CN1292041A - 用于金属表面磷酸盐化的水溶液和方法 - Google Patents

用于金属表面磷酸盐化的水溶液和方法 Download PDF

Info

Publication number
CN1292041A
CN1292041A CN99803391A CN99803391A CN1292041A CN 1292041 A CN1292041 A CN 1292041A CN 99803391 A CN99803391 A CN 99803391A CN 99803391 A CN99803391 A CN 99803391A CN 1292041 A CN1292041 A CN 1292041A
Authority
CN
China
Prior art keywords
solution
aqueous solution
nitroguanidine
aqueous
submergence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN99803391A
Other languages
English (en)
Inventor
P·舒巴赫
J·海特鲍姆
T·科尔贝格
M·弗莱施哈克尔－杰沃雷克
P·约恩斯
M·德默
R·斯蒂克勒
J·施佩赫特
M·伦哈德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of CN1292041A publication Critical patent/CN1292041A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc 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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • 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
    • C23C22/12—Orthophosphates containing zinc 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/186—Orthophosphates containing manganese cations containing also copper 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel 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
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/82—After-treatment
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Landscapes

  • 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)
  • Chemically Coating (AREA)
  • Catalysts (AREA)

Abstract

本发明涉及一种用于在铁、钢、锌、锌合金、铝或铝合金等金属表面上形成磷酸盐层的磷酸盐水溶液,该溶液含0.3—5gZn2+/l、0.1—2g硝基胍/l,和0.05－0.5g羟胺/l,而且S－值为0.03—0.3,Zn2+对P2O5的重量比=1∶5—1∶30。其次,本发明涉及一种用于使金属表面磷酸盐化的方法,其中金属表面先经清洗,接着用权利要求1—8的磷酸盐水溶液在15—70℃温度下处理5秒－10分钟,最后用水漂洗。

Description

用于金属表面磷酸盐化的水溶液和方法
本发明涉及一种在铁、钢、锌、锌合金、铝或铝合金等金属表面形成磷酸盐涂层的含磷酸盐的水溶液。其次本发明涉及利用一种磷酸盐化水溶液对金属表面进行磷酸盐化的方法。
1996年8月28日的德国专利申请书19634685．1建议采用一种含磷酸盐的水溶液在铁、钢、锌合金、铝或铝合金等金属表面形成磷酸盐涂层，该溶液含0．3-5g Zn2+／l和0．1-3g硝基胍／l，其S-值为0．03-0．3，Zn2+对P2O5的重量比=1∶5-1∶30，形成的结晶磷酸盐涂层中晶粒的最大棱长＜15μm。其次，在此德国专利申请书中提出了一种磷酸盐化方法，该方法中金属表面先经清洗，接着用上述含磷酸盐的水溶液在15-17℃的温度下处理5秒-10分钟，然后用水漂洗。
本发明的目的在于，改进德国专利申请书19634685．1中建议的含磷酸盐的水溶液和磷酸盐化方法，使在所形成的磷酸盐涂层中晶粒的最大棱长明显小于＜15μm，使形成的磷酸盐涂层的层重为2-4g／l，使所形成的磷酸盐涂层的层重和晶粒的棱长在磷酸盐浴长时间运行中保持不变和均匀。
本发明的目的是通过配制一种含磷酸盐的水溶液来达到的，该水溶液在铁、钢、锌、锌合金、铝或铝合金等金属表面形成磷酸盐涂层，该溶液含0．3-5g Zn2+／l、0．1-2g硝基胍／l和0．05-0．5g羟胺／l，其S-值为0．03-0．3，Zn2+对P2O5的的重量比=1∶5-1∶30。本发明的核心在于，在所引的德国专利申请书所建议的溶液中除增速剂硝基胍之外还含有低浓度的增速剂羟胺，而且本发明溶液中的硝基胍浓度明显低于德国专利申请书的溶液中的硝基胍浓度。
本发明认为含0．1-1．5g硝基胍／l以及0．1-0．4g羟胺／l的溶液是特别有利的和优选的。利用具有本发明特徵的溶液可以达到最佳磷酸盐化效果。
虽然，一方面由出版物EP-B 0315059已知一种使铁表面磷酸盐化的溶液，该溶液的锌浓度为0．2-2g／l，并含羟胺、羟胺盐或羟胺络合物等作为增速剂，溶液中羟胺浓度为0．5-50g／l，优选1-10g／l，另一方面由出版物EP-B 0633950已知一种在钢、镀锌钢、镀锌合金钢、铝及其合金等金属表面上形成含铜磷酸盐涂层的溶液，该溶液中锌的浓度为0．2-2g／l、铜浓度为0．5-25mg／l、P2O5浓度为5-30g／l，该溶液还含羟胺、羟胺盐和羟胺络合物等作为增速剂，溶液中羟胺浓度为0．5-5g／l，此外还可能含一种有机硝基化合物作氧化剂，但使专业人员特别吃惊的是，用较低浓度的硝基胍和羟胺能形成磷酸盐涂层，该涂层具有最优的层重2-4g／m2，其层重在长期运行中仍很均匀，其晶粒在各种情况下最大棱长＜15μm，而且其棱长通常明显＜10μm。本发明溶液令人吃惊的有利作用与另一有利作用相关，后者在于，由于本发明溶液中增速剂的浓度较低，在以后的处理工序和最终被废水从磷酸盐浴中带走的增速剂量亦较低。本发明的溶液还可保证，磷酸盐化的两种增速剂几乎是定量地引入。
专业技术人员亦不会从上面所引的当前技术中得到有关本发明溶液的启示或领悟，因为相对于德国专利申请书19634685．1所建议的溶液，本发明的溶液只用了低浓度的硝基胍，以及附加了所引两个欧洲专利说明书中用的羟胺，相对于两个欧洲专利中的溶液，本发明的溶液所用的羟胺浓度低于所引当前技术中所用的羟胺浓度，除此之外，在所引的两个欧洲专利说明书中没有公开利用硝基胍作增速剂，而且所引的两个欧洲专利说明书要求专业技术人员利用高浓度的羟胺，因为根据出版物EP-B 0315059要求优选用的羟胺浓度为1-10g／l，出版物EP-B 0633950的例1是用1．7g／l的羟胺浓度加工。应该认识到，本发明的贡献还在于，可在各种金属表面上从溶液中沉积优质的磷酸盐涂层，该溶液的羟胺含量甚低，以及硝基胍含量较低，而且本发明在羟胺含量方面并未沿着当前技术所规定的途径采用相当高的羟胺浓度。
在本发明的另一个方案中采用的溶液含0．3-3g Zn2+／l。此溶液优选用于低锌工艺的范围。其次，在本发明的另一方案中，所用的溶液还补充含有0．5-20g NO3 -／l，溶液还含0．01-3g Mn2+／l和／或0．01-3g Ni2+／l和／或1-100mg Cu2+／l和／或0．01-3g Co2+／l。1-100mg Cu2+／l的铜含量具体作用在于，在无镍的存在下能形成高质量的磷酸盐层。曾经证明，本发明特别适用于含铝表面的磷酸盐化，如果溶液含0．01-3g F-／l和／或0．05-3．5g／l的至少一种络合氟化物。根据本发明，溶液含(SiF6)2-或(BF4)-等络合氟化物。
本发明的硝酸盐含量存助于保持恒定的层重。硝酸盐以碱金属的硝酸盐和／或以系统中存在的阳离子的硝酸盐，例如以硝酸锌和／或以HNO3的形式添加到磷酸盐化溶液中。由于不含硝酸盐的水溶液亦能提供良好的磷酸盐化结果，所以已知的硝酸盐的增速作用在这种情况下可能具有较小的意义。添加到磷酸盐化溶液中的金属离子Mn2+、Ni2+、Cu2+和Co2+将进入磷酸盐层，并改善漆粘附和抗腐蚀性。如果磷酸盐化的金属表面是由铝或铝合金组成，则向磷酸盐化溶液添加自由氟化物。向磷酸盐化溶液中添加络合氟化物特别用以改善镀锌表面的磷酸盐化结果。
其次，本发明所定的目的是通过提供一种金属表面磷酸盐化的方法来达到的，该方法中，金属表面先经清洗，接着用含磷酸盐的磷酸盐化水溶液在15-70℃的温度下处理5秒-10分钟，然后用水漂洗。这种方法可用简单的技术手段实施并且操作非常安全，用本方法形成的磷酸盐层具有始终不变的高质量，盐层质量在磷酸盐浴较长的操作时间内不会降低。本发明方法的最低磷酸盐化时间比已知的，采用常规增速剂的低锌方法短。最低磷酸盐化时间是表面被遮蔽磷酸盐化的时间。曾经意外地发现，德国专利说明书19634685．1建议的方法的操作参数被证明是有效的，一般说来亦可在本发明的方法中加以利用。
根据本发明，金属表面用磷酸盐化溶液的处理可通过喷涂、浸没、喷涂浸没或辗压来实施。这类操作技术为本发明的方法开辟了各种各样的广泛应用范围。曾经证明，如果采用Zn2+对P2O5的重量比=1∶5-1∶30的磷酸盐化溶液进行喷涂，本发明特别有效，喷涂所需时间为5-300秒，如果采用Zn2+对P2O5的重量比=1∶5-1∶18的磷酸盐化溶液进行浸没，浸没所需时间为5秒-10分钟。
根据本发明，如果金属表面在清洗之后用一种含钛的磷酸盐进行活化剂处理，在很多情况下是有利的。通过这种处理有助于形成封闭的结晶磷酸盐层。此外，本发明拟在接着磷酸盐化的漂洗过程之后采用一种钝化剂处理金属表面。所用的钝化剂可以含Cr，或者不含Cr。
按照本发明的方法，在清洗金属表面的工序中要从待磷酸盐化的表面去除机械杂质和附着的油脂。金属表面的清洗属于已知的当前技术，并可有效地用一种碱金属水溶性清洗剂进行清洁。在金属表面清洗之后，用水漂洗是适宜的。清洗后的或磷酸盐化的金属表面的漂洗或用自来水或者用脱盐水进行。
按照本发明，硝基胍特别适于以一种稳定的水相悬浮液的形式引入水溶液。这可通过下列措施达到，稳定的水相悬浮液含底层硅酸盐作稳定剂，底层硅酸盐[Mg6(Si7．4Al0．6)O20(OH)4]Na0．6×XH2O或[(Mg5．4Li0．6)Si8O20(OH，F)4]Na0．6×XH2O的用量为10-30g／l硝基胍-悬浮液，或者通过下列措施达到，该稳定的水相悬浮液含由聚合糖和聚乙二醇组成的稳定剂，聚合糖和聚乙二醇的重量比为1∶1-1∶3，稳定剂的用量为5-20g／l硝基胍-悬浮液。采用含两种稳定剂硝基胍-悬浮液可有效地达到使悬浮液在数月中保持不变的目的，以及使泥浆在磷酸盐浴中易于沉降的目的。将硝基胍以一种稳定悬浮液的形式加到磷酸盐化溶液中可以避免硝基胍以粉末形式添加所引起的难于在磷酸盐化溶液中均匀分布的缺点。根据本发明制备的悬浮液易于用泵输送，并在12个月内保持稳定，这就是说，硝基胍在较长时间内不沉淀。悬浮液的制备方法是，底层硅酸盐或有机稳定剂先在全盐化水中悬浮，然后再搅入硝基胍。
在磷酸盐化溶液中存在的PH值为2-4的条件下，悬浮液到破坏，硝基胍将以微粒的型式释出并溶解。
最后，根据本发明，将本发明的溶液和本发明的方法在上漆之前，特别是在电浸没上漆之前用于处理工件。
本发明的内容将在下面根据实施例进一步叙述。
A)定义：
Zn2+∶P2O5比是以总P2O5计的。总P2O5的测定基于磷酸的滴定和／或一元磷酸盐的滴定，即从一元磷酸盐的等当点到二元磷酸盐的等当点。S-值表示自由酸对总P2O5的比值，自由酸以自由P2O5计。关于总P2O5和自由P2O5的定义和测定方法在W．Rausch“金属的磷酸盐化”1988，S．289-304有详细的叙述。
B)工艺参数：
下列对比例和实施例来用下列工艺步骤实施：
a)由钢极组成的金属工件的表面用一种弱碱性清洗剂(2％的水溶液)在60℃下清洗6分钟，特别是去除油脂。
b)接着用自来水在室温下漂洗0．5分钟。
c)然后用一种含磷酸钛的活化剂在50℃下活化0．5分钟。
d)之后在55℃下浸没3分钟进行磷酸盐化。
e)最后用自来水在室温下漂洗0．5分钟。
f)磷酸盐化的表面在80℃的炉中烘干10分钟。
C)制备磷酸盐化溶液用的浓缩物
浓缩物Ⅰ含除羟胺和Cu2+外的磷酸盐化溶液的全部无机成份。浓缩物Ⅱ由稳定的硝基胍-悬浮液组成。浓缩物Ⅲ由羟胺盐、羟胺络合物或羟胺的水溶液组成。如果需要一种含的Cu2+的磷酸盐化溶液，则可采用浓的Cu2+溶液作浓缩物Ⅳ。如果铝或铝合金金属表面要进行磷酸盐化，则可采用浓缩物Ⅴ，该浓缩物含能生成自由氟化物的化合物。本发明的磷酸盐化溶液是通过混合所需的浓缩物1-Ⅴ同时添加水来制备。在磷酸盐浴长期静置下，常常发生羟胺的部分分解，由此，带来的羟胺损失可通过向磷酸盐浴添加浓缩物Ⅲ进行补偿，可按已知的方式采用羟胺盐、羟胺络合物或羟胺的水溶液作羟胺源。
D)实施例和对比例：
根据B)所给工艺参数，将两块不同质量(Z1和Z2)的单面镀锌的钢片磷酸盐化。磷酸盐浴每次的组成如表所示，所有例中总P2O5含量均为12g P2O5／l，表中所用符号之意义如下：
Fs=自由酸
Gs=总酸
Zn=Zn2+，g／l
NG=硝基胍，g／l
HA=羟胺，g／l
Cu=Cu2+，mg／l
Mn=Mn2+，g／l
对比例1的磷酸盐化是在无增速剂的条件下进行的。对比例2只有羟胺增速剂，而对比例3仅有硝基胍增速剂。实施例4-9是在两种增速剂存在下进行的，而且两种增速剂的浓度分别处于本发明优选范围内。
表中还给出了例1-例9取得的层重和晶粒棱长。数据表明，无本发明的两种增速剂条件下进行的对比例1得到了质量不合格的磷酸盐层，因为磷酸盐层的层重以及晶粒棱长皆较大。对比例2和3得到了容许的层重和足够小的晶粒棱长，这样两种磷酸盐层可算完全合乎要求。实施例4-9表明，按照本发明可形成最优层重以及晶粒特别细的磷酸盐层。实施例4-9还证明，按本发明可形成非常高质量的磷酸盐层，而且磷酸盐浴中所用的硝基胍和羟基胺的浓度很小。当然，实施例1-9分别形成的磷酸盐层是封闭性的。表中所给晶粒棱长是由各磷酸盐层的电子显微镜图象中测出的。
例 磷酸盐浴 层重g/m2 晶粒棱长μm
Nr. FS   GS Zng/l NGg/l HAg/l  Cumg/l  Mng/l  Z1  Z2 Z1  Z2
 1  2,3  25,7 1,6  0  0 6  1,0  8,0  5,5 10-15 ＞15
 2  2,4  25,7 1,6  0  0,20 6  1,0  4,0  5,5 ＜10 ＜10
 3  2,4  24,6 1,6  0,40  0 5  1,0  6,0  6,5 ＜10 ＜10
 4  2,3  24,0 1,5  0,40  0,22 5  1,0  4,0  4,0 ＜5 ＜5
 5  2,3  23,5 1,5  0,55  0,23 4  0,9  2,3  2,3 ＜5 ＜5
 6  2,3  23,1 1,4  0,75  0,23 3  0,9  2,8  2,5 ＜3 ＜3
 7  2,3  21,0 1,2  0,67  0,15 3  0,9  2,0  2,0 ＜3 ＜3
 8  2,2  22,0 1,3  0,68  0,18 3  0,9  2,0  2,3 ＜3 ＜3
 9  2,2  22,4 1,2  0,63  0,19 2  0,9  2,2  2,4 ＜5 ＜3

Claims (20)

1．一种用于在铁、钢、锌、锌合金、铝或铝合金等金属表面上形成磷酸盐层的磷酸盐水溶液，该溶液含0．3-5g Zn2+／l、0．1-2g硝基胍／l，和0．05-0．5g羟胺／l，而且S-值为0．03-0．3，Zn2+对P2O5的重量比=1∶5-1∶30。
2．权利要求1的水溶液，该溶液含0．1-1．5g硝基胍／l。
3．权利要求1-2的水溶液，该溶液含0．1-0．4g羟胺／l。
4．权利要求1-3的水溶液，该溶液含0．3-3g Zn2+／l。
5．权利要求1-4的水溶液，该溶液含0．5-20g NO3-／l。
6．权利要求1-5的水溶液，该溶液含0．01-3g Mn2+／l和／或0．01-3g Ni2+／l和／或1-100mg Gu2+／l和／或0．01-3g Co2+／l。
7．权利要求1-6的水溶液，该溶液含0．01-3g F-／l和／或0．05-3．5g／l的至少一种络合氟化物。
8．权利要求1-7的水溶液，该溶液含作为络合氟化物(SiF6)2-或(BF4)-。
9．一种用于使金属表面磷酸盐化的方法，其中金属表面先经清洗，接着用权利要求1-8的磷酸盐水溶液在15-70℃温度下处理5秒-10分钟，最后用水漂洗。
10．权利要求9的方法，其中用磷酸盐化溶液处理金属表面是通过喷镀、浸没、喷镀-浸没或辗压实现的。
11．权利要求9-10的方法，其中喷镀所用的磷酸盐化溶液中Zn2+对P2O5的重量比=1∶5-1∶30，喷镀所需的时间为5-300秒。
12．权利要求9-10的方法，其中浸没所用的磷酸盐化溶液中Zn2+对P2O5的重量比=1∶5-1∶18，浸没所需时间为5秒-10分钟。
13．权利要求9-12的方法，其中金属表面在清洗之后用一种活化剂处理，该活化剂含有含钛的磷酸盐。
14．权利要求9-13的方法，其中金属表面在紧接磷酸盐化的漂洗之后用一种钝化剂处理。
15．权利要求9的方法，其中硝基胍以一种稳定的水相悬浮液的形式添加到该水溶液中。
16．权利要求15的方法，其中该稳定的水相悬浮液含底层硅酸盐作稳定剂。
17．权利要求16的方法，其中采用底层硅酸盐[Mg6(Si7．4Al0．6)O20(OH)4]Na0．6×XH2O或者[(Mg5．4Li0．6)Si8O20(OH，F)4]Na0．6×XH2O作为稳定剂，其量为10-30g／l硝基胍-悬浮液。
18．权利要求15的方法，其中该稳定的水相悬浮液含由聚合糖和聚乙烯二醇组成的稳定剂，而且聚糖对聚乙二醇的重量比为1∶1-1∶3，稳定剂的量为5-20g／l硝基胍-悬浮液。
19．权利要求1-8的磷酸盐水溶液和权利要求9-18的磷酸盐化方法在工件涂漆前的处理件的应用。
20．权利要求19的应用用于工件的电浸没涂漆前的处理。
CN99803391A 1998-02-27 1999-02-24 用于金属表面磷酸盐化的水溶液和方法 Pending CN1292041A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19808440A DE19808440C2 (de) 1998-02-27 1998-02-27 Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens
DE19808440.4 1998-02-27

Publications (1)

Publication Number Publication Date
CN1292041A true CN1292041A (zh) 2001-04-18

Family

ID=7859188

Family Applications (1)

Application Number Title Priority Date Filing Date
CN99803391A Pending CN1292041A (zh) 1998-02-27 1999-02-24 用于金属表面磷酸盐化的水溶液和方法

Country Status (15)

Country Link
US (1) US6497771B1 (zh)
EP (1) EP1060290B1 (zh)
JP (1) JP2002505378A (zh)
KR (1) KR20010041417A (zh)
CN (1) CN1292041A (zh)
AT (1) ATE224466T1 (zh)
AU (1) AU740987B2 (zh)
BR (1) BR9909236A (zh)
CA (1) CA2325012A1 (zh)
DE (2) DE19808440C2 (zh)
PL (1) PL342623A1 (zh)
SI (1) SI20378A (zh)
SK (1) SK12352000A3 (zh)
TR (1) TR200002495T2 (zh)
WO (1) WO1999043868A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102953055A (zh) * 2012-11-07 2013-03-06 长沙沃尔金属表面技术有限公司 一种黑色磷化液及其使用方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
AU2003250917A1 (en) * 2002-07-10 2004-02-02 Chemetall Gmbh Method for coating metallic surfaces
US20040118483A1 (en) * 2002-12-24 2004-06-24 Michael Deemer Process and solution for providing a thin corrosion inhibiting coating on a metallic surface
US20040261752A1 (en) * 2003-06-26 2004-12-30 Wolfgang Rein Phosphatized and bushingless piston and connecting rod assembly having an internal gallery and profiled piston pin
US6923153B2 (en) 2003-06-26 2005-08-02 Mahle Technology, Inc. Piston and connecting rod assembly having phosphatized bushingless connecting rod and profiled piston pin
US7581315B2 (en) 2004-11-16 2009-09-01 Mahle Technology, Inc. Connecting rod assembly for an internal combustion engine and method of manufacturing same
US8613137B2 (en) 2004-11-16 2013-12-24 Mahle International Gmbh Connecting rod lubrication recess
US7516546B2 (en) * 2004-11-16 2009-04-14 Mahle Technology, Inc. Method of manufacturing a connecting rod assembly for an internal combustion engine
KR101968836B1 (ko) * 2017-09-26 2019-04-12 현대제철 주식회사 전기아연도금강판 및 이의 제조방법
BR112020015010A2 (pt) * 2018-02-19 2021-01-19 Chemetall Gmbh Método para pré-tratamento químico e fosfatação seletiva, composição de fosfatação de zinco, concentrado, construção de metal compósito, e, uso da construção de metal compósito

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE432557A (zh) * 1938-02-04
DE977633C (de) * 1950-07-06 1967-11-02 Galvapol Ges Fuer Galvanotechn Verfahren zur Herstellung von Phosphatueberzuegen auf eisenhaltigen Metallgegenstaenden
US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
GB2148950B (en) * 1983-10-26 1987-02-04 Pyrene Chemical Services Ltd Phosphating composition and processes
CA1257527A (en) * 1984-12-20 1989-07-18 Thomas W. Tull Cold deformation process employing improved lubrication coating
DE3800835A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren zur phosphatierung von metalloberflaechen
US5137589A (en) * 1990-02-09 1992-08-11 Texo Corporation Method and composition for depositing heavy iron phosphate coatings
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
DE4210513A1 (de) * 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
ATE162233T1 (de) * 1993-09-06 1998-01-15 Henkel Kgaa Nickelfreies phosphatierverfahren
DE4417965A1 (de) * 1994-05-21 1995-11-23 Henkel Kgaa Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
DE19634685A1 (de) * 1996-08-28 1998-03-05 Metallgesellschaft Ag Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102953055A (zh) * 2012-11-07 2013-03-06 长沙沃尔金属表面技术有限公司 一种黑色磷化液及其使用方法

Also Published As

Publication number Publication date
EP1060290B1 (de) 2002-09-18
JP2002505378A (ja) 2002-02-19
KR20010041417A (ko) 2001-05-15
AU3029899A (en) 1999-09-15
EP1060290A1 (de) 2000-12-20
SK12352000A3 (sk) 2001-05-10
BR9909236A (pt) 2000-11-14
ATE224466T1 (de) 2002-10-15
US6497771B1 (en) 2002-12-24
PL342623A1 (en) 2001-06-18
SI20378A (sl) 2001-04-30
DE19808440C2 (de) 2000-08-24
WO1999043868A1 (de) 1999-09-02
AU740987B2 (en) 2001-11-22
CA2325012A1 (en) 1999-09-02
TR200002495T2 (tr) 2000-12-21
DE59902751D1 (de) 2002-10-24
DE19808440A1 (de) 1999-09-09

Similar Documents

Publication Publication Date Title
EP0315059B1 (en) Process and composition for zinc phosphate coating
EP1433875B1 (en) Chemical conversion coating agent and surface-treated metal
CA2632720C (en) Wet on wet method and chrome-free acidic solution for the corrosion control treatment of steel surfaces
US5797987A (en) Zinc phosphate conversion coating compositions and process
EP2503025B1 (de) Mehrstufige korrosionsschützende Behandlung metallischer Bauteile, die zumindest teilweise Oberflächen von Zink oder Zinklegierungen aufweisen
JPH04228579A (ja) リン酸塩で金属表面を処理する方法
CN1292041A (zh) 用于金属表面磷酸盐化的水溶液和方法
US5401381A (en) Process for phosphating metallic surfaces
JP3940174B2 (ja) 金属面を燐酸処理するための水溶液及び方法
EP0653502A2 (en) Zinc-containing metal-plated composite steel article and method of producing the same
CA1224121A (en) Process for phosphating metals
JP3137535B2 (ja) 塗装性に優れた亜鉛含有金属めっき鋼板複合体、およびその製造方法
KR20100102619A (ko) 금속 구성성분, 특히 철의 지르코늄 인산염피막처리
US5503733A (en) Process for phosphating galvanized steel surfaces
US9309602B2 (en) Electrolytic iron metallizing of zinc surfaces
JP2000504781A (ja) 低濃度のニッケル及び／又はコバルトを用いるリン酸亜鉛処理方法
US5932292A (en) Zinc phosphate conversion coating composition and process
US5135583A (en) Phosphating process
JP2001295063A (ja) 非鉄金属材料およびめっき鋼板へのりん酸塩被膜の形成方法
JP2740661B2 (ja) 燐酸塩処理性の優れたＺｎ―Ｎｉ系合金電気めっき鋼板
JPWO2018192707A5 (zh)
JP2004043913A (ja) 金属化成処理方法
CA2035048A1 (en) Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
CZ20002979A3 (cs) Vodný roztok a způsob fosfátování kovových povrchů
JPH05222502A (ja) 耐食性と耐剥離性に優れたＺｎ−Ｃｒ−Ａｌ系溶融めっき鋼材およびその製造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication