CN116804274A - 一种锌铝镁合金镀层、锌铝镁合金镀层钢板及其制备方法 - Google Patents
一种锌铝镁合金镀层、锌铝镁合金镀层钢板及其制备方法 Download PDFInfo
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- CN116804274A CN116804274A CN202310742567.5A CN202310742567A CN116804274A CN 116804274 A CN116804274 A CN 116804274A CN 202310742567 A CN202310742567 A CN 202310742567A CN 116804274 A CN116804274 A CN 116804274A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 78
- 239000010959 steel Substances 0.000 title claims abstract description 78
- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- -1 Zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 64
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000007747 plating Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 238000009713 electroplating Methods 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 4
- 238000007772 electroless plating Methods 0.000 claims description 4
- 238000005468 ion implantation Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000000992 sputter etching Methods 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 41
- 239000011247 coating layer Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000004679 hydroxides Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 229910018191 Al—Fe—Si Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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Abstract
本申请涉及涂镀技术领域,尤其涉及一种锌铝镁合金镀层、锌铝镁合金镀层钢板及其制备方法。所述镀层的内部的化学成分包括:Mg、Al以及Zn;所述镀层的表面的化学成分包括如下至少一种:Ni、Cr、Co;其中,Ni、Cr以及Co的分布表面深度≤1μm,所述Ni的含量、所述Cr的含量以及Co的含量满足如下关系式:0.01重量%≤[Ni]+[Cr]+[Co]≤20重量%,式中,[Ni]表示Ni的重量分数,[Cr]表示Cr的重量分数,[Co]表示Co的重量分数。本申请内容解决了现有锌铝镁镀层钢板在大气中使用时,容易出现表面颜色变暗的技术问题。
Description
技术领域
本申请涉及涂镀技术领域,尤其涉及一种锌铝镁合金镀层、锌铝镁合金镀层钢板及其制备方法。
背景技术
锌铝镁镀层钢板是一种新型的高耐蚀合金镀层钢板。这种镀层是在传统纯锌镀层的基础上开发出来,在镀层中加入了镁元素和铝元素,使得镀层的平面耐蚀性与切口耐蚀性显著提高,可以被广泛用于制造汽车、家电、建筑外墙面等。
然而,锌铝镁镀层钢板在大气中使用时,容易出现表面颜色变暗。
发明内容
本申请提供了一种锌铝镁合金镀层、锌铝镁合金镀层钢板及其制备方法,以解决现有锌铝镁镀层钢板在大气中使用时,容易出现表面颜色变暗的技术问题。
第一方面,本申请提供了一种锌铝镁合金镀层,所述镀层的内部的化学成分包括:
Mg、Al以及Zn;
所述镀层的表面的化学成分包括如下至少一种:Ni、Cr、Co;其中,Ni、Cr以及Co的分布表面深度≤1μm,所述Ni的含量、所述Cr的含量以及Co的含量满足如下关系式:
0.01重量%≤[Ni]+[Cr]+[Co]≤20重量%,
式中,[Ni]表示Ni的重量分数,[Cr]表示Cr的重量分数,[Co]表示Co的重量分数。
可选的,所述Mg的含量为0.6~7重量%,所述Al的含量为0.2~60重量%。
可选的,所述镀层的内部的化学成分中还包括:Si;其中,根据所述Al的含量以设定所述Si的含量。
可选的,所述根据所述Al的含量以设定所述Si的含量,包括:
若所述Al的含量≥8重量%,则所述Si的含量与所述Al的含量满足如下关系式:
0.02≤[Si]/[Al]≤0.2
式中,[Si]表示Si的重量,[Al]表示Al的重量。
第二方面,本申请提供了一种锌铝镁合金镀层钢板,所述钢板包括钢基体以及附着于所述钢基体至少部分表面的第一方面任一项实施例所述的镀层。
第三方面,本申请提供了一种锌铝镁合金镀层钢板的制备方法,用于制备第二方面任一项实施例所述的钢板,所述方法包括:
对带钢进行表面活化处理,得到钢基体;
对所述钢基体的至少部分表面进行涂覆锌铝镁合金,后进行表面处理,得到锌铝镁合金镀层钢板。
可选的,所述表面活化处理的方式包括如下至少一种方式:退火、酸洗、离子刻蚀。
可选的,所述涂覆的方式包括电镀、热浸镀、化学镀、气相沉积中的一种。
可选的,所述表面处理包括:在所述含有锌铝镁合金镀层的所述钢基体表面注引入化学成分;其中,所述化学成包括如下至少一种:Ni、Cr、Co。
可选的,所述注引入的方式包括包括气相沉积、离子注入、电镀中的一种。
本申请实施例提供的上述技术方案与现有技术相比具有如下优点:
本申请实施例提供的该锌铝镁合金镀层,镀层中的Mg-Zn化合物在镀层表面存在潮湿水膜的条件下容易与水膜中的氧发生电化学反应,Mg-Zn化合物失去电子析出Mg元素为镁离子,而氧则得到电子变为氢氧根离子。进一步镁离子在液膜中与氢氧根离子以及空气中的二氧化碳反应,形成颜色偏暗的表面氧化物、碳酸盐以及氢氧化物。在上述镀层表面加入惰性较强的金属元素(如Ni、Cr、Co元素),能够显著抑制表面水膜中氧的反应,阻碍氧变成氢氧根离子,从而阻断电化学反应过程,使得不会形成颜色偏暗的表面氧化物、碳酸盐以及氢氧化物。综上,本申请内容解决了现有锌铝镁镀层钢板在大气中使用时,容易出现表面颜色变暗的技术问题。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分,示出了符合本申请的实施例,并与说明书一起用于解释本申请的原理。
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,对于本领域普通技术人员而言,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的一种锌铝镁镀层钢板的镀层表面微观组织图;
图2为本申请实施例提供的一种锌铝镁镀层钢板的镀层截面微观组织图;
图3为本申请实施例提供的一种锌铝镁镀层钢板的制备方法的流程示意图。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚,下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本申请的一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本申请保护的范围。
本申请的各种实施例可以以一个范围的形式存在;应当理解,以一范围形式的描述仅仅是因为方便及简洁,不应理解为对本申请范围的硬性限制;因此,应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如,应当认为从1到6的范围描述已经具体公开子范围,例如从1到3,从1到4,从1到5,从2到4,从2到6,从3到6等,以及所述范围内的单一数字,例如1、2、3、4、5及6,此不管范围为何皆适用。另外,每当在本文中指出数值范围,是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中,在未作相反说明的情况下,使用的方位词如“上”和“下”具体为附图中的图面方向。另外,在本申请说明书的描述中,术语“包括”“包含”等是指“包括但不限于”。在本文中,诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。在本文中,“和/或”,描述关联对象的关联关系,表示可以存在三种关系,例如,A和/或B,可以表示:单独存在A,同时存在A和B,单独存在B的情况。其中A,B可以是单数或者复数。在本文中,“至少一个”是指一个或者多个,“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达,是指的这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a,b,或c中的至少一项(个)”,或,“a,b,和c中的至少一项(个)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。
除非另有特别说明,本申请中用到的各种原材料、试剂、仪器和设备等,均可通过市场购买得到或者可通过现有方法制备得到。
第一方面,本申请提供了一种锌铝镁合金镀层,请参见图1和图2,所述镀层的内部的化学成分包括:
Mg、Al以及Zn;
所述镀层的表面的化学成分包括如下至少一种:Ni、Cr、Co;其中,Ni、Cr以及Co的分布表面深度≤1μm,所述Ni的含量、所述Cr的含量以及Co的含量满足如下关系式:
0.01重量%≤[Ni]+[Cr]+[Co]≤20重量%,
式中,[Ni]表示Ni的重量分数,[Cr]表示Cr的重量分数,[Co]表示Co的重量分数。
镀层中的Mg-Zn化合物在镀层表面存在潮湿水膜的条件下容易与水膜中的氧发生电化学反应,Mg-Zn化合物失去电子析出Mg元素为镁离子,而氧则得到电子变为氢氧根离子。进一步镁离子在液膜中与氢氧根离子以及空气中的二氧化碳反应,形成颜色偏暗的表面氧化物、碳酸盐以及氢氧化物。目前,采用表面处理技术在镀层表面涂覆一层特殊的薄膜,以避免表面形成不利的含Mg化合物是一种解决方法。然而,因为表面处理会导致生产成本的显著上升,同时表面涂覆的薄膜在钢板加工、运输、存储等过程中容易发生破坏,从而失去效果
在本申请实施例中,控制Ni、Cr以及Co的分布表面深度≤1μm,0.01重量%≤[Ni]+[Cr]+[Co]≤20重量%的积极效果:在镀层表面加入惰性较强的金属元素,能够显著抑制表面水膜中氧的反应,阻碍氧变成氢氧根离子,从而阻断电化学反应过程,使得不会形成颜色偏暗的表面氧化物、碳酸盐以及氢氧化物。抑制表面水膜中氧的反应,阻碍氧变成氢氧根离子。若该表面深度或含量过高,在一定程度上会都会导致镀层中的Mg-Zn化合物与Ni、Cr、Co元素之间构成电偶,反而加速Mg-Zn化合物的氧化。同时若含量过高,还会使得锌铝镁镀层耐蚀性能下降,镀层溶液开裂。具体地,该Ni、Cr以及Co的分布表面深度可以为1μm、0.9μm、0.8μm、0.7μm等;[Ni]+[Cr]+[Co]的数值可以为0.01重量%、1重量%、10重量%、15重量%、20重量%等。
在一些实施方式中,所述Mg的含量为0.6~7重量%,所述Al的含量为0.2~60重量%。
控制Mg的含量为0.6~7重量%的积极效果:镀层中的Mg主要是以Mg-Zn化合物形式存在于镀层的共晶组织中,极少量以固溶态形式存在于镀层的富锌相中。锌铝镁镀层中的Mg元素能够显著提高镀层的耐大气腐蚀能力,其机理是:镀层中的Mg在大气环境中会优先溶解到镀层表面的水膜中,在水膜中与溶解的二氧化碳反应,沉淀出致密的保护膜,这种保护膜在中性和弱碱性环境下可以稳定存在,同时还能够促使镀层表面电解质溶液变为弱碱性溶液,从而提高镀层的耐蚀性。若Mg元素含量过高,可能会造成镀层中出现大量的较粗大的Mg-Zn化合物,这种化合物导致镀层开裂,降低镀层的耐腐蚀性与外观质量。具体地,该Mg的含量可以为0.6重量%、1重量%、3重量%、7重量%等。
控制Al的含量为0.2~60重量%的积极效果:锌铝镁镀层中的Al元素为镀层提供高质量的耐大气腐蚀性能,这是由于在腐蚀过程中,Al元素能够在表面形成致密的氧化物以及致密的氢氧化物。若Al的含量过低,则镀层与钢板之间结合力会很差,导致镀层无法使用,降低耐蚀性。若Al的含量过高,会出现镀层开裂问题,同样降低耐蚀性。具体地,该Al的含量可以为0.2重量%、1重量%、10重量%、30重量%、60重量%等。
在一些实施方式中,所述镀层的内部的化学成分中还包括:Si;其中,根据所述Al的含量以设定所述Si的含量。
在一些实施方式中,所述根据所述Al的含量以设定所述Si的含量,包括:
若所述Al的含量≥8重量%,则所述Si的含量与所述Al的含量满足如下关系式:
0.02≤[Si]/[Al]≤0.2
式中,[Si]表示Si的重量,[Al]表示Al的重量。
在本申请实施例中,为了克服镀层容易开裂的问题,当镀层中的Al含量较高时,需要在镀层中添加一定量的Si元素,使得Si能够与镀层中的Al以及钢基板的Fe形成韧性的Al-Fe-Si相,避免Al和钢基板形成大量脆性的Al-Fe化合物,降低镀层开裂风险,提高镀层耐蚀性。若镀层中Al元素含量≥8重量%,则镀层含有Si元素。若Si含量太多,可能会导致大量Mg与Si结合形成Mg-Si化合物,容易导致镀层表面发黑。具体地,该[Si]/[Al]的数值可以为0.02、0.1、0.2等。
第二方面,本申请提供了一种锌铝镁合金镀层钢板,所述钢板包括钢基体以及附着于所述钢基体至少部分表面的第一方面任一项实施例所述的镀层。
该锌铝镁合金镀层钢板含有上述锌铝镁合金镀层,该钢板不仅具有良好的耐蚀性,还具有良好表面质量,在大气中不容易出现表面变暗的现象。
第三方面,本申请提供了一种锌铝镁合金镀层钢板的制备方法,请参见图3,用于制备第二方面任一项实施例所述的钢板,所述方法包括:
S1、对带钢进行表面活化处理,得到钢基体;
S2、对所述钢基体的至少部分表面进行涂覆锌铝镁合金,后进行表面处理,得到锌铝镁合金镀层钢板。
在步骤1中,钢板基材表面进行活化的目的是为了使得钢板基材表面化学活性增强,从而能够与锌铝镁镀层之间形成良好的化学反应。如果不进行活化,镀层与钢板之间的结合力下降,镀层容易开裂,耐蚀性也明显下降。在步骤S1之前,还包括轧制、脱脂。
在一些实施方式中,所述表面活化处理的方式包括如下至少一种方式:退火、酸洗、离子刻蚀。
退火能够让钢板基材表面的轧制应力消失,消除表面扭曲的晶界,让钢板基材表面更加均匀,避免出现局部特别强和特别弱的化学活性点。
酸洗能够清洗掉钢板表面的高轧制应力层,消除表面扭曲的晶界,让钢板基材表面更加均匀,避免出现局部特别强和特别弱的化学活性点。
离子刻蚀可以去除钢板表面的高轧制应力层,消除表面扭曲的晶界,让钢板基材表面更加均匀,避免出现局部特别强和特别弱的化学活性点。
在一些实施方式中,所述涂覆的方式包括电镀、热浸镀、化学镀、气相沉积中的一种。
电镀技术能够将单一金属或者合金均匀涂覆在钢材表面,通过选择合适的电解质盐类以及调节溶液的pH值,得到均匀的镀层。电镀层通常致密性不如热浸镀镀层,但是优于化学镀与气相沉积镀层。通过在电镀液中添加适量的光亮剂和分散剂,能够提高镀层的致密度,从而提高镀层的耐蚀性。锌铝镁镀层可以采用传统的电镀锌工艺技术实现。
热浸镀是传统的镀层涂覆技术,是将钢板基材浸泡到锌铝镁合金镀液中一段时间,然后取出冷却到室温。这种技术实用性强,可以很容易得到锌铝镁镀层,同时镀层的致密性较好,镀层微观组织均匀,但是很难得到厚度小于5微米的镀层。
化学镀技术是将钢板基材浸泡在化学溶液中,化学溶液中的金属离子自动沉积到钢板表面。这种技术可以用于制造锌铝镁合金镀层,得到的镀层组织比电镀更细腻,但是镀层中的氧含量稍高,耐蚀性稍差一些。
气相沉积技术是将高温金属或合金蒸汽或离子沉积到钢板基材表面,得到镀层。这种技术适应性强,可以用于所有金属和合金镀层制造。通过条件沉积速率、钢板温度等参数,可以得到致密的镀层。
在一些实施方式中,所述表面处理包括:在所述含有锌铝镁合金镀层的所述钢基体表面注引入化学成分;其中,所述化学成包括如下至少一种:Ni、Cr、Co。
在一些实施方式中,所述注引入的方式包括包括气相沉积、离子注入、电镀中的一种。
完成锌铝镁合金镀层涂覆后,还需要对镀层进行表面处理。进行表面处理的目的就是为了使得锌铝镁镀层表面富含Ni、Cr、Co元素。具体的注引入的方式可以选择离子注入、气相沉积和电镀技术。上述三种技术都能够将各种技术元素涂覆或者注入到镀层表面,从而使得镀层表面富含Ni、Cr、Co元素。
下面结合具体的实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法,通常按照国家标准测定。若没有相应的国家标准,则按照通用的国际标准、常规条件、或按照制造厂商所建议的条件进行。
表1锌铝镁合金镀层的化学成分
表2锌铝镁合金镀层钢板的制备工艺参数
对按上述实施例和对比例中的工艺参数制备得到的锌铝镁镀层钢板进行腐蚀评价。腐蚀评价的方法是将镀锌钢板放入循环腐蚀试验箱中,进行一周循环腐蚀试验,然后测量试验前后镀层的质量损失,用单位面积上的质量损失量评价镀层耐蚀性。质量损失越少,耐蚀性越好。对锌铝镁镀层钢板进行表面变暗倾向评价。将锌铝镁镀层钢板置于pH值为5的酸性溶液中浸泡60秒,然后用去离子漂洗,再用干燥气流进行干燥处理,测量锌铝镁镀层钢板的表面亮度为L0,然后将样品放入湿热环境中,湿热温度为50℃,相对湿度为60%,放置120小时,然后取出测量表面亮度L1,用L0减去L1,获得亮度变化量ΔL,ΔL越大,表明镀层变暗的倾向越严重。对锌铝镁镀层钢板进行镀层结合力与开裂倾向评价。将锌铝镁镀层钢板折弯90°,弯曲直径等于钢板厚度,然后观察弯曲外缘镀层表面是否存在裂纹。如果存在肉眼可见裂纹,则表明镀层结合力较差,开裂倾向较大。
表3锌铝镁镀层钢板的镀层结合力与开裂倾向评价结果以及腐蚀评价结果
采用本申请实施例的锌铝镁合金镀层钢板,其具有优异的耐黑变性能,亮度变化量ΔL较小,以及优异的耐腐蚀性,镀层结合力较好,开裂倾向较小,而对比例未采用本申请实施方案,其锌铝镁镀层钢板的镀层结合力与开裂倾向评价结果以及腐蚀评价结果较差。
以上所述仅是本申请的具体实施方式,使本领域技术人员能够理解或实现本申请。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下,在其它实施例中实现。因此,本申请将不会被限制于本文所示的这些实施例,而是要符合与本文所申请的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种锌铝镁合金镀层,其特征在于,所述镀层的内部的化学成分包括:
Mg、Al以及Zn;
所述镀层的表面的化学成分包括如下至少一种:Ni、Cr、Co;其中,
Ni、Cr以及Co的分布表面深度≤1μm,所述Ni的含量、所述Cr的含量以及Co的含量满足如下关系式:
0.01重量%≤[Ni]+[Cr]+[Co]≤20重量%,
式中,[Ni]表示Ni的重量分数,[Cr]表示Cr的重量分数,[Co]表示Co的重量分数。
2.根据权利要求1所述的镀层,其特征在于,所述Mg的含量为0.6~7重量%,所述Al的含量为0.2~60重量%。
3.根据权利要求1所述的镀层,其特征在于,所述镀层的内部的化学成分中还包括:Si;其中,根据所述Al的含量以设定所述Si的含量。
4.根据权利要求3所述的镀层,其特征在于,所述根据所述Al的含量以设定所述Si的含量,包括:
若所述Al的含量≥8重量%,则所述Si的含量与所述Al的含量满足如下关系式:
0.02≤[Si]/[Al]≤0.2
式中,[Si]表示Si的重量,[Al]表示Al的重量。
5.一种锌铝镁合金镀层钢板,其特征在于,所述钢板包括钢基体以及附着于所述钢基体至少部分表面的权利要求1-4任意一项所述的镀层。
6.一种锌铝镁合金镀层钢板的制备方法,其特征在于,用于制备权利要求5所述的钢板,所述方法包括:
对带钢进行表面活化处理,得到钢基体;
对所述钢基体的至少部分表面进行涂覆锌铝镁合金,后进行表面处理,得到锌铝镁合金镀层钢板。
7.根据权利要求6所述的方法,其特征在于,所述表面活化处理的方式包括如下至少一种方式:退火、酸洗、离子刻蚀。
8.根据权利要求6所述的方法,其特征在于,所述涂覆的方式包括电镀、热浸镀、化学镀、气相沉积中的一种。
9.根据权利要求6所述的方法,其特征在于,所述表面处理包括:
在所述含有锌铝镁合金镀层的所述钢基体表面注引入化学成分;其中,所述化学成包括如下至少一种:Ni、Cr、Co。
10.根据权利要求9所述的方法,其特征在于,所述注引入的方式包括包括气相沉积、离子注入、电镀中的一种。
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