在使用中，将冷轧钢带的卷在展开站1展开，并通过焊机2，将相继展开长度的带首尾相连地焊接并形成连续长度的带。
然后将带相继通过累加器(accumulator)3、带清洁部分4和炉组件5。炉组件5包括预热器、预热还原炉、和还原炉。
通过对下列加工变量进行仔细控制，将带在炉组件5中进行热处理：(i)炉中的温度分布，(ii)炉中的还原气体浓度，(iii)通过炉的气体流速，和(iv)炉中的带停留时间(即线速度)。
控制炉组件5中的加工变量，以便从带表面去除氧化铁残余并从带表面去除残余的油和铁粉。
然后，通过出口喷嘴，将该经热处理的带向下进入并通过含有保持在涂布罐6中的铝-锌-硅合金的熔融浴并以铝-锌-硅合金进行涂覆。优选铝-锌-硅合金含有元素锶和/或钙。优选铝-锌-硅合金不含有元素钒和/或铬。通过使用加热感应器(未示出)，铝-锌-硅合金在涂布罐中保持熔融。在浴中，带环绕通过导辊并从该浴中向上取出。当带通过浴时，在其两面上均以铝-锌-硅合金进行涂覆。
离开涂布浴6后，带垂直通过气体擦拭站(未示出)，在该处对其涂覆表面进行擦拭气体的喷射以控制涂层厚度。
然后，将该涂覆带通过冷却部分7并进行强制冷却。
然后，将该经冷却的、涂覆带(一般为最小亮金属片带)通过用以调节涂覆带表面的轧制部分8。
其后，将该涂覆带在卷绕站10进行卷绕。
上述方法的特征在于将浴中铝-锌-硅合金的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm，更优选至少3ppm，并优选小于150ppm，且更优选小于50ppm。
如上所指出的，在本申请人进行的工作期间，本申请人证实了锶和钙的重要性。
本申请人进行该工作作为研究的一部分，以确定在本申请人的Westernport工厂的铝-锌-硅合金涂布线的生产阶段期间，导致上述缺陷数量出人意料地显著增加的原因。该涂布线生产具有标准亮金属片涂层的钢带。
该研究范围宽且广泛，而且在考虑到浴组成是导致这些表面缺陷的原因前，考虑了显著数量的导致表面缺陷的可能原因。
出人意料地，本申请人确定在涂布线的熔融浴中不存在锶是导致钢带上表面缺陷数量突然增加的原因。
本申请人发现表面缺陷显著增加的开始很好地与涂布线中熔融浴的组成变化相一致。供应用作进料物质以形成用于浴的熔融铝-锌-硅合金的铝锭的公司，对铝锭制造过程进行了改变。在该改变之前，通过该公司供给的铝包括少量的锶作为杂质，其使浴中的锶浓度估计为10-18ppm。该改变将锶完全从铝中去除。
参考图2，在1995年4月18日左右对用于一条生产线的熔融金属的铝锭进料进行了改变。保持该铝锭进料直至7月初。本申请人发现，在4月18日后生产的金属涂覆卷的表面缺陷数量显著增加。为了证实浴中的锶对表面缺陷数量的影响，本申请人决定通过添加铝-10％锶″小锭(piglet)″，向熔融浴中再引入锶。在7月初将该小锭加入熔融浴中。锶对表面缺陷数量具有显著影响。参考图3，标有“加入锶”的箭头指出加入该小锭之前和之后所生产的涂覆钢卷之间的分界线。从图3可以明显看出，在添加该小锭后生产的涂覆卷中有显著更少量的表面缺陷。本申请人进行的进一步研究表明浴的锶浓度应控制为至少2ppm且更优选为至少3ppm。
不脱离本发明的精神和范围，可对上述优选实施方式进行很多改进。

Claims (16)

1.一种控制在以铝-锌-硅合金涂覆的钢带上的在此所述类型的表面缺陷的方法，其包括下列步骤：将钢带相继通过热处理炉和熔融的铝-锌-硅合金浴，和：
(a)在热处理炉中对钢带进行热处理；和
(b)将该带在熔融浴中进行热浸涂覆，并从而在钢带上形成合金涂层；和
该方法的特征在于将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm。
2.权利要求1的方法，其中在该浴含有锶且不含钙的情况下，该方法包括将熔融浴中的锶浓度控制在2-4ppm的范围内。
3.权利要求2的方法，其中熔融浴中的锶浓度为3ppm。
4.权利要求1的方法，其中在熔融浴中含有钙且不含锶的情况下，该方法包括将熔融浴中的钙浓度控制在4-8ppm的范围内。
5.权利要求4的方法，其中钙浓度为6ppm。
6.上述权利要求中任一项的方法，包括将熔融浴中的锶和钙浓度控制在2-12ppm的范围内。
7.上述权利要求中任一项的方法，包括将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为不大于50ppm。
8.上述权利要求中任一项的方法，其中该铝-锌-硅合金不含有元素钒和/或铬作为蓄意的合金元素。
9.上述权利要求中任一项的方法，其中该铝-锌-硅合金含有镁。
10.权利要求7的方法，其中该铝-锌-硅合金具有小于1％的镁浓度。
11.上述权利要求中任一项的方法，包括通过限定铝中的锶和/或钙的最小浓度，对熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度进行控制，该铝被供给以形成用于熔融浴的铝-锌-硅合金。
12.权利要求1-8中任一项的方法，包括通过周期性地以保持浓度在所需浓度所需要的锶和/或钙的量给予熔融浴中，对熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度进行控制。
13.上述权利要求中任一项的方法，其中该铝-锌-硅合金钢带为最小亮金属片带。
14.一种控制在具有铝-锌-硅合金的最小亮金属片涂层的钢带上的在此所述类型的表面缺陷的方法，其包括下列步骤：将钢带相继通过热处理炉和熔融的铝-锌-硅合金浴，和：
(a)在热处理炉中对钢带进行热处理；和
(b)将该带在熔融浴中进行热浸涂覆，从而在钢带上形成合金涂层；和
该方法的特征在于将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm。
15.一种控制在以铝-锌-硅合金涂覆的钢带上的在此所述类型的表面缺陷的方法，其中铝-锌-硅合金含有元素锶和/或钙且不含有元素钒和/或铬，该方法包括下列步骤：将钢带相继通过热处理炉和熔融的铝-锌-硅合金浴，和：
(a)在热处理炉中对钢带进行热处理；和
(b)将该带在熔融浴中进行热浸涂覆，并从而在钢带上形成合金涂层；和
该方法的特征在于将熔融浴中的(i)锶或(ii)钙或(iii)锶和钙的浓度控制为至少2ppm。
16.通过上述权利要求中任一项的方法生产的金属涂覆钢带。
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