CN1020763C - 在钢铁表面上形成磷化膜的方法 - Google Patents

在钢铁表面上形成磷化膜的方法 Download PDF

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CN1020763C
CN1020763C CN 88105272 CN88105272A CN1020763C CN 1020763 C CN1020763 C CN 1020763C CN 88105272 CN88105272 CN 88105272 CN 88105272 A CN88105272 A CN 88105272A CN 1020763 C CN1020763 C CN 1020763C
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phosphatization
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weight percent
zinc
steel
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CN1037746A (zh
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赵先乾
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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
    • C23C22/07—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
    • 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
    • C23C22/78—Pretreatment of the material to be coated

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

一种钢铁表面上形成磷化膜的方法，该方法是先用本发明的酸洗液将钢铁表面进行处理，水冲后再将钢铁件浸入本发明的磷化液中进行磷化。本发明的磷化液是由硝酸钙、磷酸锌、硝酸镍、硝酸钴、硝酸锡、柠檬酸、酒石酸、E、O、T、A、表面活性剂OP和水组成。本发明形成磷化膜的方法，具有成本低、操作方便，不污染环境，磷化效果好等优点。

Description

一种在钢铁表面上形成磷化膜的方法。
本发明属于钢铁表面喷漆、烤漆前的表面处理方法。
在本发明以前，国内自五十年代一直沿用苏联的马日夫盐磷化液，主要用于军事武器（如;装甲车、大炮等）的磷化工艺。这种磷化液的缺点是操作工艺复杂，需要大量的硫酸和烧碱进行中和，对环境造成一定的污染;操作中，需要煮沸，并在大量沉积物的条件下进行磷化，使用一段时间后，将要排放大量有毒物质，磷化后的钢铁表面磷化膜防锈能力差;近几年来，又引进日本夏普磷化液，它是属于镍系磷化液。其最大缺点是含有毒物质亚硝酸钠，液内存在大量沉淀物，被磷化的设备加热很快被腐蚀，同时也要排放大量废液，防锈能力较差;国内第一、第二汽车制造厂所用的磷化液也含有大量的亚硝酸盐，需排放污水，磷化膜防锈能力差;上海造船设计院研制的“705”磷化液和国内目前盛行的“四合一磷化液”都是一种以磷酸铁的盐类磷化膜，这种膜迂水就能溶解，防锈能力更差;上述这些已有技术的磷化液，使用过程中，多数要加温至90℃以上，此时多放出有腐蚀性的毒性气体，污染了操作环境，腐蚀了厂房，人的皮肤和衣物。
本发明为了解决上述已有技术的不足，提出了新的技术方案，本发明采用的原料价廉易取，配制使用方便易行，不污染环境。
本发明的要点是一种在钢铁表面形成磷化膜的方法它是经酸洗，清洗和磷化等步骤完成;
（A）酸洗液的配制;将重量百比为磷酸5-50，硫尿0.005-0.015，十二烷基磺酸钠0.05-0.15，平平加0.05-0.15，氯化十六烷基三甲铵0.05-0.15，柠檬酸1-10，水93.845-39.535在容器中搅拌均匀即成。
（B）磷化液的配制;使磷酸与氧化锌反应，生成磷酸锌水溶液，使氧化钙与浓硝酸反应生成硝酸钙和水;将上述生成的磷酸锌按重量百分比为5-15，硝酸钙重量百分比为5-15及重量百分比为硝酸镍0.15-0.25，硝酸钴0.045-0.055，硝酸锡0.045-0.055，柠檬酸0.15-0.25、酒石酸为0.045-0.055，EDTA10.045-0.055，表面活性剂OP0.008-0.02，水89.512-69.26，加入固体氧化锌调节pH＝2，搅拌均匀即成。
（C）酸洗;将钢铁表面，用上述酸洗液处理4-10分钟，即完成了酸洗表面处理。
（D）清洗;将（C）中酸洗过的钢铁件，用淡水冲洗净表面的固体物。
（E）磷化;将上述冲洗净的钢铁件，置于（B）所配制的磷化液中7分钟，温度为65-70℃，钢铁表面即可形成致密的复盖层-磷化膜。
本发明中成使用的硝酸钙可以用氧化钙代替，其重量百分组分不变;磷酸锌可以用磷酸二氢锌代 替，其重量百分组分不变;本发明中的酸洗液中的柠檬酸可用氟化钠代替，其重量百分比不变;本发明的酸洗液和磷化液的浓度，可以用水在上述配方范围内调节。
本发明的酸洗液，是将钢铁表面的氧化物、油污等杂质处理得干净、彻底;磷化液中的硝酸钙、磷酸锌、硝酸镍、硝酸钴、硝酸锡在65-70℃下，可以在钢铁表面形成良好的致密复盖膜，具有防氧化耐酸的特性，柠檬酸、酒石酸、EDTA为络合剂，表面活性剂OP为活化剂，水为溶剂。
本发明与已有技术对比，有如下优点;（1）成本低，每吨酸洗液350元，每吨磷化液320元;已有技术中的磷化液，每吨多在2000元以上，而上海造船设计院研制的“705”磷化液每吨3000元。（2）本发明的磷化液，操作方便，磷化温度一般掌握在65-70℃即可，酸洗液和磷化液在40℃以下，对人的皮肤无腐蚀，使用中可减轻劳动强度，同时运输、储存都很方便。（3）本发明的酸洗液、磷化液，使用中无污染物排放，改善了操作环境，降低了设备、厂房的腐蚀率，它不含有毒元素，无味，使用后的废液加上氧化钙铵盐、尿素成为很好的复合肥料。（4）本发明的磷化液对钢制轴承在70-100℃下磷化7-20分钟，生成的磷化膜在硬脂酸中皂化后，能起到润滑、防腐、耐磨的作用，这是其它磷化液无法比的。（5）本发明磷化后的磷化膜，防锈能力强。通过对不同磷化液处理的钢铁件的破坏实验看，本发明的磷化液优于目前已有技术中的磷化液。
本发明的实施例（一）;
1.酸洗液;10%磷酸，0.01%硫尿，2%柠檬酸，0.07%十二烷基横酸钠，0.1%平平加，0.1%氯化十六烷基三甲铵，87.72%水，将其搅拌均匀。
2.磷化液：10%硝酸钙，10%磷酸锌，0.2%硝酸镍，0.05%硝酸钴，0.05%硝酸锡，0.2%柠檬酸，0.05%E、D、T、A，0.015%表面活性剂OP，0.05%酒石酸，79.385%水，将其搅拌均匀，加温至65℃。
用上述酸洗液将钢铁表面酸洗处理4-10分钟，取出后，以淡水冲洗，再置于磷化液中磷化7分钟。
另取同样的钢铁件，用马日夫盐磷化液在90℃下磷化30分钟。
将上述两种磷化液处理的钢铁件进行破坏性实验，用3%HCl，6%CuSO4，点试破坏，马日夫盐磷化液处理的钢铁件，只有10秒，表面即被破坏;而本发明的磷化液处理的钢铁件，需8分钟，才能被破坏。
本发明的实施例（二）;
1.酸洗液;15%磷酸，0.012%硫尿，4.104%柠檬酸，0.063%十二烷基磺酸钠，0.08%平平加，0.12%氯化十六烷基三甲铵，80.621%水，将其搅拌均匀。
2.磷化液;12%硝酸钙，12%磷酸锌，0.169%柠檬酸，0.22%硝酸镍，0.052%硝酸钴，0.047%硝酸锡，0.045%酒石酸，0.052%E、D、T、A，0.015%表面活性剂OP，75.4%水，将其搅拌均匀，加热至68℃。
用上述酸洗液将铁片处理4-10分钟，取出后以淡水冲洗之，再置于上述的磷化液中7分钟。
另取同样铁片二片，分别用日本夏普磷化液加热至80℃下磷化10分钟和用“705”磷化液磷化15分钟。
破坏实验仍采用3%HCl，6%CuSO4点试，结果日本夏普磷化液磷化的铁片只有6秒即被破坏;“705”磷化液磷化的铁片，只有5秒被破坏，而本发明的磷化液处理的铁片，磷化时间还短，且需要8分钟才能被破坏。

Claims (4)

1、一种在钢铁表面上形成磷化膜的方法，其特征在于该方法由酸洗、清洗、磷化等步骤完成；
(A)酸洗液的配制；将重量百分比为磷酸5-50，硫尿0.005-0.015，十二烷基磺酸钠0.05-0.1，平平加0.05-0.15，氯化十六烷基三甲铵0.05-0.15，柠檬酸1-10，水93.845-39.535在容器中搅拌均匀；
(B)磷化液的配制；将磷酸锌和硝酸钙各按重量百分比为5-15与重量百分比为0.15-0.25的硝酸镍，0.045-0.055的硝酸钴，0.045-0.055的硝酸锡，0.15-0.25的柠檬酸，0.045-0.055的酒石酸，0.045-0.055的EDTA，0.008-0.02的表面活性剂OP和89.512-69.26的水，加入固体氧化锌调节pH=2，搅拌均匀；
(C)酸洗；将钢铁表面，用上述酸洗液处理4-10分钟；
(D)清洗；将(C)中酸洗过的钢铁件，用淡水冲洗净表面的固体物。
(E)磷化；将上述冲洗净的钢铁件，置于(B)所配制的磷化液中7分钟，温度为65-70℃。
2、按照权利要求1所说的在钢铁表面上形成磷化膜的方法，其特征在于（B）中的硝酸钙可用氧化钙代替，其重量百分组分不变;磷酸锌可用氧化锌或磷酸二氢锌代替，其重量百分组分不变。
3、按照权利要求1所说的在钢铁表面上形成磷化膜的方法，其特征在于（A）中的柠檬酸可以用氟化钠代替，其重量百分组分不变。
CN 88105272 1988-05-19 1988-05-19 在钢铁表面上形成磷化膜的方法 Expired - Fee Related CN1020763C (zh)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN102978597A (zh) * 2012-12-18 2013-03-20 三达奥克化学股份有限公司 冷轧板工件喷涂涂装用喷淋型综合皮膜化成处理剂及制备方法

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CA2591141C (en) * 2004-12-28 2012-02-28 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating process that reduces laser scale resulting in improved paint adhesion
CN106222678A (zh) * 2016-08-27 2016-12-14 合肥普庆新材料科技有限公司 一种含有腰果酚聚氧乙烯醚的抑制腐蚀的铝材脱脂剂及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102978597A (zh) * 2012-12-18 2013-03-20 三达奥克化学股份有限公司 冷轧板工件喷涂涂装用喷淋型综合皮膜化成处理剂及制备方法

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