CN1085961A - 金属表面综合处理液 - Google Patents

金属表面综合处理液 Download PDF

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CN1085961A
CN1085961A CN 93102603 CN93102603A CN1085961A CN 1085961 A CN1085961 A CN 1085961A CN 93102603 CN93102603 CN 93102603 CN 93102603 A CN93102603 A CN 93102603A CN 1085961 A CN1085961 A CN 1085961A
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CN1032146C (zh
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刘振清
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations

Abstract

本发明为一种用作金属表面除油、除锈、使基体 表面生成一磷化膜的金属表面综合处理液。其配方 组分为磷酸H3PO4200～260克/毫升，酸式磷酸锰 Mn(H2PO4)220～25克/毫升及钼酸铵、硝酸钙、氯 化镁三种产生氧化气体的加速剂20～32克/升和 少量的活性剂及有机酸。清洗液用于去油、去锈表面 综合处理工艺时产生显著的效益，其工序简化为原来 的1/2～1/4，其处理时间只为原来的1/2～ 1/8，故工效大大提高，且处理液无毒、无重金属污 染，故为一种经济效益极好的综合处理液。

Description

本发明涉及一种作金属表面清洗、涂膜底层的综合处理液。
汽车、自行车车架、控制台仪表柜的台、柜架、电风扇等家用电气的部件等许多产品，在其喷涂漆、塑膜以前，均需先将金属件的油污、锈皮清洗去除，然后再磷化处理，使金属表面生成一磷化膜，作为油漆、喷塑膜的底层，从而提高涂膜与金属基体的附着力，以使涂膜不易脱落，且增强涂层抗冲击、抗形变能力，和提高漆、塑膜层的光泽性和美观。但是现常用的方法是多工位的，其除油、除锈、磷化等要经过十几道工序（参见图1），不仅占地多，投资大，工艺复杂，管理繁琐，工时多，而且清洗，除锈等工序过程中还存在酸、碱及有害重金属的污染，因此很不理想。
本发明的目的在于发明一种综合处理液，它可把除油、除锈、磷化的功能溶成一体，在一个槽内协同效应就可完成除油、除锈（包含除氧化皮）、磷化的功能。从而大大减少了工序、简化了管理程序、缩短了工时，既节省了大量的投资、占地和人力，又提高了功效。
本发明系将磷酸H3PO4、磷酸Mn（H3PO4）2及由钼酸铵（NH4）2Mo4O13·2H2O、硝酸、钙（或硝酸镁）、氯化镁MgCl2·6H2O，OP-10的活性剂组成的加速剂和有机酸酒石酸一起按一定配比量组成表面综合处理液。其中：
1.除油是由分别为非离子型和离子型表面活性剂作为除油剂，因为在该两种物质中同时含有亲油性极性基团和亲水性官能团，它们能定向地吸附在钢铁金属基体表面上而大大降低油污在此基面上的表面张力，再加上活性剂的乳化、增溶、分散、剥离的化学作用，使油污很快得到清除，一般在1.5分钟左右即行，且除油率可达99%左右，很干净。
2.除锈作用，本综合清洗处理液中的磷酸H3PO4为除锈剂，当有锈的工件放入液槽后就发生了下述反应：
通过上述反应以后，工件表面的锈蚀被除去，其中酒石酸作用在于将Fe（H2PO4）3和Fe（H2PO4）3络合从而得到干净的表体。
3.磷化作用：钢铁工件与磷酸接触后，发生下列反应：
在上述（1）～（4）的不断反应下，钢铁界面的游离酸度不断降低，待到一定值后，磷酸二氢盐和磷酸锰盐发生水解：
式中Me代表Fe铁或Mn锰。
水解后生成的磷酸氢盐和正磷酸盐在一定的pH值下超过了溶度积而在工件表面沉积生成磷化膜。
在上述磷化过程中，有氢气放出（见式4），它会停滞在基体表面阻滞过程进行，而加速剂通过化学反应产生的氧化气体则将氢气泡冲击掉，从而使基体与磷酸接触时间长而加快了磷化。
由图1、2、3所示可见，采用本综合表面处理液，其工艺流程大大简化，一般可从原来的11个工序减为3～5个工序，亦即减了6～8道工序，且时间比常规磷化工艺要提高1～4倍，如在本发明中再配合超声波振动作搅拌，则时间还可成倍减少。
下面对本发明的配方比例再予以详细说明。
附图说明：
图1为现有常规磷化工艺流程图。
图2为采用表面综合处理液除重油的综合处理工艺流程。
图3为采用表面综合处理液除轻油的综合处理工艺流程。
图中方块上部标注为每道工序所需时间（min分钟）。
本发明的金属表面综合处理液由磷酸、酸式磷酸锰及多种加速剂和少量活性剂及有机酸所组成，其配方组分如下，单位为克/升。
（1） H3PO4（磷酸）：200～260
（2） Mn（H2PO4）2（酸式磷酸锰）：20～25
（3） （NH4）2Mo4O13·2H2O（钼酸铵）：1～1.5
（4） Ca（NO3）2·4H2O（硝酸钙）：10～15
或Mg（NO3）2·6H2O（硝酸镁）：10～15
（5） MgCl2·6H2O（氯化镁）：2～3
（6） C4H6O6（酒石酸）：8～15
或C6H8O7·H2O（柠檬酸）：8～15
（7）  OP-10（活性剂）（或OP量同）：5～7
（8）  白猫牌洗洁净：2
（9） 清水H2O 余量。
本金属表面处理液用作除重油、除重锈、磷化的综合处理，其工艺流程为：
（1）先用75～90℃的碱水浸洗3分钟;
（2）然后用清水清洗1分钟;
（3）用45～55℃的本发明的综合清洗液浸洗15～25分钟，当使用超声波作搅拌时，则（3）中浸洗时间可减少为3～5分钟;
（4）再进入清水池再次清洗1分钟;
（5）后处理（填充烫干）;
然后就可转入喷涂。
用上述工艺流程其工序比常规磷化工艺流程省6道工序，时间可节省1～4倍。如采用超声波搅拌则时间可节省4～8倍，且质量好，而且能有效地代替有严重污染的三酸处理（H2SO4硫酸、HCl盐酸、HNO3硝酸）对环境保护极有好处，且除油率高，可达99%，速度快。本发明的清洗液有去除油膜厚度在10μm左右的重油层的能力，它比一般的除油清洗液相比除油效率为其10倍。
本清洗液的又一优点是组份无毒、不燃、不爆，没有有害金属的污染，因此它是一种既经济实用、又性能好、效益高、无污染的理想的金属表面综合清洗液。
由图3可见，当用本清洗液清洗磷化金属表面（冷轧钢板）为轻油轻锈的状况时，其工艺流程更为简单，其流程为：
1.综合处理，将工件直接放置于综合清洗液池中3～5分钟。
2.清洗从1中取出工件再放于清水池中清洗1分钟。
3.后处理（填充及烫干）后转喷涂。
由本除轻油的综合处理工艺可见，对于一般工件采用本清洗液不仅工艺流程非常简单，速度很快（只需6～8分钟）而且处理后工件质量好，涂层不仅表面光洁、耐冲击而且不易脱落，和无污染，从而为中小企业开辟了一种快速金属表面清洗处理，磷化处理的综合处理捷径，为提高工件质量使用寿命，减少资金投入，劳力投入等方面提供了显著的经济效益、社会效益。

Claims (3)

1、一种金属表面综合处理液由磷酸、酸式磷酸锰及多种加速剂和少量活性剂及有机酸所组成，其配方组份如下，单位为克/升。
(1)H3PO4(磷酸)：200～260
(2)Mn(H2PO4)2(酸式磷酸锰)：20～25
(3)(NH4)2Mo4O13·2H2O(钼酸铵)：1～1.5
(4)Ca(NO3)2·4H2O(硝酸钙)：10～15
或Mg(NO3)2·6H2O(硝酸镁)：10～15
(5)MgCl2·6H2O(氯化镁)：2～3
(6)C4H6O6(酒石酸)：8～15
或C6H8O7·H2O(柠檬酸)：8～15
(7)OP-10(活性剂)(或OP量同)：5～7
(8)白猫牌洗洁净：2
(9)清水H2O 余量。
2、一种用金属表面综合处理液作除重油、除锈、磷化处理的工艺，其过程为：
（1）先用75～90℃的碱水浸洗3分钟;
（2）然后用清水清洗1分钟;
（3）用45～55℃的本发明的综合清洗液浸洗15～25分钟，当使用超声波作搅拌时，则（3）中浸洗时间可减少为3～5分钟;
（4）再进入清水池再次清洗1分钟;
（5）后处理（填充烫干）;
然后就可转入喷涂。
3、一种用金属表面综合处理液作除轻油、除锈、磷化处理的工艺，其过程为：
（1）综合处理，将工件直接放置于综合清洗液池中3～5分钟。
（2）清洗从1中取出工件再放于清水池中清洗1分钟。
（3）后处理（填充及烫干）后转喷涂。
CN 93102603 1993-03-18 1993-03-18 金属表面综合处理液及其处理工艺 Expired - Fee Related CN1032146C (zh)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2374088A (en) * 2001-03-29 2002-10-09 Macdermid Plc Conversion treatment of zinc and zinc alloy surfaces
CN100357491C (zh) * 2004-08-02 2007-12-26 牛长宽 一种除锈防护液及使用其进行除锈防护的方法
CN103225075A (zh) * 2013-05-27 2013-07-31 兰州理工大学 一种钢铁表面擦拭亮化液及其制备方法
CN103952689A (zh) * 2013-05-03 2014-07-30 北京艾瑞满金属科技有限公司 一种环保型多功能金属表面处理液
CN108149234A (zh) * 2017-11-24 2018-06-12 安徽江南泵阀有限公司 一种泵体紧固件表面磷化处理方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103334099A (zh) * 2013-06-18 2013-10-02 杭州聚城环保科技有限公司 环保型多功能金属表面处理液

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2374088A (en) * 2001-03-29 2002-10-09 Macdermid Plc Conversion treatment of zinc and zinc alloy surfaces
CN100357491C (zh) * 2004-08-02 2007-12-26 牛长宽 一种除锈防护液及使用其进行除锈防护的方法
CN103952689A (zh) * 2013-05-03 2014-07-30 北京艾瑞满金属科技有限公司 一种环保型多功能金属表面处理液
CN103225075A (zh) * 2013-05-27 2013-07-31 兰州理工大学 一种钢铁表面擦拭亮化液及其制备方法
CN108149234A (zh) * 2017-11-24 2018-06-12 安徽江南泵阀有限公司 一种泵体紧固件表面磷化处理方法

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