CN102947486B - 在金属表面制备防腐层的方法 - Google Patents
在金属表面制备防腐层的方法 Download PDFInfo
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- CN102947486B CN102947486B CN201080067028.7A CN201080067028A CN102947486B CN 102947486 B CN102947486 B CN 102947486B CN 201080067028 A CN201080067028 A CN 201080067028A CN 102947486 B CN102947486 B CN 102947486B
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Abstract
本发明涉及一种为具有由锌、镁、铝或它们的一种合金构成的表面的基体制备防腐层的方法，其中使待处理表面直接连续地与两种含三价铬离子、待处理表面的金属离子和至少一种络合剂的水性处理液接触。第一种处理液的pH值为1.0-4.0，而第二种处理液的pH值为3.0-12.0。本发明的方法能产生较少量的被重金属污染的废水。
Description
技术领域
本发明涉及一种在锌、铝或镁及其合金表面上形成基本不含四价铬的防腐层的方法。
背景技术
用于提高阴极腐蚀保护***的保护作用以及作为清漆和油漆的底漆的转化层很早就已为人所知。除磷化法外，专门针对含锌、铝和镁的表面的铬化处理表面的方法也已经形成。
此处，待处理表面暴露于主要成分为四价铬化合物的处理液。因此产生的转化层也含有四价铬离子。铬化处理层通常表现出优异的抗腐蚀性和好的装饰性。而使用含四价溶液或含四价铬涂层的缺点是四价化合物的毒性。因此含四价铬转化层的使用受到例如ECDirective2000/53/EC(欧盟报废车辆技术指令)的严格限制。
作为铬化溶液的替代品，提出了与铬化处理相比通常称为“钝化处理”或“钝化液”的含三价铬的酸处理液。这些处理液，正如例子DE19615664A1中所述，主要由钴盐和在矿物酸溶液、乙二酸或羟基羧酸溶液中的三价铬盐组成。这种被称为“厚膜钝化”的方法应用于更高的温度，约40-60℃，从而获得足以在锌表面提供腐蚀保护的钝化层厚度。上述处理要在高于室温的温度下进行的必要性在于，与四价铬原子相比三价铬原子的反应性要差得多。作为提高温度的替代方案，反应时间的大幅增加出于经济原因通常是不可行的。
作为替代，US5415702中披露了一种在锌-镍合金层上用酸性的、含三价铬的，同时还含有磷的含氧酸的溶液处理得到的无四价Cr的黑色转化层。在该方法中，可形成具有优异装饰性的均匀黑色转化层。
WO03/05429披露了一种类似的转化层，其同样使用含三价铬还含磷酸根离子的酸性处理液制得。这种表面也具有优异的装饰性，但是如果没有进一步的后处理步骤如密封，就不能获得令人满意的防腐性。
EP1484432A1中披露了一种用于锌合金表面的含三价铬的黑色钝化液，其含有三价铬离子和硝酸盐以及羟酸，如酒石酸、马来酸、草酸、琥珀酸、柠檬酸、丙二酸或己二酸。为提高防腐性，使用该溶液处理过的表面必须随后进行密封处理。上述处理溶液需在高于室温的温度下使用。
US2004/0156999也公开了一种用于锌合金表面的黑色钝化处理的方法。处理液含三价铬离子和含磷的阴离子，以及硝酸盐和有机羧酸。提供的有机羧酸的例子为柠檬酸、酒石酸、马来酸、甘油酸、乳酸、乙醇酸、丙二酸、琥珀酸、草酸和戊二酸。
基本上，在制备保护层时有如下步骤：活化金属表面，在酸性钝化浴中制备转化层，通过一个或多个漂洗步骤从表面去除腐蚀性的钝化浴液，干燥和施加进一步的密封或者在后浸渍液中进行后浸渍和干燥。
该程序的缺点是被大量重金属和某些可能形成的络合物污染的漂洗污水必须以很复杂和昂贵的方式加以处置或处理。
由于上述的缺点，近来人们做了很多努力发展出了“无漂洗”方法。其中，基本上施加含有能促进钝化的金属组分，如铬、钛或锆，和由有机聚合物组成的成膜组分的转化层。这种方法主要被用于对铝表面的处理。与成膜聚合物结合的“无漂洗”磷化方法也常被披露。
于是，例如文件US6117251披露了一种包含氧化锌、磷酸、聚乙烯醇和另一种金属盐的用于对金属表面进行锌-磷化的水性溶液。
这些方法的应用仅限于锌、铝和镁的表面，尽管它们形成了嵌入有机基质的膜，但并未形成对达到令人满意的防腐性而言非常必须的封闭的氧化铬层或金属混合氧化物层。
发明内容
本发明的目的是提供一种对锌、铝或镁及其合金的金属表面进行无四价铬钝化处理的方法，通过它为表面提供优异的防腐性能且同时不会产生被污染的漂洗水。
上述目的通过在锌、铝或镁以及所述金属的合金表面形成防腐层的方法得以实现，其包括以下步骤：
i)将所述金属或金属合金的表面与包括以下组分的溶液接触：
三价铬离子，
选自表面金属或表面金属合金的金属离子，和
至少一种络合剂，其选自由羧酸、多元羧酸、羟基羧酸、氨基羧酸、醇类、胺类和醚类组成的组，
其中处理液的pH值为从1.0到4.0，
ii)然后将所述金属的表面与包括以下组成的溶液直接接触：
三价铬离子，
选自表面金属或表面金属合金的金属离子，和
至少一种络合剂，其选自由羧酸、多元羧酸、羟基羧酸、氨基羧酸、醇类、胺类和醚类组成的组，
其中处理液的pH值为从3.0到12.0。
所述在金属和金属合金表面形成防腐层的方法的特征在于，金属表面在所述方法的步骤一中被钝化和在步骤二中在组成大致相同的溶液中进行后处理。所述后处理将钝化层固定在金属表面上，从而得到持久的防腐。由于在两个步骤中使用了组成基本相同的液，因此在现有技术的方法中为避免夹带和实现良好的防腐而在两个处理步骤之间所必不可少的冲洗步骤就可以省去了。在已知方法中所必须的冲洗步骤会产生被重金属离子和其他化学成分污染的废水，其必须以相当昂贵的费用加以处理和净化且会造成环境污染。
本发明的方法首次实现了钝化和后处理使用基本上完全相同的溶液，而不会对表面的防腐性产生不利影响。
将两个步骤中的溶液有目的地设定为不同的pH值，使得可以控制本身相同的处理液的功能。
在步骤一中使用的处理液的pH值设为1.0到4.0，优选1.2到3.0，最优选1.5到2.5，其主要由三价铬盐以及用于金属锌、镁或铝及其合金的络合剂组成。基于溶液的初始pH值，可以为此采用酸或碱。最适合的酸是硫酸和硝酸。作为碱，优选使用碱金属氢氧化物，特别是NaOH和KOH。
三价离子可以以无机铬(II)盐(如碱性硫酸铬(III)、氢氧化铬(III)、磷酸二氢铬(III)、氯化铬(III)、硝酸铬(III)、硫酸铬(III)钾)的形式或以有机酸的铬(III)盐(如甲烷磺酸铬(III)、柠檬酸铬(III))的形式加入处理步骤一和步骤二的处理液中，或是在适当的还原剂存在下由适合的四价铬化合物还原产生。适合的四价铬化合物为，例如氧化铬(VI)、铬酸盐(如铬酸钾或铬酸钠)、重铬酸盐(如重铬酸钾或重铬酸钠)。用于原位产生三价铬离子的适当的还原剂为，例如，硫酸盐(如硫酸钠)、二氧化硫、亚磷酸盐(如次亚磷酸钠)、膦酸、过氧化氢、甲醇、葡萄糖酸。三价铬离子还可以以无机铬(III)盐、铬(VI)盐和适当的还原剂的混合物的形式加入。
两种处理液所含三价铬离子的量都为0.5-10g/L，优选2-6g/L，最优选2.5-3.5g/L。
步骤一的处理液的温度一般为10-50℃，尤其10-40℃，优选20-30℃。
在处理液中的处理时间优选在10-600s范围内，更优选20-120s，最优选30-90s。
在该方法的一个优选实施方案中，通过在钝化液中连接基体为阴极来辅助所述钝化处理。在此，基体的阴极电流密度优选在0.05-10A/dm2的范围内，更优选0.1-5A/dm2，最优选0.1-3A/dm2。
假定了，在步骤一中，在设定的强酸性pH值条件下明显更优先发生处理液中的含三价铬的物质的钝化反应。结果，在这个步骤中，在锌、镁或铝及其合金的整个金属表面上非常可靠地形成非渗透性的钝化层。然而，这个层还不是特别耐久，特别是其中上不能抗机械应力。
在步骤一中形成的钝化层由此在步骤二中被固定和变得耐久。
步骤二中的处理液主要由三价铬盐以及用于金属锌、镁或铝及它们的合金的络合剂组成。该溶液的pH值设为2.0到12.0，优选3.0到7.0，最优选3.5到5.0。基于溶液的初始pH值，可以为此采用酸或碱。最适合的酸是硫酸和硝酸。作为碱，优选使用碱金属氢氧化物，特别是NaOH和KOH。
步骤二的处理液的温度一般为10-80℃，尤其10-70℃，优选40-60℃。
在处理液中的处理时间优选在5-600s范围内，更优选8-120s，最优选10-90s。
在步骤二中，处理液的钝化组分实际上并不起作用，因此可对所述方法加以改进，使步骤二中的溶液开始仅由所述络合剂构成，仅在处理过程中由于夹带的结果而逐渐接近步骤一和步骤二的处理液的组成。
假定了，在步骤二中，由在设定的弱酸、中性或碱性pH值条件下明显更优先发生由处理液中的络合剂产生的固定反应。结果，之前施加在整个金属表面上的钝化层在此步骤被耐久地固定。仅作为该步骤的结果，在表面上形成能够长期承受机械和其他应力的耐久的防腐层在表面形成。
锌、镁或铝或其合金可以用电化学方法沉积在基体上，或通过其他方法如热镀锌施加，或构成待处理的制品的材料。所述方法是本领域技术人员已知的。
常规地，用于含锌表面的无四价铬钝化液一般包含三价铬离子源和一种或多种络合剂。这种溶液对本领域技术人员来说是已知的。上述处理液的pH值一般小于2。
在本发明的方法的两个步骤中，络合剂选自由羧酸、多元羧酸、羟基羧酸、氨基羧酸、醇类、醚类和胺类组成的组。
适合的络合剂为甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、己烷羧酸、环戊烷羧酸、乙酰水杨酸、苯甲酸、硝基苯甲酸、3，5-二硝基苯甲酸、四氢呋喃-2-羧酸、山梨酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、邻苯二甲酸、对苯二甲酸、亚乙基二次氮基四乙酸、乙二胺四乙酸、二亚乙基二胺五乙酸、次氮基三乙酸、酒石酸、柠檬酸、异柠檬酸、苹果酸、抗坏血酸、乳酸、葡萄糖酸、葡萄糖醛酸、没食子酸、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、1-戊醇、乙二醇、丙二醇、丁二醇和乙二醇醚。
在两种处理液中的每一种内的络合剂的总量在两种情形下各自为0.5-200g/L，尤其0.75-200g/L，优选5-100g/L，最优选10-50g/L。
当待处理表面由锌或锌合金构成时，两种处理液中含有的水溶性锌化合物的量在两种情形下各自为0.75-200mmol/L，优选3-100mmol/L，最优选10-40mmol/L。
当待处理表面由镁或镁合金构成时，两种处理液中含有的水溶性镁化合物的量在两种情形下各自为2-210mmol/L，优选8-75mmol/L，最优选12-40mmol/L。
当待处理表面由铝或铝合金构成时，两种处理液中含有的水溶性铝化合物的量在两种情形下各自为1.8-185mmol/L，优选7.5-85mmol/L，最优选11-40mmol/L。
步骤一和步骤二的两种浴液中任选地含有氟离子源，其选自由NaF、KF、NH4F、NaHF2、KHF2和NH4HF2组成的组。氟离子的添加量在两种情形下各自为中0.001-10g/L，优选0.01-5g/L，最优选0.05-2g/L。
步骤一和步骤二的两种浴液中任选地含有氯离子源，其选自由NaCl、KCl和NH4Cl组成的组。氯离子的添加量在两种情形下各自为0.01-20g/L，优选0.1-10g/L，最优选0.5-5g/L。
步骤一和步骤二的浴液中的另一种可选组分为磷酸盐化合物，至少一种磷酸盐化合物选自由正磷酸、多磷酸、偏磷酸、这些酸的盐、具有含最多12个碳原子的有机基团的这些酸的酯，以及这些化合物的混合物。磷酸盐化合物的添加量在两种情形下各自为0.5-100g/L，优选3-50g/L，更优选5-20g/L。
为了提高防腐性，可选地将至少一种选自由Sc、Y、Ti、Zr、Mo、W、Mn、Fe、Co、Ni、Zn、B、Al、Si组成的组的金属或准金属加入到步骤一和步骤二的两种处理液中。这些元素可以以它们的盐的形式或以配合物阴离子或这些阴离子的相应酸(例如，六氟硼酸、六氟硅酸、六氟钛酸或六氟高酸、四氟硼酸或六氟磷酸或其盐)的形式加入。
本发明的方法可用于很多钝化***。当可溶性钴盐在两种情形下各自以0.2-3g/L，优选0.5-1g/L的量加入步骤一和步骤二的各个浴中时，黑色钝化处理能实现优秀的防腐性能。
作为后处理，从处理液2中取出的基体可以无需冲洗直接干燥。干燥，可以例如在滚筒中进行。附着在滚筒上的处理液2的残留物可以用热碱性溶液去除。
实施例
制备具有以下组成的水性反应溶液：
用于步骤一的反应溶液1：
3.61g/L的三价铬离子，其作为74％重量浓度的硝酸铬(III)溶液添加，10.9g/L的磷酸根离子，2.5g/L的锌离子，12.1g/L的葡萄糖酸，10g/L的酒石酸，0.088g/L的氟离子和1.22g/L的氯离子。
用硝酸将溶液的pH值调节至1.8。
用于步骤二的反应溶液2：
3.61g/L的三价铬离子，其用74％重量浓度的硝酸铬(III)溶液添加，10.9g/L的磷酸盐离子，2.5g/L的锌离子，12.1g/L的葡萄糖酸，10g/L的酒石酸，0.088g/L的氟离子和1.22g/L的氯离子。
用氢氧化钠将溶液的pH值调节至4。
在酸性锌电解液(商品名：购自AtotechDeutschlandGmbH的UnizinkNCZ420)中为钢部件镀覆10μm厚的锌层。所述钢部件随后在20℃的硝酸/水混合物(约0.2％硝酸)中浸渍10s以活化表面。该部件随后用脱矿物质水冲洗并立刻浸入如前述所制备的反应液1中，在25℃下持续40s。不用进一步冲洗，部件随后被立即浸入如前述所制备的反应液2中，在50℃下持续15s。让反应液自然滴落后，构件不需最终冲洗就在120℃下干燥15分钟。
在基于DIN50021SS的盐雾试验中，所述表面保持400h无变化，仅在700h后出现5％的白锈腐蚀，以及仅在超过1000h后出现红锈腐蚀。通过本发明所述方法实现的防腐至少与现有技术的方法可以实现的防腐一样好，不同的是本发明的方法产生的有重金属污染的废水的量显著降低。
Claims (13)
1.在锌、铝或镁及其合金表面形成防腐层的方法，其包括以下步骤：
i）将所述金属或金属合金的表面与包括以下组分的溶液接触：
三价铬离子，
选自表面金属或表面金属合金的金属离子，和
至少一种络合剂，其选自由羧酸、醇类、胺类和醚类组成的组，
其中处理液的pH值为1.0-4.0，
ii）然后，无需漂洗操作，直接将所述金属的表面与以下组成的溶液直接接触：
三价铬离子，
选自表面金属或表面金属合金的金属离子，和
至少一种络合剂，其选自由羧酸、醇类、胺类和醚类组成的组，
其中处理液的pH值为3.0-12.0，其中两个步骤i）和ii）中的溶液具有不同的pH值，
以及
iii）在与两种处理液接触后，无需进行最终冲洗步骤，直接干燥。
2.如权利要求1所述的方法，其中所述两种处理液各自含有0.5-200g/L的络合剂。
3.如权利要求1所述的方法，其中所述两种处理液都含有至少一种水溶性钴化合物。
4.如权利要求1所述的方法，其中所述两种处理液各自含有至少一种选自以下组的磷酸盐化合物：正磷酸、多磷酸、偏磷酸、这些酸的盐、具有含最多12个碳原子的有机基团的上述酸的酯、以及这些化合物的混合物。
5.如权利要求1所述的方法，其中所述两种处理液都含有氟离子，且各自所含氟离子的量为0.001-10g/L。
6.如权利要求1所述的方法，其中所述两种处理液都含有氯离子，且各自所含氯离子的量为0.1-10g/L。
7.如权利要求1所述的方法，其中步骤一中的处理液的温度是10-50℃。
8.如权利要求1所述的方法，其中步骤二中的处理液的温度是10-80℃。
9.如权利要求1所述的方法，其中在所述两个步骤中在两种处理液中的处理时间都在10-600s的范围内。
10.如权利要求1所述的方法，其中在所述两种处理液每个中都加入的可溶性三价铬离子的量为0.5-10g/L。
11.如权利要求1所述的方法，其中通过在钝化液中连接基体为阴极来辅助步骤一的钝化处理。
12.如权利要求11所述的方法，其中所述基体上的阴极电流密度在0.05-10A/dm2的范围内。
13.如权利要求1所述的方法，其中羧酸是多元羧酸、羟基羧酸或氨基羧酸。
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2492372A1 (en) * | 2011-02-23 | 2012-08-29 | Enthone, Inc. | Aqueous solution and method for the formation of a passivation layer |
| CN104060249B (zh) * | 2013-09-05 | 2016-06-29 | 攀钢集团攀枝花钢铁研究院有限公司 | 金属表面铬处理剂及其制备方法和热镀金属材料 |
| CN104060252B (zh) * | 2013-09-05 | 2016-07-06 | 攀钢集团攀枝花钢铁研究院有限公司 | 表面处理剂及其制备方法和热镀金属材料 |
| ES2732264T3 (es) | 2014-02-13 | 2019-11-21 | Doerken Ewald Ag | Procedimiento para la preparación de un sustrato provisto de una pasivación libre de cobalto y libre de cromo-VI |
| US10415148B2 (en) * | 2014-03-07 | 2019-09-17 | Macdermid Acumen, Inc. | Passivation of micro-discontinuous chromium deposited from a trivalent electrolyte |
| CN105937031B (zh) * | 2016-06-29 | 2018-10-30 | 周少霞 | 一种热镀锌板用钝化液的制备方法 |
| CN107557773A (zh) * | 2016-06-30 | 2018-01-09 | 比亚迪股份有限公司 | 一种铜保护剂、制备方法及铜的保护方法 |
| PT3360989T (pt) | 2017-02-13 | 2019-04-02 | Atotech Deutschland Gmbh | Método para passivar eletroliticamente uma camada de crómio exterior ou de liga de crómio exterior para aumentar a sua resistência à corrosão |
| US10683576B2 (en) * | 2017-03-27 | 2020-06-16 | Baker Hughes, A Ge Company, Llc | Corrosion inhibitors for passivation of galvanized coatings and carbon steel |
| US10450668B2 (en) | 2017-04-11 | 2019-10-22 | Savannah River Nuclear Solutions, Llc | Development of a passivated stainless steel surface |
| CN109423681B (zh) * | 2017-08-30 | 2021-02-23 | 比亚迪股份有限公司 | 一种镁合金阳极氧化液及其制备方法及镁合金阳极氧化方法 |
| EP3502320B1 (en) | 2017-12-22 | 2020-07-22 | ATOTECH Deutschland GmbH | A method for increasing corrosion resistance of a substrate comprising an outermost chromium alloy layer |
| US20190226094A1 (en) * | 2018-01-19 | 2019-07-25 | Baker Hughes, A Ge Company, Llc | Phosphorous-free, and iron activating agent-free rust removal, inhibition, and passivation |
| CN109576695A (zh) * | 2019-01-17 | 2019-04-05 | 温岭德利众机械制造有限公司 | 一种铝件用钝化剂和铝件表面处理的方法 |
| US11982003B2 (en) | 2019-03-30 | 2024-05-14 | Bl Technologies, Inc. | Concentrated aluminum compositions for aqueous corrosion control |
| CN110158068B (zh) * | 2019-06-17 | 2021-03-05 | 上海德修化工有限公司 | 一种环保型锌镍合金黑色钝化液及其使用方法 |
| CN112458452B (zh) * | 2020-12-08 | 2023-04-07 | 江门市瑞期精细化学工程有限公司 | 一种用于镀锌三价铬黑色钝化膜的封闭剂和制备方法及其在封闭处理中的工艺 |
| CN112813425A (zh) * | 2020-12-30 | 2021-05-18 | 江门市瑞期精细化学工程有限公司 | 一种用于镀锌三价铬钝化液和制备方法及应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287704B1 (en) * | 1996-04-19 | 2001-09-11 | Surtec Produkte Und System Fur Die Oberflachenbehandlung Gmbh | Chromate-free conversion layer and process for producing the same |
| JP2003171778A (ja) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | 金属の保護皮膜形成方法及び金属の保護皮膜 |
| CN1950544A (zh) * | 2004-03-03 | 2007-04-18 | 迪普索尔化学株式会社 | 用于降低三价铬酸盐处理溶液的转化膜总摩擦系数的试剂，三价铬酸盐处理溶液和其制备方法，以及总摩擦系数降低的三价铬酸盐转化膜和其制备方法 |
| CN101421434A (zh) * | 2006-02-17 | 2009-04-29 | 迪普索尔化学株式会社 | 用于在锌或锌合金上形成黑色的3价铬化学转化膜的处理溶液和在锌或锌合金上形成黑色的3价铬化学转化膜的方法 |
| CN101668882A (zh) * | 2007-03-05 | 2010-03-10 | 安美特德国有限公司 | 含锌表面的无铬(vi)黑色钝化 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3392008B2 (ja) * | 1996-10-30 | 2003-03-31 | 日本表面化学株式会社 | 金属の保護皮膜形成処理剤と処理方法 |
| BE634984A (zh) * | 1962-10-15 | |||
| JPS50102538A (zh) * | 1974-01-18 | 1975-08-13 | ||
| US3932198A (en) * | 1974-05-24 | 1976-01-13 | Amchem Products, Inc. | Coating solution having trivalent chromium and manganese for coating metal surfaces |
| AU513298B2 (en) * | 1978-06-02 | 1980-11-27 | International Lead Zinc Research Organization Inc. | Electrodeposition of black chromium |
| DD136979A1 (de) * | 1978-06-07 | 1979-08-08 | Alexander Strauch | Mittel zum schwarzchromatieren von zink |
| GB2051861B (en) * | 1979-06-29 | 1983-03-09 | Ibm | Deposition of thick chromium films from trivalent chromium plating solutions |
| US4263059A (en) * | 1979-12-21 | 1981-04-21 | Rohco, Inc. | Coating solutions of trivalent chromium for coating zinc and cadmium surfaces |
| US4328046A (en) * | 1980-10-14 | 1982-05-04 | Western Electric Co., Inc. | Chromate conversion coatings |
| US4578122A (en) * | 1984-11-14 | 1986-03-25 | Omi International Corporation | Non-peroxide trivalent chromium passivate composition and process |
| US4586989A (en) * | 1985-05-07 | 1986-05-06 | The Boeing Company | Method of plating a conductive substrate surface with silver |
| JP4856802B2 (ja) * | 1999-03-31 | 2012-01-18 | 日本表面化学株式会社 | 金属表面処理方法 |
| JP3774415B2 (ja) * | 2002-03-14 | 2006-05-17 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成するための処理溶液及び亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成する方法。 |
| US20050109426A1 (en) * | 2002-03-14 | 2005-05-26 | Dipsol Chemicals Co., Ltd. | Processing solution for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers, and method for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers |
| JP4625244B2 (ja) * | 2003-07-02 | 2011-02-02 | ディップソール株式会社 | ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法 |
| JP4628726B2 (ja) * | 2004-03-02 | 2011-02-09 | 日本表面化学株式会社 | アルミニウム部材及びその製造方法と製造用薬剤 |
| JP2005325401A (ja) * | 2004-05-13 | 2005-11-24 | Nippon Paint Co Ltd | 亜鉛又は亜鉛系合金メッキ鋼材の表面処理方法 |
| JP5110505B2 (ja) * | 2007-04-04 | 2012-12-26 | 奥野製薬工業株式会社 | 亜鉛又は亜鉛合金上に形成された化成皮膜に対するオーバーコート用組成物 |
| JP5336742B2 (ja) * | 2008-01-22 | 2013-11-06 | ディップソール株式会社 | 亜鉛又は亜鉛合金めっき上に加熱耐食性の良い３価クロム化成処理皮膜を形成するための化成処理方法 |
| JP5186642B2 (ja) * | 2008-05-27 | 2013-04-17 | ユケン工業株式会社 | 仕上げ剤、および仕上げ剤から形成されたオーバーコートを備える部材 |
| EP2281923A1 (de) * | 2009-07-03 | 2011-02-09 | ATOTECH Deutschland GmbH | Korrosionsschutzbehandlung für Oberflächen aus Zink und Zinklegierungen |
-
2010
- 2010-05-26 US US13/699,322 patent/US9738790B2/en active Active
- 2010-05-26 WO PCT/EP2010/057241 patent/WO2011147447A1/en active Application Filing
- 2010-05-26 KR KR1020127030938A patent/KR101726470B1/ko active IP Right Grant
- 2010-05-26 EP EP10721503.0A patent/EP2576861B1/en active Active
- 2010-05-26 JP JP2013511545A patent/JP5623632B2/ja active Active
- 2010-05-26 CN CN201080067028.7A patent/CN102947486B/zh active Active
- 2010-05-26 ES ES10721503.0T patent/ES2526658T3/es active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287704B1 (en) * | 1996-04-19 | 2001-09-11 | Surtec Produkte Und System Fur Die Oberflachenbehandlung Gmbh | Chromate-free conversion layer and process for producing the same |
| JP2003171778A (ja) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | 金属の保護皮膜形成方法及び金属の保護皮膜 |
| CN1950544A (zh) * | 2004-03-03 | 2007-04-18 | 迪普索尔化学株式会社 | 用于降低三价铬酸盐处理溶液的转化膜总摩擦系数的试剂，三价铬酸盐处理溶液和其制备方法，以及总摩擦系数降低的三价铬酸盐转化膜和其制备方法 |
| CN101421434A (zh) * | 2006-02-17 | 2009-04-29 | 迪普索尔化学株式会社 | 用于在锌或锌合金上形成黑色的3价铬化学转化膜的处理溶液和在锌或锌合金上形成黑色的3价铬化学转化膜的方法 |
| CN101668882A (zh) * | 2007-03-05 | 2010-03-10 | 安美特德国有限公司 | 含锌表面的无铬(vi)黑色钝化 |
Non-Patent Citations (1)
| Title |
|---|
| 三价铬钝化研究的进展;赖奂汶等;《材料保护（增刊）》;20081031;第41卷(第10期);第188－194页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101726470B1 (ko) | 2017-04-12 |
| KR20130109938A (ko) | 2013-10-08 |
| WO2011147447A1 (en) | 2011-12-01 |
| US20130078382A1 (en) | 2013-03-28 |
| ES2526658T3 (es) | 2015-01-14 |
| CN102947486A (zh) | 2013-02-27 |
| EP2576861A1 (en) | 2013-04-10 |
| JP2013526656A (ja) | 2013-06-24 |
| EP2576861B1 (en) | 2014-11-26 |
| US9738790B2 (en) | 2017-08-22 |
| JP5623632B2 (ja) | 2014-11-12 |
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