CN110799670A - 防锈构件及其制造方法 - Google Patents
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Abstract
作为具备含有Si的皮膜且耐腐蚀性优异的防锈构件,提供一种具备基材、设置于所述基材上的锌系镀层以及设置于所述锌系镀层上且含有Si的化成皮膜的防锈构件,且所述防锈构件的特征在于:所述化成皮膜在表层侧以100nm以上的厚度具有富Si区域,所述富Si区域的Si含量相对于Zn含量的原子比为1以上。
Description
技术领域
本发明是涉及一种防锈构件及其制造方法。
背景技术
专利文献1中记载有一种耐腐蚀性基材,其在设置有锌或锌合金镀层的应进行处理的基材的表层具备包含下层与上层且通过单液处理而形成的两层结构化成处理皮膜,所述下层含有Cr,所述上层包含SiO2。
现有技术文献
专利文献
专利文献1:日本专利第3620510号公报
发明内容
发明所要解决的问题
本发明的目的在于提供一种具备如专利文献1中所记载般的含有Si的皮膜且耐腐蚀性优异的防锈构件及所述防锈构件的制造方法。
解决问题的技术手段
(1)一种防锈构件,其包括基材、设置于所述基材上的锌系镀层以及设置于所述锌系镀层上且含有Si的化成皮膜;且所述防锈构件的特征在于:所述化成皮膜在表层侧以100nm以上的厚度具有富Si区域,所述富Si区域的Si含量相对于Zn含量的原子比为1以上。
(2)根据所述(1)所记载的防锈构件,其中所述化成皮膜在所述富Si区域与所述锌系镀层之间具有倾斜区域,所述倾斜区域中,越接近所述锌系镀层,Zn的含量越增大。
(3)根据所述(2)所记载的防锈构件,其中所述倾斜区域的厚度为50nm以上。
(4)根据所述(2)或(3)所记载的防锈构件,其中所述富Si区域与所述倾斜区域在厚度方向上连续。
(5)根据所述(1)至(4)中任一项所记载的防锈构件,其中所述化成皮膜还含有选自由Cr、P、B、C、S、O、Li、Ca、Mg、Mo、V、Nb、Ta、W、Zr、Fe、Ni、Co、Cu、Si、Ti、Zn、Al、Sn及Bi以及镧系元素所组成的群组中的一种或两种以上的元素。
(6)根据所述(1)至(5)中任一项所记载的防锈构件,其中所述化成皮膜为反应型的化成皮膜。
(7)根据所述(1)至(6)中任一项所记载的防锈构件,其中所述化成皮膜含有氧化硅。
(8)根据所述(1)至(7)中任一项所记载的防锈构件,其中所述化成皮膜实质上不含有有机粘合剂成分。
(9)一种防锈构件的制造方法,所述防锈构件为根据所述(7)所记载的防锈构件,且所述防锈构件的制造方法的特征在于包括:镀敷工序,在所述基材上形成所述锌系镀层而获得具备所述基材与所述锌系镀层的被处理构件;以及化成处理工序,包含使所述被处理构件与化成处理液接触,其后,对所述被处理构件进行清洗,从而在所述被处理构件上形成所述化成皮膜;并且所述化成处理液包含含有进行化成反应的元素的含化成元素的物质及氧化硅。
发明的效果
根据本发明,可提供一种具备含有Si的皮膜且耐腐蚀性优异的防锈构件。另外,还可提供一种所述防锈构件的制造方法。
附图说明
图1是实施例1的防锈构件的深度分布。
图2是表示基于图1等的深度分布而算出的Si/Zn比的深度方向上的推移的曲线图。
图3是实施例2的防锈构件的深度分布。
图4是实施例3的防锈构件的深度分布。
图5是比较例的防锈构件的深度分布。
图6是表示实施例1的防锈构件的表面观察结果的图。
图7是表示比较例的防锈构件的表面观察结果的图。
图8是实施例4的防锈构件的深度分布。
图9是表示基于图8的深度分布而算出的Si/Zn比的深度方向上的推移的曲线图。
具体实施方式
以下,对本发明的实施方式进行说明。
本发明的一实施方式的防锈构件如以下说明般具备基材、锌系镀层及化成皮膜。
构成基材的材料为任意。作为具体例,可列举:铝系材料、铁系材料等金属系材料;氧化铝等陶瓷系材料;液晶塑料等有机系材料;以及分散有玻璃填料的环氧树脂等复合材料。基材的形状也为任意。可为平板状,也可为具有凹凸的复杂形状。作为具有这种复杂形状的构件的具体例,可列举制动钳(brake caliper)。
锌系镀层形成于基材上。锌系镀层可通过电解电镀来形成,也可通过非电解电镀来形成。在通过电解电镀来形成的情况下,有时优选为实施用以对基材赋予导电性的处理。构成锌系镀层的材料可仅为锌,也可包含锌以外的物质。在包含锌以外的物质的情况下,锌系镀层也可包含含有Ni等Zn以外的元素的锌合金。
化成皮膜为通过构成锌系镀层的金属元素与化成处理液中所含的元素产生的化成反应而形成的皮膜。因此,化成皮膜包含锌系镀层的构成元素、特别是Zn。包含于化成处理液中且承担化成反应的元素(在本说明书中也称为“化成元素”)的种类及其状态并不限定,可例示Cr(三价铬)。本发明的一实施方式的防锈构件所具备的化成皮膜含有Si。所含的Si的形态为任意。就皮膜的稳定性的观点而言,优选为以作为具有Si-O键的物质而含有的成分的形式包含于化成皮膜中,作为具体例,可列举胶体二氧化硅、气相二氧化硅等氧化硅。也可对氧化硅实施表面处理。
本发明的一实施方式的防锈构件所具备的化成皮膜在表层侧以100nm以上的厚度具有富Si区域,所述富Si区域的Si含量(单位:原子%)相对于Zn含量(单位:原子%)的比(原子比,在本说明书中也称为“Si/Zn比”)为1以上。即,富Si区域为在化成皮膜中满足下述式(1)的区域。
[Si]≧[Zn] (1)
在本说明书中,[Si]为化成皮膜中的Si含量(单位:原子%),[Zn]为化成皮膜中的Zn含量(单位:原子%)。
在本说明书中,化成皮膜及锌系镀层的组成是指通过X射线光电子分光(X-rayphotoelectron spectroscopy,XPS)分析而测定的结果,防锈构件的深度方向上的组成分布(深度分布)是指一边通过溅射来去除防锈构件的表面一边进行XPS分析而获得者。
例如,关于专利文献1中所记载的两层结构化成处理皮膜所具有的包含SiO2的上层,虽然Si含量相对较高,但如后述的实施例所示,所述上层中的Si含量(单位:原子%)小于Zn含量(单位:原子%)。因此,专利文献1中所记载的两层结构化成处理皮膜不具有在本说明书中所定义的富Si区域。与此相对,本发明的一实施方式的化成皮膜以100nm以上的厚度具有Si含量为Zn含量以上的富Si区域。由于具有这种富Si区域,因此可适当保护位于化成皮膜的内侧的锌系镀层,可获得耐腐蚀性、特别是耐白锈性优异的防锈构件。就使防锈构件的耐腐蚀性进一步稳定地提高的观点而言,富Si区域的厚度有时优选为150nm以上。
在位于富Si区域的Si源自氧化硅的情况下,认为氧化硅由源自锌系镀层的Zn及化成元素等化成皮膜中所含的Si以外的元素的氧化物或氢氧化物保持。
本发明的一实施方式的防锈构件所具备的化成皮膜在富Si区域与锌系镀层之间具有倾斜区域,所述倾斜区域中,越接近锌系镀层,Zn的含量越增大。在本说明书中,所谓倾斜区域,是指与富Si区域相接且位于锌系镀敷侧,且Zn含量以相对于锌系镀层中的Zn含量的比例计而为0.8以下的区域。因此,倾斜区域满足下述式(2-1)及下述式(2-2)。
[Si]/[Zn]≧1 (2-1)
[Zn]≦0.8×[Zn]0(2-2)
这里,[Zn]0为锌系镀层中的Zn含量(单位:原子%)。因此,例如在锌系镀层包含Zn-Ni合金镀敷,且所述镀敷的Ni共析率为18原子%的情况下,[Zn]0为82原子%,所述式(2-2)为[Zn]≦65.6原子%。锌系镀层的组成只要使用测定镀层的厚度时通常使用的荧光X射线膜厚计等来测定即可。
倾斜区域中,如上所述,越接近锌系镀层,Zn的含量越增大,另一方面,越接近锌系镀层,Si的含量越少。通过具有这种倾斜区域,位于锌系镀层的表面上的富Si区域中所含的氧化硅等含有Si的成分不易自防锈构件脱落。就使富Si区域中所含的成分脱落的可能性进一步稳定地降低的观点而言,倾斜区域的厚度有时优选为50nm以上,有时更优选为100nm以上,有时特别优选为150nm以上。
在化成皮膜中,富Si区域与倾斜区域优选为在厚度方向上连续。通过将这些区域连续而不易产生这些区域的界面处的剥离。如后述的实施例所示,本发明的一实施方式的防锈构件的化成皮膜中,明确确认到:在富Si区域与倾斜区域的边界区域即Si/Zn比为1附近的区域中,Si/Zn比的变化是连续的,富Si区域与倾斜区域在厚度方向上连续。
就提高锌系镀层与化成皮膜的密合性的观点而言,化成皮膜有时优选为反应型的化成皮膜。另外,化成皮膜也可实质上不含有有机粘合剂成分。与有机粘合剂成分相比,就提高尺寸精度的观点或耐腐蚀性的经时稳定性的观点而言,有时优选为包含Zn或化成元素的成分作为氧化硅等含有Si的成分的粘合剂而主体地发挥功能。
化成皮膜也可包含Si及源自锌系镀层的Zn以外的元素。作为这种元素,可例示Cr、P、B、C、S、O、Li、Ca、Mg、Mo、V、Nb、Ta、W、Zr、Fe、Ni、Co、Cu、Si、Ti、Zn、Al、Sn及Bi以及镧系元素。可以所述化成元素的形式或出于其他目的而含有选自由这些元素所组成的群组中的一种或两种以上的元素。所述元素的含量可在实现含有的目的的范围内适当设定。再者,在化成皮膜中所含的含有Si的成分包含氧化硅的情况下,化成皮膜包含作为氧化硅的构成元素的O(氧)。
本发明的一实施方式的防锈构件的制造方法并不限定。基材可通过压延、切削、压制等机械加工、成形加工等来形成。准备了基材后,通过实施以下说明的镀敷工序及化成处理工序而可制造防锈构件。
镀敷工序中,在基材上形成锌系镀层而获得具备基材与锌系镀层的被处理构件。如上所述,锌系镀层可通过电解电镀来形成,也可通过其他方法来形成。
化成处理工序中,首先,通过将被处理构件浸渍于化成处理液中等方法来使其接触。所述情况下的化成处理液包含含有化成元素的含化成元素的物质及氧化硅。化成处理液的温度、浸渍时间等处理条件可考虑化成处理液的组成及应形成的化成皮膜的组成来适当设定。在化成处理液为反应型的情况下,使其与化成处理液接触规定时间之后,使用水等来清洗被处理构件而使化成反应停止,从而获得化成皮膜。如此,可在被处理构件上形成化成皮膜。
以上说明的实施方式是为了容易理解本发明而记载,并非用以限定本发明而记载。因此,所述实施方式中所公开的各要素为也包含属于本发明的技术范围内的所有设计变更或等同物的主旨。例如,化成皮膜也可包含有机粘合剂成分。在所述情况下,提供有机粘合剂成分的成分可包含于化成处理液中,也能够作为所述无机系的化成皮膜的有机系外涂层而定位的区域可形成于富Si区域上。
实施例
以下,基于实施例对本发明的效果进行说明,但本发明并不限定于此。
(实施例1)
在下述条件下制作防锈构件。
基材:钢板
锌系镀层:电镀锌
化成处理液:以Cr(三价铬)为化成元素,含有胶体二氧化硅
化成处理:在化成处理液中浸渍40秒钟并进行水洗、干燥
针对所获得的防锈构件,使用XPS分析装置来测定厚度方向上的组成分析(深度分布)。将表示测定结果的曲线图及表示根据所述结果而算出的Si/Zn比的深度方向上的推移的曲线图分别示于图1及图2中。如图1及图2所示,富Si区域的厚度为220nm左右,化成皮膜的厚度为300nm左右。因此,实施例1中,连续位于富Si区域的倾斜区域的厚度为80nm左右。作为如上所述般较厚地形成化成皮膜的理由,可列举调整化成处理的条件等而使化成反应缓慢进行。
另外,将防锈构件供于日本工业标准(Japanese Industrial Standards,JIS)Z2371:2015中所记载的中性盐水喷雾试验中,每隔规定时间以目视进行观察,观察是否产生白锈及在产生白锈的情况下,进行白锈产生面积比率的测定。将测定结果示于表1中。
[表1]
(实施例2)
虽与实施例1相同,但将在化成处理液中的浸渍时间自40秒变更为20秒而获得防锈构件。针对所述防锈构件,也测定深度分布并算出Si/Zn比。将这些结果示于图3及图2中。如图3及图2所示,富Si区域的厚度为130nm左右,化成皮膜的厚度为200nm左右。因此,实施例2中,连续位于富Si区域的倾斜区域的厚度为70nm左右。
(实施例3)
虽与实施例1相同,但将在化成处理液中的浸渍时间自40秒变更为60秒而获得防锈构件。针对所述防锈构件,也测定深度分布并算出Si/Zn比。将这些结果示于图4及图2中。如图4及图2所示,富Si区域的厚度为300nm左右,化成皮膜的厚度为400nm左右。因此,连续位于富Si区域的倾斜区域的厚度为100nm左右。
(比较例)
虽与实施例1相同,但进行专利文献1的实施例1中所示的化成处理而获得防锈构件。针对所述防锈构件,也测定深度分布并算出Si/Zn比。将这些结果示于图5及图2中。比较例的防锈构件的化成皮膜中,不存在Si/Zn比为1以上的富Si区域,化成皮膜的厚度为60nm左右。进行比较例的化成皮膜的表面观察,结果如图7所示,与实施例1的化成皮膜的表面(图6)的表面形态大不相同。另外,与实施例1同样地进行中性盐水喷雾试验。将其结果示于表1中。
(实施例4)
虽与实施例1相同,但通过利用电镀Zn/Ni合金代替电镀锌来形成锌系镀层而获得防锈构件。使用荧光X射线膜厚计来确认所形成的锌系镀层的组成,结果Zn为82原子%,Ni为18原子%。因此,根据所述式(2-2),实施例4的防锈构件所具备的化成皮膜的倾斜区域中的锌含量为65.6原子%以下。
对以所述方式获得的防锈构件测定深度分布,并算出Si/Zn比。将这些结果示于图8及图9中。如图8及图9所示,与锌系镀层包含电镀锌的情况同样地,在锌系镀层包含电镀Zn-Ni合金的情况下,也在防锈构件的化成皮膜上存在Si/Zn比为1以上的富Si区域,其厚度为120nm左右,化成皮膜的厚度为190nm左右。因此,实施例4中,连续位于富Si区域的倾斜区域的厚度为70nm左右。这些结果为与图3等所示的实施例2相近的结果。
(实施例5至实施例17)
根据下述条件而制作具有反应型的化成皮膜的防锈构件。
基材:钢板
锌系镀层:如表2所示
Zn:与实施例1相同的电镀锌
Zn-Ni:与实施例4相同的电镀Zn-Ni合金
化成处理液:以表2所示的元素为化成元素,含有胶体二氧化硅
化成处理:在化成处理液中浸渍40秒钟并进行水洗、干燥
[表2]
针对以所述方式获得的防锈构件,与实施例1同样地测定深度分布,根据所获得的深度分布而求出Si/Zn比为1以上的富Si区域的厚度(单位:nm)。将结果示于表2中。再者,在表2中,就容易进行对比的观点而言,也示出实施例1至实施例4的结果。如表2所示,确认到:除实施例1至实施例4中所使用的Cr以外,即便使用P、Mg、Ti、Mo等各种元素作为化成元素,也能够形成具有100nm以上的厚度的富Si区域的化成皮膜。另外,确认到:即便在使用多种化成元素的情况下,也能够形成具有100nm以上的厚度的富Si区域的化成皮膜。
Claims (9)
1.一种防锈构件,其包括基材、设置于所述基材上的锌系镀层以及设置于所述锌系镀层上且含有Si的化成皮膜;且所述防锈构件的特征在于:
所述化成皮膜在表层侧以100nm以上的厚度具有富Si区域,所述富Si区域的Si含量相对于Zn含量的原子比为1以上。
2.根据权利要求1所述的防锈构件,其中所述化成皮膜在所述富Si区域与所述锌系镀层之间具有倾斜区域,所述倾斜区域中,越接近所述锌系镀层,Zn的含量越增大。
3.根据权利要求2所述的防锈构件,其中所述倾斜区域的厚度为50nm以上。
4.根据权利要求2或3所述的防锈构件,其中所述富Si区域与所述倾斜区域在厚度方向上连续。
5.根据权利要求1至4中任一项所述的防锈构件,其中所述化成皮膜还含有选自由Cr、P、B、C、S、O、Li、Ca、Mg、Mo、V、Nb、Ta、W、Zr、Fe、Ni、Co、Cu、Si、Ti、Zn、Al、Sn及Bi以及镧系元素所组成的群组中的一种或两种以上的元素。
6.根据权利要求1至5中任一项所述的防锈构件,其中所述化成皮膜为反应型的化成皮膜。
7.根据权利要求1至6中任一项所述的防锈构件,其中所述化成皮膜含有氧化硅。
8.根据权利要求1至7中任一项所述的防锈构件,其中所述化成皮膜实质上不含有有机粘合剂成分。
9.一种防锈构件的制造方法,所述防锈构件为如权利要求7所述的防锈构件,且所述防锈构件的制造方法的特征在于,包括:
镀敷工序,在所述基材上形成所述锌系镀层而获得包括所述基材与所述锌系镀层的被处理构件;以及
化成处理工序,包含使所述被处理构件与化成处理液接触,其后,对所述被处理构件进行清洗,从而在所述被处理构件上形成所述化成皮膜;并且
所述化成处理液包含含有进行化成反应的元素的含化成元素的物质及氧化硅。
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