CN116113719A - 镀敷钢板 - Google Patents
镀敷钢板 Download PDFInfo
- Publication number
- CN116113719A CN116113719A CN202180051908.3A CN202180051908A CN116113719A CN 116113719 A CN116113719 A CN 116113719A CN 202180051908 A CN202180051908 A CN 202180051908A CN 116113719 A CN116113719 A CN 116113719A
- Authority
- CN
- China
- Prior art keywords
- steel sheet
- plating layer
- phase
- plated steel
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 106
- 239000010959 steel Substances 0.000 title claims abstract description 106
- 238000007747 plating Methods 0.000 claims abstract description 130
- 229910017706 MgZn Inorganic materials 0.000 claims abstract description 46
- 229910018137 Al-Zn Inorganic materials 0.000 claims abstract description 34
- 229910018573 Al—Zn Inorganic materials 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 210000001787 dendrite Anatomy 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 98
- 238000000576 coating method Methods 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 53
- 239000012535 impurity Substances 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- 239000012071 phase Substances 0.000 description 89
- 230000007797 corrosion Effects 0.000 description 64
- 238000005260 corrosion Methods 0.000 description 64
- 239000011701 zinc Substances 0.000 description 46
- 238000001816 cooling Methods 0.000 description 23
- 239000011777 magnesium Substances 0.000 description 23
- 230000005496 eutectics Effects 0.000 description 20
- 238000000137 annealing Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 11
- 229910000765 intermetallic Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 description 7
- 239000008397 galvanized steel Substances 0.000 description 7
- 238000010583 slow cooling Methods 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- 229910018134 Al-Mg Inorganic materials 0.000 description 4
- 229910018467 Al—Mg Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910004860 CaZn Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910004706 CaSi2 Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
该镀敷钢板具有钢板和镀层,该镀层被形成于所述钢板的表面的至少一部分,所述镀层的化学组成以质量%计,含有Al:6.00~35.00%、Mg:3.00~15.00%、La+Ce:合计0.0001~0.5000%、以及Zn,关于所述镀层,在表面中,(Al-Zn)相和MgZn2相层状地排列的层状组织的面积率为10~95%,所述层状组织的层状间隔为2.5间隔以下,(Al-Zn)枝晶的面积率为10%以下。
Description
技术领域
本发明涉及一种镀敷钢板。
本申请基于2020年10月20日于日本申请的日本特愿2020-175786号来主张优先权,并将其内容援引于此。
背景技术
近年来,对于汽车结构构件,从防锈的观点出发,使用了镀敷钢板,主要在日本国内市场中,应用了合金化热浸镀锌钢板等热浸镀锌钢板。合金化热浸镀锌钢板为一种如下的镀敷钢板:在对钢板实施热浸镀锌后,进行合金化热处理,使Fe从钢板(基底钢板)扩散到镀层内,由此提高了焊接性及涂装后耐腐蚀性。然而,针对热浸镀锌钢板,需要涂装后耐腐蚀性及耐红锈性等进一步的耐腐蚀性的提高。
作为使热浸镀锌钢板的耐腐蚀性提高的方法,可举出向Zn系镀层添加Al。例如,在建材领域中,作为高耐腐蚀性镀敷钢板,热浸镀Al-Zn系镀敷钢板被广泛地实用化。这样的热浸镀Al-Zn系的镀层由从熔融状态最初结晶的枝晶状的α-(Zn,Al)相(Al初晶部:在Al-Zn系二元状态图等中,作为初晶而结晶的α-(Zn,Al)相。不一定为富Al相,作为Zn和Al的固溶体而结晶)、以及由形成于枝晶状的Al初晶部的间隙的Zn相和Al相构成的组织(Zn/Al混相组织)形成。因为Al初晶部钝化,且与Al初晶部相比,Zn/Al混相组织的Zn浓度较高,所以腐蚀会集中于Zn/Al混相组织。作为结果,腐蚀在Zn/Al混相组织中虫蛀状地进展,腐蚀进展路径变得复杂,因此腐蚀会难以容易地到达基底钢板。由此,与镀层的厚度相同的热浸镀锌钢板相比,热浸镀Al-Zn系镀敷钢板具有更优异的耐腐蚀性。
在将这种热浸镀Al-Zn系镀敷钢板作为汽车外板面板来使用的情况下,镀敷钢板在以连续式熔融镀敷设备中实施了镀敷的状态下被供给到汽车制造商等,因此一般在加工为面板部件形状后,实施化学转化处理,再实施电沉积涂装、中涂涂装、上涂涂装这些汽车用综合涂装。然而,关于使用了热浸镀Al-Zn系镀敷钢板的外板面板,在涂膜中发生了损伤时,由于由上述Al初晶部和Zn/Al混相组织这两相构成的独特的镀敷相结构,导致Zn的优先溶解(Zn/Al混相组织的选择腐蚀)会以伤部为起点在涂膜/镀敷界面中发生。其会向涂装完整部的深处进展,引发较大的涂膜膨胀,结果会存在无法确保足够的耐腐蚀性(涂装后耐腐蚀性)这样的问题。
以耐腐蚀性提高为目的,也在探讨向Al-Zn系镀中进一步添加Mg等元素。然而,因为推测为即使添加Mg,在热浸镀Al-Zn系镀敷钢板中也依然会形成具有钝化皮膜的Al初晶部,所以在实施了涂装后,涂膜中发生损伤时的耐腐蚀性(涂装后耐腐蚀性)的问题未被解决。
针对这样的问题,在专利文献1中,公开了一种涂装后耐腐蚀性优异的热浸镀Zn系镀敷钢板。在专利文献1中,公开了:在镀层含有Zn、Al、Mg及Si,且镀层中含有以面积率的合计值计5%以上的、层状Zn相与层状Al相交替排列的层状组织的情况下,进行了涂装的状态下的涂膜膨胀会被抑制。
在专利文献2中,公开了一种热浸镀Al-Zn系镀敷钢板,其特征在于,具有镀层,该镀层以质量%计,含有Al:25~90%及Sn:0.01~10%,还含有从由Mg、Ca及Sr构成的组中选择的一种以上合计0.01~10%。在专利文献2中,公开了:由于Sn,使得被形成于上述α-Al相的周围的Al氧化膜被破坏,α-Al相的溶解性上升,因此会发生α-Al相和富Zn相这两者溶解的镀层的均匀腐蚀,由此能够抑制富Zn相的选择腐蚀,涂装后耐腐蚀性会提高。
此外,在专利文献3中,公开了一种化学转化处理钢板,其以
〔Al/Zn/Zn2Mg的三元共晶组织〕占镀层最表面的比例为60面积%以上的熔融Zn-Al-Mg合金镀敷钢板为基材,镀层表面由化学转化皮膜覆盖。
此外,在专利文献4中,公开了一种锌系合金镀敷钢板,其具有Zn-Al系合金镀层,该Zn-Al系合金镀层含有Al:0.18~5%,还含有Mg:0.01~0.5%、La:0.001~0.5%、以及Ce:0.001~0.5%中的任意1种或2种以上,剩余部分由Zn构成。在专利文献4中,公开了:Zn-Al-Mg系、Zn-Al-Mg-Si系等锌系合金镀层与以往的Zn系镀层相比,耐腐蚀性更高。
汽车用部件有时会在水会积存的环境下被使用,需要在那样严酷的环境下也具有足够的耐腐蚀性。本发明人们进行了研究,结果得知:含一定量以上的Al的Zn-Al-Mg系镀层具有优异的牺牲防蚀性,另一方面,在水会积存的环境下,易发生涂膜剥离,涂装后耐腐蚀性会存在问题。然而,在专利文献1~4中,针对这种严酷的环境下的涂装后耐腐蚀性,并未进行考虑。
此外,在专利文献1的技术中,需要为了组织控制而实施复杂的热历程的处理,也会存在制造成本増加这样的问题。
此外,在专利文献2的镀敷钢板中,与汽车用电沉积涂膜的密接性会变差。此外,在专利文献2中,必须进行Sn添加,因此也会存在合金成本増加,进而镀浴的管理变难这样的问题。
此外,在专利文献3中,通过对化学转化皮膜的构成进行控制来谋求耐腐蚀性的提高。此外,为了提高与化学转化皮膜的反应性,针对镀层,以Al/Zn/Zn2Mg的三元共晶组织为主相。因此,认为尽管在进行通常的化学转化处理的情况下,化学转化处理性会提高,但是不会充分地得到涂装后耐腐蚀性。
因此,以往,并未提出近年来的汽车结构构件所需的、可确保足够的涂装后耐腐蚀性的热浸镀锌系镀敷钢板。
先行技术文献
专利文献
专利文献1:日本国特许第6350780号公报
专利文献2:日本国特开2015-214747号公报
专利文献3:日本国特许第4579715号公报
专利文献4:日本国特开2006-249521号公报
发明内容
发明要解决的技术问题
本发明鉴于上述问题而完成。本发明的目的在于,以热浸镀锌系镀敷钢板为前提,提供一种涂装后耐腐蚀性优异的镀敷钢板。
用于解决技术问题的技术手段
本发明人们在具有含Al、Mg及Zn的镀层的钢板(Zn-Al-Mg合金镀敷钢板)中,进行了用于提高涂装后耐腐蚀性的研究。
结果,新发现了:通过使镀层含有La及/或Ce,并在镀层的表面中,对镀层组织进行控制,从而涂装后耐腐蚀性会提高。具体而言,发现了:通过在镀层的表面中,使(Al-Zn)相和MgZn2相的层状组织的面积率变大,并且使(Al-Zn)枝晶的面积率变小,从而涂装后耐腐蚀性会提高。
本发明基于上述认识而完成,其主旨如下。
[1]本发明的一个方案的镀敷钢板为一种镀敷钢板,其具有钢板和镀层,该镀层被形成于所述钢板的表面的至少一部分,所述镀层的化学组成以质量%计,含有Al:6.00~35.00%、Mg:3.00~15.00%、La+Ce:合计0.0001~0.5000%、Si:0~2.00%、Ca:0~2.00%、Fe:0~2.00%、Sb:0~0.50%、Sr:0~0.50%、Pb:0~0.50%、Sn:0~1.00%、Cu:0~1.00%、Ti:0~1.00%、Ni:0~1.00%、以及Mn:0~1.00%,剩余部分由Zn及杂质构成,关于所述镀层,在表面中,(Al-Zn)相和MgZn2相层状地排列的层状组织的面积率为10~95%,所述层状组织的层状间隔为2.5间隔以下,(Al-Zn)枝晶的面积率为10%以下。
[2]也可以是,在如上述[1]所述的镀敷钢板中,所述镀层的所述化学组成以质量%计,含有Al:11.00~30.00%、Mg:5.00~11.00%、La+Ce:合计0.0010~0.1000%中的1种以上。
[3]也可以是,在如上述[1]或[2]所述的镀敷钢板中,关于所述镀层,在所述表面中,所述层状组织的面积率为60~95%。
[4]也可以是,在如上述[3]所述的镀敷钢板中,关于所述镀层,在所述表面中,所述层状组织的面积率为80~95%。
发明效果
根据本发明的上述方案,能够提供一种涂装后耐腐蚀性优异的镀敷钢板。
附图说明
图1是作为比较例的No.23的镀层的表面的组织照片。
图2是作为发明例的No.19的镀层的表面的组织照片。
图3是作为发明例的No.19的镀层的表面的组织照片。
具体实施方式
本发明的一个实施方式的镀敷钢板(本实施方式的镀敷钢板)具有钢板和镀层,该镀层被形成于钢板的表面的至少一部分。此外,本实施方式的镀敷钢板中,镀层的化学组成以质量%计,含有Al:6.00~35.00%、Mg:3.00~15.00%、La+Ce:合计0.0001~0.5000%、Si:0~2.00%、Ca:0~2.00%、Fe:0~2.00%、Sb:0~0.50%、Sr:0~0.50%、Pb:0~0.50%、Sn:0~1.00%、Cu:0~1.00%、Ti:0~1.00%、Ni:0~1.00%、以及Mn:0~1.00%,剩余部分由Zn及杂质构成。此外,关于本实施方式的镀敷钢板的镀层,在表面中,(Al-Zn)相和MgZn2相层状地排列的层状组织的面积率为10~95%,所述层状组织的层状间隔为2.5间隔以下,(Al-Zn)枝晶的面积率为10%以下。
<钢板>
本实施方式的镀敷钢板的重点在于镀层,针对钢板的种类,不被特别地限定。可以根据所应用的产品或所需的强度或板厚等来决定。例如,能够使用JIS G3193:2008所记载的热轧钢板或JIS G3141:2017所记载的冷轧钢板。
<镀层>
在本实施方式的镀敷钢板中,在钢板的表面的至少一部分,具备镀层。镀层既可以被形成于钢板的单面,也可以被形成于两面。
镀层的附着量优选15~250g/m 2。
[化学组成]
以下,针对本实施方式的镀敷钢板的镀层的化学组成进行说明。各元素的含量的%意味着质量%。此外,夹着“~”地示出的数值范围将其两端的值作为上下限而包含。
Al:6.00~35.00%
Al为在包含铝(Al)、锌(Zn)、镁(Mg)的镀层中,对于确保涂装后耐腐蚀性有效的元素。而且是在本实施方式的镀敷钢板的镀层中,为了形成层状组织所需的元素。此外,Al也是有助于合金层(Al-Fe合金层)的形成,对于确保镀敷密接性有效的元素。为了充分地得到上述效果,将Al含量设为6.00%以上。Al含量优选为11.00%以上。
另一方面,当Al含量超过35.00%时,(Al-Zn)枝晶的面积率会变高,涂装后耐腐蚀性及镀层的切断端面的耐腐蚀性会降低。因此,将Al含量设为35.00%以下。优选的是,为30.00%以下。
Mg:3.00~15.00%
Mg是具有提高镀层的涂装后耐腐蚀性的效果的元素。而且是在本实施方式的镀敷钢板的镀层中,为了形成层状组织所需的元素。为了充分得到上述效果,将Mg含量设为3.00%以上。Mg含量优选为5.00%以上。
另一方面,当Mg含量超过15.00%时,层状组织不会被充分地形成,不仅涂装后耐腐蚀性降低,而且镀层的加工性会降低。此外,会产生镀浴的渣滓产生量増大等制造上的问题。因此,将Mg含量设为15.00%以下。Mg含量优选为11.00%以下。
La+Ce:合计0.0001~0.5000%
La及Ce为对于在镀层中使层状组织稳定化有效的元素。即使不使镀层中含有La、Ce,在镀层的内部中,在表层部以外的区域中,有时也能够形成层状组织。然而,当La与Ce的合计含量小于0.0001%时,不会在表层部形成层状组织。因此,无法充分地确保镀层的表面中的层状组织的面积率。
另一方面,当La与Ce的合计含量超过0.5000%时,镀浴的粘性上升,镀浴的建浴本身多会变得困难,无法制造镀敷性状良好的镀敷钢材。因此,优选将La与Ce的合计含量设为0.5000%以下。
Si:0~2.00%
Si是与Mg一同形成化合物,从而有助于涂装后耐腐蚀性的提高的元素。此外,Si也是一种具有以下效果的元素:在将镀层形成在钢板上时,抑制被形成在钢板与镀层之间的合金层被形成得过厚的情况,从而提高钢板与镀层的密接性。因此,也可以含有Si。在要得到上述效果的情况下,优选将Si含量设为0.10%以上。更优选的是,为0.20%以上。
另一方面,当使Si含量超过2.00%时,在镀层中,过剩的Si会结晶,
此外,层状组织不会被充分地形成,涂装后耐腐蚀性会降低。此外,镀层的加工性也会降低。因此,将Si含量设为2.00%以下。关于Si含量,更优选的是,为1.50%以下。不一定需要使其含有Si,含量的下限为0%。
Ca:0~2.00%
当在镀层中含有Ca时,伴随Mg含量的増加,易在镀敷操作时被形成的渣滓的形成量会减少,镀敷制造性会提高。因此,也可以含有Ca。不一定需要含有Ca,下限为0%,但在要得到上述效果的情况下,优选将Ca含量设为0.03%以上,更优选的是,设为0.10%以上。
另一方面,当Ca含量较多时,层状组织不会被充分地形成,进而,以CaZn11相为代表的Ca系金属间化合物作为其他金属间化合物相,以面积率计会生成10%以上,涂装后耐腐蚀性会降低。此外,镀层的平面部的涂装后耐腐蚀性本身存在劣化的倾向,焊接部周围的耐腐蚀性有时也会劣化。因此,将Ca含量设为2.00%以下。Ca含量优选为1.00%以下。
Fe:0~2.00%
在制造镀层时,Fe会作为杂质混入到镀层中。Fe有时会被含有到2.00%左右,但当为该范围时,对本实施方式的镀敷钢板的特性的不良影响较小。因此,优选将Fe含量设为2.00%以下。更优选的是,为1.50%以下,进一步优选的是,为1.00%以下。
另一方面,如上所述,Fe会作为杂质混入到镀层中。为了完全防止Fe的混入,会显著地花费成本,因此也可以将Fe含量设为0.10%以上。
本实施方式的镀敷钢板的镀层的化学组成的基础在于,具有上述化学组成,剩余部分为Zn及杂质。杂质的含量优选为5.0%以下,更优选的是,为3.0%以下。
然而,也可以进一步取代Zn的一部分地,本实施方式的镀敷钢板的镀层例如在以下的范围内包含Sb、Pb、Cu、Sn、Ti、Sr、Ni、Mn(无论是有意图的添加还是作为杂质而含有)。因为也不是必须包含这些元素,所以含量的下限为0%。
Sb:0~0.50%
Sr:0~0.50%
Pb:0~0.50%
当镀层中含有Sr、Sb、Pb时,镀层的外观会变化,形成锌花,从而确认金属光泽提高。因此也可以含有Sr、Sb、Pb。在要得到上述效果的情况下,优选含有Sb、Sr、Pb中的1种以上0.01%以上。另一方面,当这些元素的含量超过0.50%时,会形成各种金属间化合物相,加工性及耐腐蚀性会恶化。此外,当这些元素的含量过剩时,镀浴的粘性会上升,镀浴的建浴本身多会变得困难,无法制造镀敷性状良好的镀敷钢板。因此,优选的是,将Sr含量设为0.50%以下,将Sb含量设为0.50%以下,将Pb含量设为0.50%以下。
Sn:0~1.00%
Sn是在含Zn、Al、Mg的镀层中,使Mg溶出速度上升的元素。当Mg的溶出速度上升时,平面部耐腐蚀性会恶化。因此,优选将Sn含量设为1.00%以下。
Cu:0~1.00%
Ti:0~1.00%
Ni:0~1.00%
Mn:0~1.00%
这些元素是有助于耐腐蚀性的提高的元素。因此,也可以含有。在要得到上述效果的情况下,优选将Cu、Ni、Ti、Mn中的1种以上的含量设为0.01%以上。另一方面,当这些元素的含量过剩时,镀浴的粘性会上升,镀浴的建浴本身多会变得困难,无法制造镀敷性状良好的镀敷钢板。因此,优选将各元素的含量分别设为1.00%以下。
镀层的化学组成通过以下方法来进行测定。
首先,得到以含有抑制剂的酸对镀层进行剥离溶解而成的酸液,其中,该抑制剂用于抑制钢基(钢材)的腐蚀。接着,通过以ICP分析对得到的酸液进行测定,从而能够得到镀层的化学组成。关于酸的种类,只要为可溶解镀层的酸,就没有特别的限制。关于化学组成,作为平均化学组成来进行测定。
[镀层所包含的组织(相)]
本实施方式的镀敷钢板的镀层例如如图2所示,在表面中,包含(Al-Zn)相和MgZn2相层状地排列的层状组织,其面积率为10~95%。此外,在本实施方式的镀敷钢板的镀层中,在表面中,(Al-Zn)枝晶的面积率为10%以下。(为了比较,在图1中示出以往的镀敷钢板的镀层的表面的组织照片)
一般地,当对浸渍于含Zn、Mg、Al的镀浴中的钢板进行冷却时,在镀层中,会生成作为初晶的(Al-Zn)枝晶、以及Zn/Al/MgZn2的三元共晶组织。该(Al-Zn)枝晶的耐腐蚀性较低,因此在即使进行了钢板的涂装的情况下,在涂膜产生损伤时等,腐蚀也会在镀层的内部进展,并发生涂膜膨胀。对此,如果镀层的表面的耐腐蚀性较高,则即使在涂膜产生损伤的情况下,也能够在镀层的表面中抑制腐蚀的进展。由本发明人们的研究结果可知:(Al-Zn)相和MgZn2相层状地排列的层状组织的耐腐蚀性较高,通过将(Al-Zn)相和MgZn2相层状地排列的层状组织以一定面积率以上形成于表面,耐腐蚀性会提高。
因此,在本实施方式的镀敷钢板的镀层中,在镀层的表面中,将有助于涂装后耐腐蚀性的提高的(Al-Zn)相和MgZn2相层状地排列的层状组织的面积率设为10%以上。表面中的层状组织的面积率优选为60%以上,更优选的是80%以上。层状组织不仅具有涂装后耐腐蚀性,也具有提高耐LME性的效果。
另一方面,在以上述化学组成为前提的情况下,使层状组织的面积率超过95%在工业上并不容易。因此,将层状组织的面积率设为95%以下。
此外,在本实施方式的镀敷钢板的镀层中,在表面中,将使涂装后耐腐蚀性降低的(Al-Zn)枝晶的面积率设为10%以下。优选(Al-Zn)枝晶的面积率较少,也可以为0%。
层状组织例如如图3所示,为(Al-Zn)相和MgZn2相层状地排列的组织,而其层状间隔越是微细,涂装后耐腐蚀性及耐LME性的提高效果就会越大。可得到足够的性能的层状间隔为2.5μm以下(2500nm以下),优选为500nm以下。这种层状组织也被称为羽毛状组织。
Zn/Al/MgZn2的三元共晶组织以面积%计,由Zn相:45~60%、MgZn2相:35~45%、Al相:3~10%构成,与此不同,层状组织为如下的组织:各相的分率以面积%计,为Zn相:0~10%,MgZn2相:40~65%,Al相:30~45%。
也可以是,在本实施方式的镀敷钢板的镀层中,在表面中,作为上述层状组织及(Al-Zn)枝晶以外的相,也可以包含块状MgZn2相、Zn/Al/MgZn2的三元共晶组织、以及其他金属间化合物。剩余部分的合计优选为50%以下,更优选的是,为30%以下。
块状MgZn2相有助于涂装后耐腐蚀性的提高。在要得到足够的效果的情况下,优选将块状MgZn2相的面积率设为5%以上。另一方面,从加工性这点出发,MgZn2相的面积率优选为40%以下。
Zn/Al/MgZn2的三元共晶组织的面积率优选设为45%以下。当Zn/Al/MgZn2的三元共晶组织的面积率超过45%时,会顾虑涂装后耐腐蚀性的降低。
此外,因为MgSi2相及其他金属间化合物会使涂装后耐腐蚀性降低,所以优选分别以面积率计设为10.0%以下。更优选的是,以合计的面积率计,为10.0%以下。作为其他金属间化合物相,例如可举出CaZn11相、Al2CaSi2相、Al2CaZn2相等。
针对镀层的组织(各相的面积率、层状间隔),用以下的方法来测定。
从本实施方式的镀敷钢板中,提取与轧制方向直角方向上25mm×轧制方向上15mm尺寸的样本,将其埋入到树脂中并进行研磨,使得该样本的镀层的表面成为观察面,此后,得到SEM像、以及基于EDS的元素分布像。关于镀层的、层状组织、块状MgZn2相、Zn/Al/MgZn2三元共晶组织、(Al-Zn)枝晶、以及其他金属间化合物的面积率,是从不同的5个样本中,对镀层的截面EDS映射像各拍摄1个视野,合计拍摄5个视野(倍率1500倍:60μm×50μm/1视野),并根据图像来算出。
此时,由Al、Zn构成的(Al-Zn)相和MgZn2相层状地排列,若层状间隔为4μm以下,则判断为层状组织,即使(Al-Zn)相与MgZn2相相邻,只要(Al-Zn)相或MgZn2相的短径超过4μm,也分别将其判断为(Al-Zn)枝晶、块状MgZn2相,若为层状间隔4μm以下的Zn相、α相、MgZn2的层状组织,则判断为Zn/Al/MgZn2三元共晶组织,在相中含有10%以上的(Zn、Al、Mg、Si)以外的金属情况下,判断为是其他金属间化合物。
此外,层状组织的层状间隔通过以下方式求得:根据SEM观察,针对形成层状组织的相内的、面积率最低的相,对到相邻的相的间隔进行测定,并算出其10处平均值。
此外,层状组织、构成Zn/Al/MgZn2三元共晶组织的Zn相、MgZn2相、Al相的面积率能够以如下方法求得:用图像处理软件等,以线对截面SEM像上的该组织所存在的区域进行包围,并算出以线包围的区域的面积。
<制造方法>
粘接,针对本实施方式的镀敷钢板的优选的制造方法进行说明。关于本实施方式的镀敷钢板,与制造方法无关,只要具有上述特征,就会得到该效果。然而,根据以下的方法,能够稳定地进行制造,因此是优选的。
具体而言,本实施方式的钢板能够通过包含以下工序(I)~(IV)的制造方法进行制造。
(I)退火工序,其对钢板进行还原退火
(II)镀敷工序,其将钢板浸渍于包含Al、Mg、Zn、以及La及Ce中的1种或2种的镀浴,从而将其制成镀敷原板
(III)控制冷却工序,其将所述镀敷原板以15℃/秒以上的平均冷却速度,冷却到(Al-Zn/MgZn2二元共晶温度-30)℃~(Al-Zn/MgZn2二元共晶温度-10)℃的冷却停止温度
(Iv)缓冷却工序,其在所述控制冷却工序后,以到335℃的平均冷却速度为5℃/秒以下的方式,冷却到335℃以下
[退火工序]
在退火工序中,在镀敷工序之前,针对以公知的方法得到的钢板(热轧钢板或冷轧钢板),进行退火(还原退火)。针对退火条件,可以为公知的条件,例如在露点为-10℃以上的5%H2-N2气体氛围下加热到750~900℃,并保持30~240秒。
[镀敷工序]
在镀敷工序中,在退火后的降温过程中,使钢板浸渍于镀浴,形成镀层,将其制成镀敷原板。
关于镀浴,优选的是,以质量%计,包含Al:6.00~35.00%、Mg:3.00~15.00%、La+Ce:0.0001~0.5000%、Si:0~2.00%、Ca:0~2.00%,剩余部分由Zn及杂质构成。进而,也可以是,根据需要,包含Fe、Sb、Sr、Pb、Sn、Cu、Ti、Ni、Mn。镀浴的组成与被形成的镀层的组成大致相同,因此可以根据欲得到的镀层的化学组成进行调整。
[控制冷却工序]
在控制冷却工序中,在对镀敷工序后的(从镀浴中提起的)镀敷原板,以N2等吹扫气体调整了镀敷附着量后,进行冷却。在冷却时,以平均冷却速度为15℃/秒以上的方式,冷却到(Al-Zn/MgZn2二元共晶温度-30)℃~(Al-Zn/MgZn2二元共晶温度-10)℃的冷却停止温度。
通过以上述条件进行冷却,(Al-Zn)枝晶的生成被抑制,并且层状组织的生成核被形成,在后续的缓冷却工序中,会生成层状组织。
当平均冷却速度小于15℃/秒时,(Al-Zn)相和MgZn2相不会形成层状组织,(Al-Zn)枝晶会大量生成,涂装后耐腐蚀性会降低。
此外,当冷却停止温度低于(Al-Zn/MgZn2二元共晶温度-30)℃时,会难以在后续的缓冷却工序中使层状组织生成足够的量。此外,当高于(Al-Zn/MgZn2二元共晶温度-10)℃时,会无法满足α相和MgZn2相共晶凝固的条件,作为结果,会成为(Al-Mg)枝晶生成得较多的原因。
平均冷却速度的上限无需限定,但也可以是,由于设备等的制约,将平均冷却速度设为40℃/秒以下。
Al-Zn/MgZn2二元共晶温度例如能够根据Zn-Al-Mg三元系的液相面投影图来求得。
[缓冷却工序]
在缓冷却工序中,以到335℃的平均冷却速度为5℃/秒以下的方式,将控制冷却停止后的镀敷原板冷却到335℃以下。
通过该缓冷却工序,在控制冷却工序中形成的层状组织的生成核会生长,在表面中,会得到预定的层状组织的面积率。
当到335℃的平均冷却速度超过5℃/秒时,核生长会变得不充分,层状组织的面积率会不足够。
根据上述制造方法,会得到本实施方式的镀敷钢板。
实施例
作为供退火、镀敷的钢板,准备了板厚1.6mm的冷轧钢板(0.2%C-2.0%Si-2.3%Mn)。
在将该钢板切断为100mm×200mm后,用分批式的热浸镀试验装置,持续进行了退火及热浸镀。
在退火时,在氧浓度20ppm以下的炉内,在由含有5%的H2气体、剩余部分为N2的气体构成,且露点为0℃的气氛下,以860℃进行了120秒的退火。
在退火后,以N2气体对钢板进行气冷,在钢板温度到达了浴温+20℃后,使其浸渍于表1所示的浴温的镀浴约3秒钟。
针对形成有镀层的镀敷原板,在以N2气体将镀敷的附着量调整到40~80g/m2后,以表2所示的条件进行控制冷却及缓冷却,并冷却到室温。控制冷却停止温度均为(Al-Zn/MgZn2二元共晶温度-30)℃~(Al-Zn/MgZn2二元共晶温度-10)℃的范围内。
钢板的温度用点焊于镀敷原板中心部的热电偶进行了测定。
被形成的镀层的组成如表1所示。表1的剩余部分为Zn及5.0%以下的杂质。
针对得到的镀敷钢板,用以下的方法,对镀层所包含的各相的面积率及层状组织的层状间隔进行了测定。
从得到的镀敷钢板中,提取与轧制方向直角方向上25mm×轧制方向上15mm尺寸的样本,将其埋入到树脂中并进行研磨,使得该样本的镀层的表面成为观察面,此后,得到SEM像、以及基于EDS的元素分布像。关于镀层的、层状组织、块状MgZn2相、Zn/Al/MgZn2三元共晶组织、(Al-Zn)枝晶、以及其他金属间化合物的面积率,从不同的5个样本中,对镀层的截面EDS映射像各拍摄1个视野,合计拍摄5个视野(倍率1500倍:60μm×50μm/1视野),并根据图像来算出。
此外,层状组织的层状间隔通过以下方式并求得:根据SEM观察,针对形成层状组织的相内的、面积率最低的相,对到相邻的相的间隔进行测定,并算出其10处平均值。
针对层状组织,均为由以面积%计,Zn相:0~10%、MgZn2相:40~65%、Al相:30~45%构成的组织。
此外,针对得到的镀敷钢板,对涂装后耐腐蚀性进行了评价。
具体而言,从镀敷钢板中提取50×100mm的样本,实施磷酸Zn处理(SD5350系统:日本paint industrial coding公司制标准),然后,实施电沉积涂装(PN110Powernix(注册商标)grey:日本paint industrial coding公司制标准),使得厚度成为20μm,以烧结温度150℃、20分钟进行了烧结。然后,将钢板使用60°、曲率半径为10mm的模具将钢板赋予V弯曲,在将弯曲复原后,再在50℃、5%的NaAl水溶液中浸渍500h,进行将粘接带仅粘贴于实施了V弯曲加工的面,并对其进行瞬间剥离的带剥离试验,针对粘贴了粘接带的面积,求得涂装剥离的面积的比例,并由此以如下方式进行了评价。
(评价)
B:剥离面积比例25%以上
A:剥离面积比例为15~小于25%
AA:剥离面积比例为10~小于15%
AAA:剥离面积比例小于10%
此外,针对得到的钢板,用以下的条件进行点焊,对焊接部的截面进行观察,按龟裂(LME裂纹)的长度进行了评价。
即,将表中所记载的2张No.1~30的镀敷钢板重叠,以击打角为7°、载荷为400kgf的方式,按压通电电极,将电流模式设定成焊点直径为3.5×√t~5.5×√t(t:板厚),并进行了点焊。对于通电电极,使用了JIS标准下的型的Cu-Cr电极。
在点焊后,与设置了击打角的方向平行地沿钢板的板厚方向进行了切断。在切断后,以光学显微镜对通过机械研磨和化学研磨精加工为镜面抛光的焊接部的截面进行观察,并对塑性金属环区(日语:コロナボンド)跟前外部的LME龟裂长度进行了测定。
根据有无龟裂,以如下方式进行了判断。
(评价)
A:有0.3mm以下的龟裂
AA:无龟裂
将结果在表2中示出。
[表1]
[表2]
由表1~2可知,针对作为发明例的No.2、3、5、7~10、12~17、19~22、24、26~29,得到了优异的涂装后耐腐蚀性。
另一方面,作为比较例的No.1、4、6、11、18、23、25、30中,镀层的化学组成、镀层的表面中的组织的构成在本发明的范围外,因此涂装后耐腐蚀性较差。
工业可利用性
根据本发明,能够提供一种涂装后耐腐蚀性比以往的汽车用镀敷钢板更为优异的镀敷钢材,并能够通过汽车用镀敷钢板的长寿命化来助力产业的发展。
附图标记说明
1(Al-Zn)相和MgZn2相的层状组织
2(Al-Zn)枝晶
3Zn/Al/MgZn2的三元共晶组织
Claims (4)
1.一种镀敷钢板,其特征在于,具有:
钢板,以及
镀层,其被形成于所述钢板的表面的至少一部分;
所述镀层的化学组成以质量%计,含有
Al:6.00~35.00%、
Mg:3.00~15.00%、
La+Ce:合计0.0001~0.5000%、
Si:0~2.00%、
Ca:0~2.00%、
Fe:0~2.00%、
Sb:0~0.50%、
Sr:0~0.50%、
Pb:0~0.50%、
Sn:0~1.00%、
Cu:0~1.00%、
Ti:0~1.00%、
Ni:0~1.00%、以及
Mn:0~1.00%,剩余部分由Zn及杂质构成;
关于所述镀层,在表面中,
(Al-Zn)相和MgZn2相层状地排列的层状组织的面积率为10~95%,
所述层状组织的层状间隔为2.5间隔以下,
(Al-Zn)枝晶的面积率为10%以下。
2.如权利要求1所述的镀敷钢板,其特征在于,
所述镀层的所述化学组成以质量%计,含有
Al:11.00~30.00%、
Mg:5.00~11.00%、以及
La+Ce:合计0.0010~0.1000%中的1种以上。
3.如权利要求1或2所述的镀敷钢板,其特征在于,
关于所述镀层,在所述表面中,所述层状组织的面积率为60~95%。
4.如权利要求3所述的镀敷钢板,其特征在于,
关于所述镀层,在所述表面中,所述层状组织的面积率为80~95%。
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