CN1131444A - 单面镀锌钢条的磷化处理方法 - Google Patents

单面镀锌钢条的磷化处理方法 Download PDF

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CN1131444A
CN1131444A CN94193432A CN94193432A CN1131444A CN 1131444 A CN1131444 A CN 1131444A CN 94193432 A CN94193432 A CN 94193432A CN 94193432 A CN94193432 A CN 94193432A CN 1131444 A CN1131444 A CN 1131444A
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K·比特纳
W·K·M·詹森
K·P·莫尔
T·温德尔
H·威特佐里克
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Abstract

在对单面镀锌或合金镀锌的钢条或钢板的磷化处理过程中，使钢条或钢板与45-80℃温度下的磷化溶液接触4-20秒钟，磷化溶液含有0.5-5克/升锌、3-20克/升P2O5、0.05-0.2克/升NO2、3-30克/升NO3、0.2-2.5克/升铁的络合剂，其S值为0.08-0.30，并且对于热浸镀锌或热浸合金镀锌的钢条或钢板，另含有0.2-4克/升复杂和/或简单氟化物(以F计)。
特别合适的络合剂是螯合形成物，诸如酒石酸、柠檬酸、乙二胺四乙酸、次氮基三乙酸和/或草酸。磷化溶液优选含有其它双价阳离子，尤其是锰和/或镍离子。

Description

单面镀锌钢条的磷化处理方法
本发明涉及通过使用含有锌、硝酸根和亚硝酸根的磷化溶液进行单面镀锌或合金镀锌的钢条或钢板的磷化处理方法。
金属磷化的目的是为了在金属表面产生坚固的金属/磷酸盐共生层，这可以提高其抗腐蚀性，而且可与油漆和其它有机涂料结合而极大提高附着性和涂料下面的抗腐蚀蠕变性。另外，这些磷化层充当绝缘物以抑制电流通过并且与润滑剂结合使滑移操作易于进行。
对于涂漆前的预处理，低锌磷化过程尤其合适，其中磷化溶液含有相对较低含量的锌离子，例如0.5—1.5克/升(DE—C—2232067，EP—B—39093)。在这样的条件下，在钢板上产生磷酸千枚岩(Zn2Fe(PO4)2·4H2O)含量很高的磷化层，磷酸千枚岩的抗腐蚀性比从具有更高锌含量的磷化溶液中沉淀出的磷锌矿(Zn3(PO4)2·4H2O)高得多。通过向低锌磷化溶液中添加镍和/或锰离子，并与油漆协同可使保护质量进一步提高(EP—A—228151，EP—B—414296，EP—B—414301，EP—A—544650，DE—A—3918136)。例如，添加0.5—1.5克/升的锰离子和0.3—2.0克/升镍离子的低锌方法，即所谓的三阳离子方法可广泛用于制备油漆金属表面上，例如汽车车体的阴极电原子浸渍上漆过程。
特别对于电解镀锌或热浸镀锌钢条，研究出了允许磷化层在短处理时间内形成的磷化过程。这样，例如自DE—A—3245411中我们知道的电解镀锌钢条，有一个层质量小于2克/平方米的磷化层，其中所用溶液含有1—2.5克/升锌离子，自由酸含量为0.8—3点(Punkt)并且总酸/自由酸的酸比为5—10。这些条件下处理时间不超过5秒。在另一种电解镀锌和/或热浸镀锌的钢条的磷化过程中，所用磷化溶液含有0.02—0.75克/升锌离子、0.2—2.0克/升锰离子、0.1—2.0克/升镍离子、10—20克/升磷酸根离子和0.5—30克/升的硝酸根离子，在40—70℃的温度范围下，处理周期为2—30秒。此时自由酸含量必须在1.6—3.0点范围内，总酸含量在12—40点范围内，并且镍离子与硝酸根离子的质量比在1∶10到1∶60之间，锰离子与硝酸根离子的质量比在1∶1到1∶40之间(DE—A—3927131)。
当在双面镀锌或热浸镀锌的钢条上使用前面提到的允许短处理时间的磷化溶液时，并无严重的混乱现象发生。但是最近单面镀锌的钢条应用增加，尤其在汽车工业中。当在单面镀锌的钢条上应用前面所说的短时间方法时，在磷化溶液中强烈形成磷酸盐淤渣，其数量已可具有干扰性。另外，在钢面上开始形成磷化层，这对于诸如汽车车体的以后磷化是尤其不利的。
本发明的目的就是提供一种适于单面镀锌或合金镀锌的钢条或钢板的磷化处理方法，此方法对抑制淤渣形成具有长远的影响，可阻止钢面上磷化层的形成，对钢的镀锌和合金镀锌面上的磷化层的形成和质量无不利影响，并且使用简单和经济。
为了达到这个目标，依据本发明开始时提及的此方法以以下方式进行，使镀锌或合金镀锌钢条或钢板与磷化溶液在45—80℃温度下接触4—20秒，溶液含有
0.5—5克/升锌
3—20克/升P2O5
0.005—0.2克/升NO2
3—30克/升NO3
0.2—2.5克/升铁络合剂，并且S值为0.08—0.30；另外，对于热浸镀锌或热浸合金镀锌钢条或钢板，另外含有0.2—4克/升复杂和/或简单氟化物(以F计算)。
据发现使用上述浓度的铁络合剂和亚硝酸根，自未经镀锌或合金镀锌的钢条或钢板面上溶下的铁，大部分经过了配位键合。无法确定在钢面上层的形成。在磷化溶液中磷酸盐淤渣的形成完全停止或被减少至最多为别的条件下观察到的淤渣量的10％。所需的镀锌或合金镀锌面的磷化结果并未受到不利影响。
所指出的络合剂范围限制是很重要的，太高的络合剂浓度通过与形成层的阳离子配合对磷化层的形成有不利影响。如果所加的络合剂太少，就不可避免磷化溶液中磷酸盐淤渣的形成和钢面上磷化层的产生。使用太高或太低的亚硝酸根浓度，镀锌或合金镀锌的钢面上的磷化和溶解铁的配合都会受到不利影响。例如，使用过高的亚硝酸根浓度时，钢面上初始层的形成就不可避免。该初始层形成对在汽车部件上的后续磷化有不利影响，至少导致不需要的淤渣形成。
为了防止在正常生产能力下由于自动催化亚硝酸根形成所带来的亚硝酸根浓度超过上限值；一般有必要采取合适的反措施。一个特别有效的反措施是通过使用分解亚硝酸根的物质可保持磷化溶液中亚硝酸根浓度在上述限制中，例如尿素和/或氨基磺酸。这可以由连续或间歇添加实现。一个尤其好的方法是使磷化溶液中尿素浓度为1—3克/升和/或氨基磺酸浓度为0.5—2克/升，以保持亚硝酸根浓度在所要求的范围内。这样可以形成一个静态，其中尿素或氨基磺酸正好分解由自动催化产生的亚硝酸根。
依据本发明所使用的钢条或钢板其镀锌或合金镀锌面上镀层为电解锌(ZE)、热浸锌(Z)、或基于锌/镍(ZNE)、锌/铁(ZF)或锌/铝(ZA或AZ)的合金。后者一般也包括例如55％重量的Al和45％重量的Zn的合金。
本发明的的一个优选的实施方案是使镀锌或合金镀锌的钢条或钢板与磷化溶液接触，溶液含有
1—2.5克/升锌
10—20克/升P2O5
0.020—0.060克/升NO2
5—15克/升NO3
0.2—2.5克/升铁络合剂，并且其S值为0.12—0.20。本发明的此实施方案的优点在于形成的淤渣特别少和在镀锌或合金镀锌面上形成非常好的磷化层。
使用本发明如下有利的实施方案会产生特别优良的结果，使镀锌或合金镀锌钢条或钢板与如下溶液相接触，其中含有螯合物质作为络合剂，如酒石酸、柠檬酸、乙二胺四乙酸、次氮基三乙酸和/或草酸。此前述络合剂在磷化溶液中的优选含量为：
0.5—2.5克/升酒石酸
0.2—0.4克/升柠檬酸
0.2—2.5克/升次氮基三乙酸或乙二胺四乙酸(以乙二胺四乙酸计)。
所得磷化层的质量可以依据本发明的另一种实施方案而得以提高，即使镀锌或合金镀锌的钢条或钢板与含有其它双价阳离子尤其是锰离子和/或镍离子的磷化溶液相接触。在这种情况下，最好是调节磷化溶液中这些离子的浓度为1—3克/升，特别是1.5—2.5克/升锰离子和/或0.1—2.5克/升，特别是0.5—1.5克/升镍离子。
由于磷化溶液需要具有较高的活性，当处理热浸镀锌或热浸合金镀锌钢条或钢板时，必不可少的是使用含有复杂和/或简单氟化物的磷化溶液。
但是，依据本发明更为有利的实施方案，当处理电解镀锌钢条或钢板时，所用磷化溶液也含有复杂和/或简单氟化物，优选量为0.1—3克/升(以F计)。作为复杂氟化物，优选氟硼酸盐、氟硅酸盐、氟钛酸盐和/或氟锆酸盐。
钢条或钢板的磷化处理可以使用传统方法，即浸或喷涂。但是，特别有利的是通过喷涂法使用溶液。
磷化溶液通常用补加浓度进行补充，其中例如使用电导测量计进行自动控制。合适的补加浓度包含，例如10—30％重量的P2O5，3—20％重量的NO3和0—2％重量的锌。补加浓度中锌的含量主要依赖于钢条或钢板上存在的锌或合金锌层的活性。如果锌层活性较高，并且由于酸浸效应有较大量的锌进入镀槽，就可以使用较低锌浓度的补加溶液，如在0—20％重量浓度之间。在极端情况下，即特别当进行刚镀锌完毕的钢条的磷化处理时，补加浓度中也可以无锌。
依据本发明的优选实施方案—使用含有镍和/或锰离子的磷化溶液—补加浓度另外含有0.2—2％重量的镍和/或1—4％重量的锰。
原则上，补加溶液也可以含有铁的络合剂，并且如果需要的话，还有NO2分解剂；但是为了更好调节所需浓度，一般优选分别补加这两种物质。
使用依据本发明的方法得到的磷化层重量大约为1—2克/平方米。
本发明将举例说明并更详细的参考以下实施例：实施例
在钢条的电解镀锌之后，立即使用含以下物质的溶液进行磷化：
锌：1.8克/升
P2O5：14.5克/升
镍：1.3克/升
锰：2.0克/升
酒石酸：1克/升
尿素：1克/升
NO3：7克/升
NO2：0.040克/升
磷化溶液的S值为0.17，其温度调至50—55℃。喷涂8秒钟完成。
磷化处理在25立方米的镀槽中进行16小时。此后可以测出磷化溶液的湿淤渣量为2ml/L。这相当于大约每平方米钢表面上有0.6毫升淤渣。在锌面上形成了极好的磷化层，该层重量为1.6克/平方米。钢面处于理想状态，即几乎没有膜层形成。
在一个对比实验中，不加络合剂和NO2分解剂，而其它条件相同，测到磷化溶液中湿淤渣量为28ml/L。这相当于大约每平方米钢面上有8.4毫升淤渣。锌面上层重量也达到1.6g/m2，但是钢面上有初始磷化层形成。

Claims (11)

1.单面镀锌或合金镀锌的钢条或钢板的磷化处理方法，使用含有锌、硝酸根和亚硝酸根的磷化溶液，其特征为，使单面镀锌或合金镀锌的钢条或钢板与45—80℃温度下的磷化溶液接触4—20秒，溶液含有
0.5—5克/升锌
3—20克/升P2O5
0.005—0.2克/升NO2
3—30克/升NO3
0.2—2.5克/升铁络合剂，其S值为0.08—0.30，对于热浸镀锌或热浸合金镀锌的钢条或钢板磷化处理情况，另外含有0.2—4克/升复杂和/或简单氟化物(以F计)。
2.根据权利要求1的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，其中亚硝酸根浓度使用尿素和/或氨基磺酸保持在0.005—0.2克/升范围内。
3.根据权利要求2的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，其中亚硝酸根浓度通过使用尿素浓度1—3克/升和/或氨基磺酸浓度为0.5—2克/升而保持在0.005—0.2克/升。
4.根据权利要求1，2或3的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液含有
1—2.5克/升锌
10—20克/升P2O5
0.020—0.060克/升NO2
5—15克/升NO3
0.2—2.5克/升铁络合剂，且其S值为0.12—0.20。
5.根据权利要求1—4的一项或多项的方法，特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液含有一种螯合形成物作为络合剂，例如酒石酸、柠檬酸、乙二胺四乙酸、次氮基三乙酸和/或草酸。
6.根据权利要求5的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液含有
0.5—2.5克/升酒石酸
0.2—0.4克/升柠檬酸
0.2—2.5克/升次氮基三乙酸或乙二胺四乙酸(以乙二胺四乙酸计)。
7.根据权利要求1—6一项或多项的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液中含有其它双价阳离子，尤其为锰和/或镍离子。
8.根据权利要求7的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液含有1—3克/升，优选为1.5—2.5克/升锰离子，和/或0.1—2.5克/升，优选为0.5—1.5克/升镍离子。
9.根据权利要求1—8一项或多项的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液中含有复杂和/或简单氟化物，优选量为0.1—3克/升(以F计)。
10.根据权利要求9方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板与一种磷化溶液相接触，溶液含有氟硼酸盐、氟硅酸盐、氟钛酸盐和/或氟锆酸盐作为复杂氟化物。
11.根据权利要求1—10一项或多项的方法，其特征为，使单面镀锌或合金镀锌的钢条或钢板通过喷涂处理与磷化溶液相接触。
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ATE170931T1 (de) 1998-09-15
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