CN1282803A - 耐孔洞性优良的镀锌钢板 - Google Patents
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Abstract
本发明提供镀锌钢板,在钢板表面上具有一面附着量20—60g/m2的镀锌层和在该镀锌层上一面附着量0.5—3.0g/m2的磷酸锌被膜,该被膜中含有0.5—10.0质量%镁、0.1—2.0质量%镍和0.5—8.0质量%锰,锰和镍的含量满足(Ni)×7.6—10.9≤(Mn)≤(Ni)×11.4([Mn]是锰质量%,[ Ni]是镍质量%)。其是不损害汽车车身用途要求的其他特性,电泳涂漆后的耐孔洞性优良的镀锌钢板。在磷酸锌被膜中,将镁限定在2.0—7.0质量%、镍限定在0.1—1.4质量%、锰限定在0.5—5.0质量%,就成为耐孔洞性、冲压加工性也优良的镀锌钢板。
Description
本发明是关于作为汽车车身使用的镀锌钢板,特别是关于不牺牲其他性能,格外提高电泳涂漆后的耐孔洞性的镀锌钢板。
为了防止汽车车身的车身强度由于在长期的腐蚀环境下使用而降低,广泛地使用施行了镀锌系的钢板,在日本,通常使用镀锌系合金的镀锌-镍合金钢板和镀锌-铁合金钢板。这些镀锌系合金,通过使镍或铁与锌合金化,能够赋予钢板高耐蚀性,但因为是合金镀敷,所以存在几个问题。
例如,镀锌-镍合金的钢板,采用电镀法制造,但镍的价格昂贵,因而成本提高。另外,镍含量通常必须控制在大约12±1质量%的极狭窄的范围,也存在制造困难的问题。
另一方面,镀锌-铁合金钢板,可以采用电镀法和热浸镀法的任一种方法进行制造。
但是,在采用电镀法制造镀锌-铁合金钢板时,与镀锌-镍合金钢板时同样,也存在难以将镀锌层中的铁含有率控制在极狭窄的范围的所谓合金控制的难题。除此之外,镀液中的Fe2+离子容易被氧化,因此镀敷变得不稳定,使制造困难。其结果,存在成本变高的问题。
一般来说,镀锌-铁合金钢板,往往采用热浸镀法进行制造。在采用热浸镀法制造镀锌-铁合金钢板时,在钢板表面被覆熔融的锌后,在高温下保持,使钢板与锌进行合金化。可是,该方法由于热浸镀锌浴中的铝浓度或者合金化过程的温度或时间等的影响,品质会发生很大的变动,为了制造均一的合金镀层,需要高度的技术。结果,同样提高了成本。
如以上所述,镀锌系合金在制造上都是困难的,而且还有成本高的问题。
另一方面,仅镀锌的镀锌钢板是低成本的,采用电镀法或者热浸镀法的任一种方法都可以制造。但是,很少在汽车车身上使用。其原因是,仅镀锌的话,耐蚀性不够,特别是镀锌钢板长期暴露在腐蚀环境下时,由于腐蚀,钢板容易产生孔洞,在保证车身的强度上存在问题。
通常,在汽车车身的制造中,将钢板或者镀敷钢板进行冲压加工后,再依次进行表面化学处理、电泳涂漆、喷涂涂装后作为汽车车身使用。另外,在汽车车身上,一般认为由于腐蚀最容易产生孔洞的部分是门的下部。其原因是,门下部进行弯曲加工,通过窗户的缝隙等浸入的水容易积留在门的内部,因此腐蚀的进行速度往往比车身的其他部分要快。
在车身的冲压加工后施行的处理中,表面化学处理和电泳涂漆虽然也能够扩展至门下部的弯曲部分,但在其后进行的喷涂涂装时,涂料不能达到狭小的弯曲部内。这样,就不能期待由喷涂涂装而产生的防腐蚀效果,因此电泳涂漆后的耐孔洞性是特别重要的。
在这样的背景下,作为提高镀锌钢板的耐蚀性的方法,已公开了通过表面化学处理(磷酸盐处理),在镀锌系层上形成含有镁的磷酸盐被膜的技术。
例如,在特开平1-312081号公报中,公开了在电镀锌层上形成含有0.1质量%以上镁的磷酸盐被膜的表面处理金属材料。像这样,在磷酸盐被膜中含有镁的表面处理金属材料,被认为对盐雾试验下的生锈有抑制效果。但是,如果进行与汽车车身实际上的腐蚀情况充分一致的复合循环腐蚀试验,就可知道耐孔洞性是不够的。
另外,在特开平3-107469号公报中公开了在电镀锌系层上形成含有1~7%镁的磷酸盐被膜的材料。但是即使在此情况下,因为在磷酸盐被膜中仅含有镁,虽然对盐雾试验下的生锈有抑制效果,但对与汽车车身实际的腐蚀情况充分一致的复合循环腐蚀试验下的耐孔洞性来说还是不够的。
另外,在特开平7-138764号公报中,公开了含有锌的金属镀敷钢板,在含有锌的金属镀层的表面上,形成按重量比(锌/磷)含有锌和磷为2.504∶1~3.166∶1、而且含有0.06~9.0质量%的从铁、钴、镍、钙、镁和锰中选择的至少一种金属的磷酸锌复合被膜。但是,该镀敷钢板,虽然汽车车身制造时的高速冲压加工性优良,但没有考虑耐蚀性,因而耐孔洞性不够。
如上所述,镀锌系合金是高成本的。另一方面,如果在汽车车身上使用成本低的镀锌,耐蚀性就成问题。因此,为了提高镀锌的耐蚀性,正在做各种尝试。其中公开了形成含有镁的磷酸盐被膜的技术,但在镀锌层上仅形成只控制镁含量的磷酸盐被膜,难以得到足够的耐孔洞性。
本发明的目的在于,以低的成本提供作为汽车车身使用的镀锌钢板,该镀锌钢板在不牺牲其他的性能的情况下,具有良好的电泳涂漆后的耐孔洞性。
本发明人为了解决上述问题而进行了反复研究,结果发现,如果在钢板表面上依次层叠形成规定附着量的镀锌层和磷酸锌被膜的同时,使磷酸锌被膜中的镁、镍和锰的含量适当化,在不牺牲其他性能的情况下,就能够大大提高电泳涂漆后的耐孔洞性,从而完成了本发明。
即,本发明是耐孔洞性优良的镀锌钢板,在该钢板表面上具有每一面的附着量是20~60g/m2的镀锌层和在该镀锌层上每一面的附着量是0.5~3.0g/m2的磷酸锌被膜,在该磷酸锌被膜中含有0.5~10.0质量%的镁、0.1~2.0质量%的镍和0.5~8.0质量%的锰,而且锰和镍的含量满足下述(1)式,
〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕×11.4………(1)
式中,〔Mn〕是锰质量%,〔Ni〕是镍质量%。
另外,这种镀锌钢板,在该磷酸锌被膜中如果含有2.0~7.0质量%的镁、0.1~1.4质量%的镍和0.5~5.0质量%的锰,不仅耐孔洞性好而且冲压加工性也得到提高,因而是特别优选的。另外,在特别强调提高冲压加工性时,在该磷酸锌被膜中,磷酸锌可以是长边不到2.5μm的粒状晶体。
以下,说明将本发明限定在上述发明特定事项的理由。
(1)镀锌层
每一面的附着量:20~60g/m2
镀锌层,每一面的附着量规定为20~60g/m2。这是因为,如果上述附着量不到20g/m2,耐孔洞性就不够,反之,如果超过60g/m2,耐孔洞性是足够的,但附着大量的镀锌层,不仅使成本提高,而且也使冲压加工性或焊接性劣化。
另外,上述镀锌层可以采用公知的电镀法和热浸镀法的任一种的镀敷方法来形成。
采用各种镀敷法形成的镀锌层,一般是在镀锌层中不可避免地混入锡、镍、铁、铝等杂质,因此在本发明中也包含不可避免地混入这些杂质的镀锌层。此时,镀锌层中的上述不可避免的杂质的各个含量最好是1质量%以下。
(2)磷酸锌被膜
(ⅰ)每一面的附着量:0.5~3.0g/m2
磷酸锌被膜,每一面的附着量规定为0.5~3.0g/m2的范围。这是因为,上述附着量如果不到0.5g/m2,耐孔洞性不够,反之,如果超过3.0g/m2,虽然能够充分地得到耐孔洞性,但被膜的形成需要长时间,不仅成本增加,而且表面的摩擦阻力也变大,因此使冲压加工性劣化。
(ⅱ)磷酸锌被膜中的成分组成
磷酸锌被膜中的成分组成规定为:0.5~10.0质量%的镁、0.1~2.0质量%的镍和0.5~8.0质量%的锰,而且要满足
〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕× 11.4的关系式。特别是,在不仅需要提高耐孔洞性,而且也需要提高冲压加工性时,磷酸锌被膜中的成分组成规定为:2.0~7.0质量%的镁、0.1~1.4质量%的镍和0.5~5.0质量%的锰,而且满足上述的关系式为佳。
以下,说明关于采用上述成分组成的原委。
在汽车车身的制造过程中,一般是将冲压加工后通过焊接等组合的车身进行表面化学处理,再进行电泳涂漆、喷涂涂装。但在由于腐蚀而容易产生孔洞的部位,无法充分进行喷涂涂装,所以不能期待由这种涂装产生的防腐蚀作用,因此电泳涂漆后的耐孔洞性变得十分重要。
依次进行了表面化学处理和上述各种涂装的镀锌钢板暴露在腐蚀环境下时,由于腐蚀环境中的水分,表面化学处理被膜产生冷凝水(保持吸附水或者结合水),容易发生涂膜膨胀,结果往往导致腐蚀进行加快。因此,一般认为,汽车用的镀锌钢板通过在该表面化学处理(磷酸锌)被膜中含有镍或锰,能够防止这种冷凝水,改善电泳涂漆后的耐蚀性。
另外也知道,如果在磷酸锌被膜中含有镁,也提高耐蚀性。
本发明人认为,如果在磷酸锌被膜中能够适量含有镁和镍及锰,由于镁的提高耐蚀性效果和镍、锰的防止涂膜膨胀效果两者的协同作用,能够提高电泳涂漆后的耐孔洞性,并对此进行了深入的研究。
但是,在磷酸锌被膜中如果含有规定量以上的镁,在上述被膜中就不能含有适量的镍和锰,与此相反,在磷酸锌被膜中如果含有规定量以上的镍和锰,在上述被膜中就不能含有适量的镁。总之,在磷酸锌被膜中难以同时含有适量的镁和适量的镍及锰,结果,就得不到足够的耐孔洞性。
因此,本发明人对为了使磷酸锌被膜中的镁和镍及锰全部适量的含有进一步进行了研究。结果,如果将镁限定在0.5~10.0质量%的范围,就能谋求耐蚀性的提高,同时成功地含有能够发挥防止涂膜膨胀效果量的镍和锰。进而发现,通过谋求镍和锰的含量的适当化,大大地提高电泳涂漆后的耐孔洞性,从而完成了本发明。
即,在该磷酸锌被膜中,将镁含量限定在0.5~10.0质量%,同时将镍含量规定为0.1~2.0质量%、锰含量规定为0.5~8.0质量%,而且锰和镍的含量限定在满足〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕×11.4的范围内。也就是说,在将镁含量限定在0.5~10.0质量%的同时,可以将镍和锰的含量限制在以图3的斜线表示的范围内。
之所以将磷酸锌被膜中的镁含量限定在0.5~10.0质量%的范围,是因为如果镁含量比上述范围少时,不能充分地得到耐孔洞性,反之,如果比上述范围多,就不能含有能够发挥防止涂膜膨胀效果的量的镍和锰,在腐蚀环境下的涂膜膨胀变大,耐孔洞性变得不充分。
另一方面,之所以将磷酸锌被膜中的镍和锰的含量限定在上述范围,是因为如果镍含量不到0.1质量%,或者锰含量不到0.5质量%,在腐蚀环境下的涂膜膨胀就会增大,不能充分地得到耐孔洞性。反之,如果镍含量超过2.0质量%,或者锰含量超过8.0质量%,磷酸锌被膜中的镁含量达到上述适当范围的下限值0.5质量%都变得极为困难,结果不能充分得到耐孔洞性。
此外,如果锰含量比将镍含量代入(1)式中的{〔Ni〕×7.6-10.9}中时的值小,在腐蚀环境下的涂膜膨胀将增大,耐孔洞性不够。反之,如果锰含量比将镍含量代入(1)式中的{〔Ni〕×11.4}中时的值大,在磷酸锌被膜中以0.5质量%以上含有镁就变得极为困难,结果,不能充分得到耐孔洞性。
因此,本发明以下述作为必须的发明特定事项,即,在磷酸锌被膜中含有0.5~10.0质量%的镁、0.1~2.0质量%的镍和0.5~8.0质量%的锰,而且锰和镍的含量要满足〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕×11.4的关系式,这样,在不牺牲其他性能的情况下,能够大大提高耐孔洞性。
另外,在本发明中,为了在提高耐孔洞性的同时,也提高冲压加工性,在该磷酸锌被膜中,在将镁含量限定在2.0~7.0质量%,同时,将镍含量限定在0.1~1.4质量%、将锰含量限定在0.5~5.0质量%,而且锰和镍的含量限定在满足〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕×11.4的范围内。即,将镁含量限定在2.0~7.0质量%的同时,将镍和锰的含量限定在图3的斜线范围与横线范围两者重合的范围内。
如果将本发明的磷酸锌被膜中的镁含量限定在2.0~7.0质量%的范围,磷酸锌晶体是粒状,而且该晶体的大小(长边)不到2.5μm,是细小的,结果飞跃地提高冲压加工性。虽然其机理尚不清楚,但可以认为,如果磷酸锌晶体是粒状、而且细小,在与冲压加工时的金属模接触中滑动摩擦阻力就变小。
再者因为,如果上述的镁含量不到2.0质量%,磷酸锌晶体成为鳞片状(参照图2(a)、(b))、而且该晶体大小(长边)是2.5μm以上,提高冲压加工性的效果变得不明显。反之,如果镁含量超过7.0质量%,磷酸锌晶体本身会变脆,显著地丧失冲压加工性提高的效果。
本发明人制作了磷酸锌被膜中的镁含量不同的各种镀锌钢板,将这些镀锌钢板,冲裁成直径100mm的坯料,在阳模直径:φ50mm,阴模直径:φ52mm,防皱褶压:1t和阳模速度:120mm/分的条件下进行冲压加工试验,对冲压加工性进行评价。结果示于图1中。纵轴是冲压加工时的阳模载荷(t),横轴是磷酸锌被膜中的镁含量(质量%),由此可知,上述阳模载荷越小,冲压加工性越好。
另外,图2是表示磷酸锌被膜中的镁含量不同的4种镀锌钢板的磷酸锌被膜表面的SEM(扫描电子显微镜)的图像。
从图1和图2可知,如果将上述镁含量限定在2.0~7.0质量%的范围,磷酸锌晶体的大小(长边)成为不到2.5μm的细小粒状(参照图2(c)、(d)),冲压加工性大大提高。
在此所说的粒状是指,以SEM的图像观察的、如图4那样表示1个晶体时,短边c/长边a之比超过0.2。
因此,在需要进一步提高冲压加工性时,最好将上述镁含量规定为2.0~7.0质量%的范围。在此情况下,如果磷酸锌被膜中的镍含量超过1.4质量%,或者锰含量超过5.0质量%,磷酸锌晶体就是鳞片状、而且该晶体大小不细小,长边照样是2.5μm以上,因此难以得到冲压加工性提高的效果。
上面所描述的仅仅是表示本发明的实施方式的一例,在权利要求的范围内可以附加各种各样的变更。
实施例
下面,说明本发明的实施例。
按表1所示的镀敷方法制造规定的镀锌附着量的各种镀锌钢板,以该镀锌钢板为对象,按表2所示的条件、采用浸渍法进行磷酸锌处理。所得到的磷酸锌被膜具有表3所示的性状即附着量、镍、锰和镁的含量以及磷酸锌晶体的形状和大小。另外,在磷酸锌处理前,根据需要进行脱油处理后,进行通常的表面调整处理。
进行了磷酸锌处理的镀锌钢板,按照汽车车身制造工艺,使用日本ペィント制“SD2500”进行表面化学处理,然后进行日本ペィント制“V20”阳离子型电泳涂漆(膜厚10μm)。电泳涂漆后的试样,利用刀片进行横切后,进行图5的复合循环腐蚀试验,测定最大腐蚀深度(板厚减小值),根据该测定值评价耐孔洞性。其结果示于表3中。表3中的腐蚀深度的数值越小,意味着耐孔洞性越好,在本发明中,以腐蚀深度为0.3mm以下作为合格水平。
另外,将上述处理钢板冲裁成直径100mm的坯料,以阳模直径:φ50mm、阴模直径:φ52mm、防皱褶压:1t、阳模速度:120mm/min进行圆筒冲压加工,测定阳模载荷,作为判断加工性的良否的指标。阳模载荷越小,意味着加工性越好。在本发明中,将阳模载荷是3.4t以下规定为冲压加工性特别优良。另外,目视观察加工面(圆筒侧面)的损伤程度,以“O”和“×”2个等级进行判定,对冲压加工性进行评价.这些评价结果示于表3中.表3中的“O”意味着损伤是轻度以下、合格水平以上,“×”意味着损伤是中度以上、不合格。
[表1]
镀锌钢板
符号 | 镀锌附着量(g/m2) | 镀敷方法 |
E G A | 23 | 电镀法 |
E G B | 30 | 电镀法 |
G I A | 45 | 热浸镀法 |
G I B | 58 | 热浸镀法 |
[表2]
磷酸锌处理液条件
PO4 3- | 5~30g/L |
Zn2+ | 0.5~3.0 g/L |
Ni2+ | 0.1~10.0g/L |
Mn2+ | 0.3~10.0g/L |
Mg2+ | 3~50g/L |
NO3 - | 1~150 g/L |
全氟 | 0.1~0.8 g/L |
处理温度 | 40~60℃ |
[表3]
表3的评价结果表明,实施例1~8耐孔洞性都优良,特别是实施例1、2、4~6和8冲压加工性也优良。另一方面,磷酸锌被膜中的镁、镍和锰的含量至少有一个是在适当范围以外的比较例1~5,耐孔洞性都没有达到合格水平。
按照本发明,能够提供电泳涂漆后的耐孔洞性优良而且生产成本低的镀锌钢板,特别适合作为汽车车身使用。
另外,如果将磷酸锌被膜中的镁、镍和锰的含量的适当范围进一步限定在特定的狭窄范围内,就能够提供不仅耐孔洞性优良,而且冲压加工性也优良的镀锌钢板。
附图的简单说明
图1是对磷酸锌被膜中的镁含量不同的各种钢板进行冲压加工试验,将此时的阳模载荷相对于磷酸锌被膜中的镁含量绘成曲线的图。
图2(a)~(d)分别是用SEM观察磷酸锌被膜中的镁、镍和锰的含量不同的4种镀锌钢板的磷酸锌被膜表面时的图像。
图3是用来说明在本发明的镀锌钢板上形成的磷酸锌被膜中的锰和镍的含量的适当范围的图。
图4是用来说明在本发明的镀锌钢板上形成的粒状磷酸锌晶体的图。
图5是用来说明复合循环腐蚀试验的图。
Claims (3)
1.镀锌钢板,其特征是,在钢板表面上具有每一面的附着量是20~60g/m2的镀锌层和在该镀锌层上每一面的附着量是0.5~3.0g/m2的磷酸锌被膜,该磷酸锌被膜中含有0.5~10.0质量%的镁、0.1~2.0质量%的镍和0.5~8.0质量%的锰,而且锰和镍的含量满足下述(1)式,
〔Ni〕×7.6-10.9≤〔Mn〕≤〔Ni〕×11.4………(1)
式中,〔Mn〕是锰质量%,〔Ni〕是镍质量%。
2.权利要求1所述的镀锌钢板,其中,在该磷酸锌被膜中含有2.0~7.0质量%的镁、0.1~1.4质量%的镍和0.5~5.0质量%的锰。
3.权利要求2所述的镀锌钢板,其中,在该磷酸锌被膜中,磷酸锌是长边不到2.5μm的粒状晶体。
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CN107475707A (zh) * | 2016-06-08 | 2017-12-15 | 现代自动车株式会社 | 用于Zn电镀钢板的磷酸盐膜的组合物,涂覆有其的Zn电镀钢板和其涂覆所述钢板的方法 |
CN109477222A (zh) * | 2016-07-29 | 2019-03-15 | 杰富意钢铁株式会社 | 磷酸锌处理镀锌钢板及其制造方法 |
CN112719065A (zh) * | 2020-12-23 | 2021-04-30 | 成都宏明双新科技股份有限公司 | 一种改善产品在落料时下层电泳漆层保留量的方法 |
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JP2001131763A (ja) * | 1999-11-09 | 2001-05-15 | Nippon Steel Corp | 有機複合亜鉛系メッキ鋼板 |
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CN109477222A (zh) * | 2016-07-29 | 2019-03-15 | 杰富意钢铁株式会社 | 磷酸锌处理镀锌钢板及其制造方法 |
CN109477222B (zh) * | 2016-07-29 | 2020-11-10 | 杰富意钢铁株式会社 | 磷酸锌处理镀锌钢板及其制造方法 |
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TW475002B (en) | 2002-02-01 |
CN1143008C (zh) | 2004-03-24 |
KR20010015193A (ko) | 2001-02-26 |
CA2313549A1 (en) | 2001-01-08 |
US6322906B1 (en) | 2001-11-27 |
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