CN1478155A - 钝化方法 - Google Patents

钝化方法 Download PDF

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Publication number
CN1478155A
CN1478155A CNA018197477A CN01819747A CN1478155A CN 1478155 A CN1478155 A CN 1478155A CN A018197477 A CNA018197477 A CN A018197477A CN 01819747 A CN01819747 A CN 01819747A CN 1478155 A CN1478155 A CN 1478155A
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CN
China
Prior art keywords
aforementioned
passivation
coating
chromium
passivation layer
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Pending
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CNA018197477A
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English (en)
Inventor
E・W・希勒布兰特
E·W·希勒布兰特
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Hillebrand Walter GmbH and Co KG
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Hillebrand Walter GmbH and Co KG
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Publication of CN1478155A publication Critical patent/CN1478155A/zh
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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C22/46—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 oxalates
    • 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
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Abstract

本发明涉及一种钝化锌、镉或它们的合金，特别是锌－镍合金的方法，是借助含有弱的配合剂，优选二元或三元羧酸，优选铬(III)－草酸盐配合物和Co2+的不含铬(VI)的溶液，特征在于Co2+浓度大于30g/l。

Description

钝化方法
本发明涉及一种钝化锌和锌合金层及镉和镉合金层的方法，要求德国专利申请100 55 215.3的优先权，该专利申请引入本申请供参考。
众所周知，为了提高耐腐蚀性要用金属或金属合金电镀涂敷金属表面。另外，已知可通过改性和通过另外的涂敷体系来进一步提高该涂层的抗腐蚀作用。具有好的抗腐蚀作用的体系是电镀涂敷的锌-镍合金，然后镀铬并可另外用有机或无机涂层处理。通过用铬(VI)钝化锌-镍层来实现良好的耐腐蚀性。
铬(VI)化合物的毒性与它们的良好抗腐蚀品质成对照。因此，长期以来人们在尝试确立不含铬(VI)来提供足够好的耐腐蚀性的体系。
已知如US4 171 231所述的含铬(III)钝化溶液用于此目的，但由于溶液中也存在氧化剂，这不会产生不含铬(VI)的钝化层，因为处理过程中铬(III)被氧化。
从DE 41 35 524 C2已知一种钝化方法，将其引入本说明书中，并完全参考其内容，通过含草酸盐配合物的含铬(III)钝化溶液实现抗腐蚀值的提高(表II；表III)。用于钝化的铬(III)化合物的不同例子在所提及文件的表IV中给出。此文件中所述钝化方法良好的抗腐蚀作用归因于使用草酸盐作为配合剂，相对于已知配合剂，有利于将铬引入钝化层中。
用此种钝化方法人们已实现了良好的抗腐蚀结果。另外，已知通过使用钴提高由铬(III)基钝化方法提供的抗腐蚀保护作用。
用钴提高抗腐蚀保护作用记载于WO97/40208，在此引入本申请中。
如由此文件还可看出的，专业人士目的是要制备尽可能紧密的转化层以实现该层所需的耐腐蚀性和耐化学性。
本发明的目的在于提供一种具有进一步改善的抗腐蚀保护作用的钝化方法和一种相应的涂敷体系。
根据独立权利要求的方法和钝化溶液实现了此目的。有利的方面是从属权利要求的主题。
本发明是基于如下发现：放弃集中在紧密转化层上的努力并因而旨在制备一个多孔转化层，当孔隙度用于结合在至少一个其它层时得到改善的最终产物。
实现本发明是通过用含有铬(III)和一种弱的配合剂优选二元或三元羧酸如草酸的钝化溶液使用钴情况下进行钝化。
通过使用大于30g/l浓度的钴，优选浓度为70g/l-100g/l，特别是约90g/(浓度-12％)，根据DIN50021SS在盐喷射箱中根据DIN50961在制备中已实现了令人惊奇的直到出现初步腐蚀240h的腐蚀保护值。有利的铬-钴比率是1.7∶2.0∶0.85。
该方法优选在直到55℃的温度和0.5-5.5的pH值下实施。钝化优选在pH4下实施。用不含硫酸盐的溶液可达到特别好的结果。这所基于的想法是使用硫酸盐会导致催化反应阻碍并干扰抗腐蚀铬层的形成。
钝化层用渗透到多孔转化层的有机或无机涂料再处理。优选AquaresTM(Enthone-OMI GmbH，Neuss)涂层施涂到钝化层上。通过双Aquares层可实现特别良好的腐蚀保护。在本发明的一些变化方案中Aquares层在REM中令人惊奇地不再可检测到。
借助含有干燥润滑剂的面漆，腐蚀保护性和耐化学性都可进一步提高。根据本发明此涂层也参与了对多孔转化层的具体粘结。借此可同时实现所需的磨擦和流动值。
通过干燥的润滑剂MolykoteD-7100(Dow corning)和根据本发明钝化的锌-镍合金的结合展示了令人惊奇的性能。与已知的涂敷体系比较，此体系特别耐化学性和耐边缘清洁器。因此特别适于车轮螺钉。另外还表明了根据本发明的结合令人惊奇的温度不敏感性。
优选此干燥的润滑剂层施涂于双Aquares层上。

Claims (15)

1.钝化锌、镉或它们的合金，特别是锌-镍合金的方法，是借助含有弱的配合剂，优选二元或三元羧酸，优选铬(III)-草酸盐配合物和Co2+的不含铬(VI)的溶液，特征在于Co2+浓度大于30g/l。
2.根据权利要求1的方法，特征在于Co2+浓度为70-110g/l。
3.根据权利要求1的方法，特征在于Co2+浓度大约90g/l。
4.根据前述权利要求之一的方法，特征在于钝化作用在20℃-55℃实施。
5.根据前述权利要求之一的方法，特征在于钝化作用在pH0.5-5.5实施。
6.根据前述权利要求之一的方法，特征在于钝化作用在pH4实施。
7.根据前述权利要求之一的方法，特征在于铬与钴的比率是1.7∶2.0。
8.根据前述权利要求之一的方法，特征在于溶液不含硫酸盐。
9.根据前述权利要求之一的方法，特征在于钝化层用另外的涂层处理。
10.根据前述权利要求之一的方法，特征在于用AquaresTM涂层处理。
11.根据前述权利要求之一的方法，特征在于用AquarestTM两次涂层处理。
12.根据前述权利要求之一的方法，特征在于钝化层用一种干燥的润滑剂处理。
13.根据前述权利要求之一的方法，特征在于钝化层用一种有机面漆涂敷。
14.根据前述权利要求之一的方法，特征在于钝化层用一种含有PTFE的涂层处理。
15.根据前述权利要求的方法，  特征在于钝化层用MolykoteD7100涂敷。
CNA018197477A 2000-11-07 2001-11-07 钝化方法 Pending CN1478155A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10055215.3 2000-11-07
DE10055215A DE10055215A1 (de) 2000-11-07 2000-11-07 Passivierungsverfahren

Publications (1)

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CN1478155A true CN1478155A (zh) 2004-02-25

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US (1) US20040011431A1 (zh)
EP (1) EP1346081A1 (zh)
JP (1) JP2004513240A (zh)
CN (1) CN1478155A (zh)
AU (1) AU2002221819A1 (zh)
BR (1) BR0115161A (zh)
CA (1) CA2428138A1 (zh)
CZ (1) CZ20031237A3 (zh)
DE (1) DE10055215A1 (zh)
MX (1) MXPA03004019A (zh)
SK (1) SK5442003A3 (zh)
WO (1) WO2002038829A1 (zh)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN1307323C (zh) * 2004-06-14 2007-03-28 广州市集胜化工有限公司 镀锌用三价铬彩虹色钝化剂及其制造方法

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JP3332373B1 (ja) † 2001-11-30 2002-10-07 ディップソール株式会社 亜鉛及び亜鉛合金めっき上に六価クロムフリー防錆皮膜を形成するための処理溶液、六価クロムフリー防錆皮膜及びその形成方法。
EP1677371A1 (en) * 2004-12-30 2006-07-05 STMicroelectronics S.r.l. Dual resistance heater for phase change devices and manufacturing method thereof
US7276424B2 (en) * 2005-06-29 2007-10-02 Hewlett-Packard Development Company, L.P. Fabrication of aligned nanowire lattices
JP4993959B2 (ja) * 2006-07-10 2012-08-08 日本化学工業株式会社 有機酸クロム（ｉｉｉ）水溶液及びその製造方法
DE102016005656A1 (de) 2016-05-11 2017-11-16 Surtec International Gmbh Konversionsschichten für metallische Oberflächen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1307323C (zh) * 2004-06-14 2007-03-28 广州市集胜化工有限公司 镀锌用三价铬彩虹色钝化剂及其制造方法

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AU2002221819A1 (en) 2002-05-21
CA2428138A1 (en) 2002-05-16
SK5442003A3 (en) 2003-10-07
BR0115161A (pt) 2003-10-21
MXPA03004019A (es) 2004-02-12
WO2002038829A1 (de) 2002-05-16
JP2004513240A (ja) 2004-04-30
US20040011431A1 (en) 2004-01-22
DE10055215A1 (de) 2002-05-08
EP1346081A1 (de) 2003-09-24
CZ20031237A3 (cs) 2003-10-15

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