EP0149720B1 - Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre - Google Patents

Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre Download PDF

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Publication number
EP0149720B1
EP0149720B1 EP84111060A EP84111060A EP0149720B1 EP 0149720 B1 EP0149720 B1 EP 0149720B1 EP 84111060 A EP84111060 A EP 84111060A EP 84111060 A EP84111060 A EP 84111060A EP 0149720 B1 EP0149720 B1 EP 0149720B1
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EP
European Patent Office
Prior art keywords
solutions
ethanate
cations
metal surfaces
nickel
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.)
Expired
Application number
EP84111060A
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German (de)
English (en)
Other versions
EP0149720A2 (fr
EP0149720A3 (en
Inventor
Reinhard Opitz
Kurt Hosemann
Heinz Portz
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.)
Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Publication of EP0149720A2 publication Critical patent/EP0149720A2/fr
Publication of EP0149720A3 publication Critical patent/EP0149720A3/de
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Publication of EP0149720B1 publication Critical patent/EP0149720B1/fr
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the invention relates to a method for the 'post-passivation of phosphated metal surfaces.
  • Such phosphate layers not only improve the corrosion protection of the metal surfaces, but also increase the adhesion for paints to be applied to the surface. In certain cases, they can also help to improve the properties of metal sheets during cold forming and when using deep-drawing processes.
  • the phosphate layer on the metal surfaces is not completely closed. Rather, there are more or less large “pores” that have to be closed in the course of a so-called “post-passivation” in order not to leave a point of attack for corrosive influences on the metal surfaces.
  • concentration of fluoride ions in these solutions is 0.01 to 25 g / l.
  • solutions disclosed in the abovementioned application contain anions which have a highly corrosive effect on system parts (for example Cl - , So 4 2- ) and / or are known to disrupt the passivation process (for example F - ).
  • Manganese (II) ethanate and cobalt (II) ethanate the content of Mn (II) cations and Co (II) cations in the solutions in each case being 0.05 to 1 g / l.
  • Nickel (II) ethanate and copper (II) ethanate the content of Ni (II) cations in the solutions 0.1 to 1 g / I and the content of Cu (II) cations in the same 0.03 is up to 1 g / l.
  • the pH of the application solutions is in the acidic to neutral range, i.e. in the range of 3.0 to 7.0.
  • the solutions are preferably adjusted, for example using ethanoic acid (acetic acid) or phosphoric acid on the one hand or sodium hydroxide solution on the other hand, in such a way that they have a pH between 4.0 and 5.0.
  • the solutions containing titanium and / or manganese and / or cobalt and / or nickel and / or copper salts used according to the inventive method can be used in the temperature range from 20 to 120 ° C., but are preferably used in the temperature range from 30 to 50 ° C worked. Treatment times of approximately 1 minute are sufficient to achieve excellent post-passivation of the phosphated metal surfaces even at these temperatures.
  • the process according to the invention is carried out in such a way that cleaned phosphated metal surfaces are first rinsed with water and then, according to the present process, with an acidic, titanium (IV) - and / or manganese (II) - and / or cobalt (II) - and / or solution containing nickel (II) and / or copper (II) salts in the temperature range of preferably 30 to 50 ° C., which can be obtained by adding solid or liquid concentrates containing the corresponding salts in a suitable amount dissolves in water in a manner known per se.
  • the treatment time is usually 1 minute.
  • the post-passivated metal surfaces are rinsed with deionized water and then dried with compressed air.
  • the metal surfaces post-passivated in accordance with the method according to the invention are outstandingly suitable for subsequent coating with paints, lacquers, varnishes and the like.
  • the post-passivated metal surfaces in this way offer an outstandingly suitable reason for cathodic electrocoat materials.
  • the phosphated and post-passivated metal surfaces are also suitable for other post-treatment processes.
  • Steel parts were sprayed with an alkaline cleaning solution for 2 min at 50 ° C. and then rinsed with water. They were then phosphated with a zinc phosphate solution for 2 minutes in a spray at 50 ° C. and then rinsed with water.
  • the steel parts were then post-passivated with the post-passivation solution containing 0.3 g of copper (II) ethanate hydrate per liter at 35 ° C. for 1 min in spraying. It was then rinsed with deionized water and dried with compressed air.
  • the post-passivation solution containing 0.3 g of copper (II) ethanate hydrate per liter at 35 ° C. for 1 min in spraying. It was then rinsed with deionized water and dried with compressed air.
  • the dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes.
  • the dry film thickness of the paint was 18 ⁇ m.
  • the parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.
  • Ni (CH 3 COO) 2 .4H 2 0 was made into a 0.7 g to prepare a post-passivation solution.
  • 1- 1 containing solution dissolved in water, corresponding to 0.17 g Ni per liter of solution.
  • Steel parts were immersed for 10 minutes at 80 ° C with an alkaline cleaning solution and then rinsed with water. The parts were then dipped in a zinc phosphate solution at 50 ° C. for 3 minutes and rinsed again.
  • the solution containing 0.7 g of nickel (II) ethanate tetrahydrate per liter at 35 ° C. was used for the post-passivation, the treatment time being 1 min in immersion.
  • the post-passivated parts were rinsed with deionized water and dried with compressed air.
  • an electro-dip coating was applied cathodically, which was dried by heating to 185 ° C. for 20 minutes.
  • the dry film thickness of the lacquer was 18 ⁇ m.
  • the painted parts were then provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 hours.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.4 to 0.6 mm.
  • Ni (CH 3 COO) 2 .4H 2 0 and C U (CH 3 -COO) 2 .H 2 0 were dissolved in water to give a solution containing 0.5 g ⁇ I -1 nickel (II) ethanate tetrahydrate and 0.1 g - I -1 copper (II) ethanate hydrate contained. This corresponds to a content of 0.12 g Ni and 0.03 g Cu per liter of solution.
  • the parts were treated with the solution containing nickel and copper ions prepared as described above for 1 min at 40 ° C. in an immersion, then rinsed with deionized water and dried with compressed air.
  • the parts passivated in this way were then coated with a cathodic electrocoating material and dried for 20 minutes by heating to 185.degree.
  • the dry film thickness of the lacquer was 18 pm.
  • the parts were provided with individual cuts and subjected to the salt spray test (DIN 50 021) for 480 h.
  • the evaluation according to DIN 53 167 showed an infiltration of 0.2 to 0.4 mm.
  • Example 1 To prepare the rinse solutions, the cations listed in Table 1 were dissolved individually in water (Examples 4 to 9) or in combination (Examples 10 to 14) to give solutions containing 0.1 gl -1 of total cation (s).
  • the salts used were the ethanates (acetates) or (in the case of Ti (IV) the 2,4-pentanedionate (titanylacetylacetonate).
  • the steel parts were then post-passivated with the post-passivation solutions containing the cations in the amount listed in Table I, rinsed with demineralized water and dried with compressed air.
  • the dried parts were coated with a cathodic electrocoating material and dried at 185 ° C. for 20 minutes.
  • the dry film thickness of the paint was 18 ⁇ m.
  • the parts were provided with individual cuts and subjected to the alternating climate test according to VW standard P 12 10 30 days.

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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)

Claims (8)

1. Procédé de post-passivation de surfaces métalliques phosphatées à base de fer, d'acier, d'acier zingué ou d'aluminium au moyen de solutions aqueuses de sels d'ions métalliques multiva- lents, acides à neutres, dans lequel on rince en premier lieu les surfaces métalliques phosphatées avec de l'eau, ensuite traite avec des solutions aqueuses qui manifestent une valeur de pH dans la zone de 3 à 7 ainsi qu'une température dans la zone de 20 à 120°C, et contiennent un ou plusieurs des sels énumérés ci-après:
a) 2,4-pentanedionato-titane (IV)-oxyde (acétyl- acétonate de titanyle),
b) éthanoate de manganèse (II) (acétate de)
c) éthanoate de cobalt (II) (acétate de)
d) éthanoate de nickel (II) (acétate de)
e) éthanoate de cuivre (II) (éthanoate de)

dans lesquelles la teneur en cation métallique s'élève dans les solutions respectivement à 0,01 à 10 g/l et également lors de la présence de plusieurs des cations mentionnés ne dépasse pas la valeur de 10 g/I et dans lequel on rince par la suite avec de l'eau et le cas échéant sèche.
2. Procédé selon la revendication 1, caractérisé en ce que les solutions contiennent un ou plusieurs sels mentionnés de a à e, dans lequel la teneur en cations Ti (IV), Mn (II), Co (II) ou Ni (II) dans les solutions s'élève de 0,1 g/l à 1 g/I et la teneur en cations Cu (II) dans celles-ci s'élève de 0,03 à 1 g/l.
3. Procédé selon la revendication 1, caractérisé en ce que les solutions contiennent:
b) de l'éthanoate de manganèse (II) et
c) de l'éthanoate de cobalt (II)

dans lesquelles la teneur en cations Mn (II) et en cations Co (II) dans les solutions s'élève respectivement à 0,05 à 1 g/I.
4. Procédé selon la revendication 1, caractérisé en ce que les solutions contiennent:
d) de l'éthanoate de nickel (II) et
e) de l'éthanoate de cuivre (II)

dans lesquelles la teneur en cations Ni (II) dans les solutions s'élève à 0,1 à 1 g/I et la teneur en cations Cu (II) dans les mêmes s'élève à 0,03 à 1 g/l.
5. Procédé selon la revendication 1, caractérisé en ce que les solutions contiennent:
a) du (2,4-pentanedionato)titane (II) oxyde,
c) de l'éthanoate de cobalt (II), et
d) de l'éthanoate de nickel (II)

dans lesquelles la teneur en cations Ti (IV), Co (II) et Ni (II) dans les solutions s'élève respectivement à 0,01 à 1 g/I.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que les solutions manifestent une valeur de pH dans la zone de 4 à 5.
7. Procédé selon les revendications 1 à 6, caractérisé en ce que les solutions présentent une température dans la zone de 30 à 50°C.
8. Procédé selon les revendications 1 à 7, caractérisé en ce que l'on traite les surfaces métalliques phosphatées avec les solutions, selon un processus de pulvérisation, ou d'immersion, et par la suite, rince avec de l'eau complètement déminéralisée ou pauvre en minéraux et sèche.
EP84111060A 1984-01-07 1984-09-17 Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre Expired EP0149720B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843400339 DE3400339A1 (de) 1984-01-07 1984-01-07 Verfahren zur nachpassivierung von phosphatierten metalloberflaechen unter verwendung von nickel- und/oder kupfer-kationen enthaltenden loesungen
DE3400339 1984-01-07

Publications (3)

Publication Number Publication Date
EP0149720A2 EP0149720A2 (fr) 1985-07-31
EP0149720A3 EP0149720A3 (en) 1985-08-14
EP0149720B1 true EP0149720B1 (fr) 1988-10-26

Family

ID=6224446

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84111060A Expired EP0149720B1 (fr) 1984-01-07 1984-09-17 Procédé de post passivation de surfaces métalliques phosphatées, utilisant des solutions contenant des cations de titane et/ou manganèse et/ou cobalt et/ou nickel et/ou cuivre

Country Status (6)

Country Link
US (1) US4600447A (fr)
EP (1) EP0149720B1 (fr)
JP (1) JPS60159175A (fr)
DE (2) DE3400339A1 (fr)
ES (1) ES8703167A1 (fr)
ZA (1) ZA85105B (fr)

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US4673445A (en) * 1986-05-12 1987-06-16 The Lea Manufacturing Company Corrosion resistant coating
DE4031817A1 (de) * 1990-10-08 1992-04-09 Henkel Kgaa Verfahren zur passivierenden nachbehandlung von phosphatierten metalloberflaechen
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
DE4138218C2 (de) * 1991-11-21 1994-08-04 Doerken Ewald Ag Verwendung von Nachtauchmitteln für die Nachbehandlung von chromatierten oder passivierten Verzinkungsschichten
FR2685352A1 (fr) * 1991-12-24 1993-06-25 Pont A Mousson Revetement multicouche, avec son procede d'obtention et son application.
JPH0790614A (ja) * 1993-09-22 1995-04-04 Elna Co Ltd アルミニウムまたはアルミニウム合金類およびこれらの化成処理方法
JPH07278891A (ja) * 1994-04-12 1995-10-24 Nippon Parkerizing Co Ltd 金属材料の塗装前処理方法
MX9605901A (es) * 1994-05-27 1997-12-31 Herberts & Co Gmbh Procedimiento para revestir substratos metalicos fosfatados.
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19606018A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt
US6485580B1 (en) * 1998-05-20 2002-11-26 Henkel Corporation Composition and process for treating surfaces or light metals and their alloys
AU4308099A (en) * 1998-05-20 1999-12-06 Henkel Corporation Composition and process for treating surfaces of light metals and their alloys
DE19834796A1 (de) 1998-08-01 2000-02-03 Henkel Kgaa Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung
AU4566900A (en) * 1999-05-28 2000-12-18 Henkel Kommanditgesellschaft Auf Aktien Post-passivation of a phosphatized metal surface
DE19956383A1 (de) * 1999-11-24 2001-05-31 Henkel Kgaa Verfahren zur Phospatierung mit metallhaltiger Nachspülung
DE10115244A1 (de) * 2001-03-28 2002-10-02 Henkel Kgaa Nachpassivierung einer phosphatierten Metalloberfläche im Bandverfahren
MD3008G2 (ro) * 2005-06-27 2006-10-31 Государственный Университет Молд0 Procedeu de repatinare a pieselor vechi din bronz şi alamă restaurate
CN102605361B (zh) * 2011-01-24 2016-11-23 北京中科三环高技术股份有限公司 一种烧结钕铁硼磁性材料的表面处理方法
DE102013107505A1 (de) * 2013-07-16 2015-01-22 Thyssenkrupp Rasselstein Gmbh Verfahren zum Auftragen einer wässrigen Behandlungslösung auf die Oberfläche eines bewegten Stahlbands

Citations (1)

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Publication number Priority date Publication date Assignee Title
JPS58130282A (ja) * 1982-01-29 1983-08-03 Nippon Steel Corp 塗装用金属の前処理方法

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US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
JPS4964530A (fr) * 1972-07-10 1974-06-22
US3852123A (en) * 1972-11-20 1974-12-03 Pennwalt Corp Sealing rinses for phosphate coatings on metal
JPS535622B2 (fr) * 1973-02-12 1978-03-01
US3895970A (en) * 1973-06-11 1975-07-22 Pennwalt Corp Sealing rinse for phosphate coatings of metal
JPS5145604B2 (fr) * 1973-12-21 1976-12-04
JPS5292836A (en) * 1976-01-30 1977-08-04 Nippon Packaging Kk Zinc or its alloys subjected to chemical conversion
SU914652A1 (ru) * 1980-04-07 1982-03-23 Inst Mekhaniki Metallopolimern Способ дополнительной обработки пористых фосфатных покрытий1
FR2520758A1 (fr) * 1982-01-29 1983-08-05 Produits Ind Cie Fse Composition et procede pour le traitement de surfaces metalliques phosphatees
JPS6018752B2 (ja) * 1982-05-14 1985-05-11 新日本製鐵株式会社 化成処理前処理法

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Publication number Priority date Publication date Assignee Title
JPS58130282A (ja) * 1982-01-29 1983-08-03 Nippon Steel Corp 塗装用金属の前処理方法

Also Published As

Publication number Publication date
DE3400339A1 (de) 1985-08-29
JPS60159175A (ja) 1985-08-20
ES8703167A1 (es) 1987-02-01
DE3474839D1 (en) 1988-12-01
ZA85105B (en) 1985-08-28
US4600447A (en) 1986-07-15
ES539387A0 (es) 1987-02-01
EP0149720A2 (fr) 1985-07-31
EP0149720A3 (en) 1985-08-14

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