EP0209143B1 - Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech - Google Patents

Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech Download PDF

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Publication number
EP0209143B1
EP0209143B1 EP19860109842 EP86109842A EP0209143B1 EP 0209143 B1 EP0209143 B1 EP 0209143B1 EP 19860109842 EP19860109842 EP 19860109842 EP 86109842 A EP86109842 A EP 86109842A EP 0209143 B1 EP0209143 B1 EP 0209143B1
Authority
EP
European Patent Office
Prior art keywords
solution
stage
chromium
ions
zinc
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 - Lifetime
Application number
EP19860109842
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0209143A3 (en
EP0209143A2 (de
Inventor
Akimitsu Fukuda
Yutaka Tsuchiya
Kazuyuki Oyama
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.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
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 Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Publication of EP0209143A2 publication Critical patent/EP0209143A2/de
Publication of EP0209143A3 publication Critical patent/EP0209143A3/de
Application granted granted Critical
Publication of EP0209143B1 publication Critical patent/EP0209143B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/05—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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C22/73—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 characterised by the process
    • 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

  • a zinc plating layer is coated with the aid of a solution which contains at least 0.002% nickel ions, 0.002 to 0.10% iron III ions and complexing agents and an alkaline aqueous solution with a pH of 11 or greater, a second plating layer is applied. A dilute acidic aqueous solution containing chromium VI ions is then brought into contact with the surface. This is followed by rinsing with water and drying.
  • the application of a second layer to the zinc layer as taught in this document is not the purpose of the present invention.
  • the object of the invention is to provide a method by means of which the corrosion resistance and the adhesion of a lacquer applied in a later phase to steel sheets which are provided with a zinc-aluminum alloy can be improved without thereby having to accept a complex method to have to.
  • the alloy layer is formed from a zinc-aluminum alloy containing 1 to 70 wt .-% aluminum, after process step a) rinsing in water and that then the metal surface in process step b) is brought into contact with a solution which additionally contains silica until a layer weight of 10 to 400 mg / m 2 measured after drying has been produced.
  • the metal ions contained in the alkaline solution according to stage a) are usually used as inorganic salts, e.g. B. nitrates, sulfates, carbonates, chlorides and the like. the like. However, other compounds are also suitable as long as they are soluble in the alkaline medium.
  • the concentration of the metal ions is generally 0.01 to 10 g / l, preferably 0.05 to 5 g / l.
  • These metal ions must be bound by a sufficient amount of complexing agent to ensure that they are and remain in the dissolved state.
  • the amount of complexing agent is therefore about 0.1 to 20 g / l.
  • the complexing agents can be inorganic or organic in nature.
  • Suitable inorganic complexing agents are, for example, condensed phosphates, ammonia or amine compounds.
  • Suitable organic complexing agents are, for example, dicarboxylic acids, in particular malonic acid, fumaric acid, amino acids, such as glycine, hydroxycarboxylic acids, such as citric acid, gluconic acid and lactic acid, polyhydroxyaliphatic compounds, such as sorbitol or 1,2-ethanediol, phenylcarboxylic acids, such as salicylic acid and phthalic acid, aminocarboxylic acids, such as ethylenedic acid, Polyamino acids, such as diethanolamine methanephosphonate, lignin sulfonate and the like.
  • Particularly preferred complexing agents are hexahydroxyheptanoic acid, sodium gluconate and sodium ethylenediaminetetraacetate.
  • the treatment solution according to stage a) is applied at a temperature between room temperature and the boiling point of the solution in spraying or dipping for a time sufficient to selectively dissolve aluminum out of the alloy layer.
  • Treatment at a temperature of 50 to 80 ° C. for a period of 4 to 10 seconds with a continuously operating belt system is particularly expedient. If necessary, shorter treatment times can also be used, in which case solutions of higher concentration and higher temperature should be used.
  • the treatment solution according to process stage b) is obtained in the simplest way by dissolving chromic acid and incorporating colloidal silica.
  • the layer formed with this solution should - after
  • Drying on - have a layer weight of 10 to 400 mg / m2.
  • the purpose pursued by the invention is only incompletely achieved, with higher layer weights there is a risk that the paint adhesion will decrease.
  • Preferred refinements of the invention provide to use a treatment solution in process stage b) which additionally contains chromium III ions and / or phosphate ions.
  • the chromium III ion content is created in the simplest manner by adding a reducing agent, such as starch, oxalic acid, tannin or alcohol, to the aqueous solution of chromate in certain amounts.
  • the metal surfaces in process step b) into contact with a solution in which the weight ratio of SiO2: chromium VI is in the range from 0.6 to 15.
  • the chromium III: chromium VI weight ratio should be 0.2 to 1. If the solution contains phosphate, it is advisable to set the weight ratio of PO4: Chrom-VI to a value in the range of 0.6 to 3.
  • the process according to the invention is intended for the treatment of steel sheets provided with zinc / aluminum alloys, in which the aluminum content in the alloy layer is 1 to 70% by weight.
  • the adhesion to organic coatings mediated by the layer formed is particularly high if an epoxy lacquer is applied in step d).
  • at least the base lacquer should be an epoxy lacquer.
  • Steel sheets of the nature mentioned in the test example were at 57 to 63 ° C. for 10 seconds with an alkaline solution containing 0.17 g / l Fe (III) and 0.24 g / l Ni ions (each introduced as nitrate) as well as 1.7 g / l sodium hexahydroxy heptonate and 22 g / l sodium hydroxide and had a pH of 13.6, treated by spraying, rinsed with water and with an aqueous solution containing provided by roll order. It was then dried. The layer weight was 190 mg / m2.
  • the solution for producing the chromate coating used in comparative experiment la of table 2 had the same nature as the aforementioned solution.
  • test sheets which were again the same, were pretreated with an alkaline solution at 55 to 60 ° C. and for 6 seconds in spraying, the 0.17 g / l Fe (III) and 0.24 g / l co-ions (in each case as nitrate introduced), 1.7 g / l Contained sodium hexahydroxy heptonate and 22 g / l sodium hydroxide.
  • the pH of the solution was 13.6. It was then rinsed with water and a solution was applied by roller application contained and had a pH of 1.5. After drying, the layer weight was 280 mg / m2.
  • the chromium-containing solution used in Table 2 in Comparative Example 2 had the same nature as the last-mentioned solution.
  • the sheets treated as in Examples 1 and 2 above were subjected to two different coatings.
  • it was a two-layer lacquer structure with an epoxy lacquer as the base lacquer, which was applied with a layer thickness of 5 ⁇ m and then baked at 190 ° C.
  • a polyester lacquer which was applied with a layer thickness of 13 ⁇ m and baked at 200 ° C., served as the topcoat.
  • the other painting consisted of a single-layer paint structure, for which a polyester top coat had been used. It was applied with a layer thickness of 14 ⁇ m and baked at 210 ° C.
  • a device from Du Pont was used to carry out the impact test. It works with a beater bar with a diameter of 12.7 mm, which is loaded with 1 kg and hits the painted sheet metal surface from a height of 50 cm. The paint adhesion is again determined using adhesive tape, as stated above.
  • the evaluation is as follows.
  • a cut was made with a knife to determine corrosion resistance and paint infiltration down to the metal surface.
  • Such scored sheets and sheets deformed in accordance with the bending test were subjected to the salt spray test, which works with a 5% saline solution, for 500 hours (with a single-layer paint structure) or for 1000 hours (with a two-layer paint structure) in accordance with JIS-Z-2371. The evaluation takes place at the interfaces, on the edges and at the bending point.
  • the treated sheets were exposed to the weather for a period of 3 years.
  • the evaluation was carried out according to the following standards:

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)
  • Application Of Or Painting With Fluid Materials (AREA)
EP19860109842 1985-07-19 1986-07-17 Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech Expired - Lifetime EP0209143B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15801685A JPS6220880A (ja) 1985-07-19 1985-07-19 亜鉛−アルミニウム合金めつき鋼板の表面処理方法
JP158016/85 1985-07-19

Publications (3)

Publication Number Publication Date
EP0209143A2 EP0209143A2 (de) 1987-01-21
EP0209143A3 EP0209143A3 (en) 1988-10-26
EP0209143B1 true EP0209143B1 (de) 1991-06-19

Family

ID=15662426

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860109842 Expired - Lifetime EP0209143B1 (de) 1985-07-19 1986-07-17 Verfahren zur Oberflächenbehandlung von mit einer Zink/Aluminium-Legierung versehenem Stahlblech

Country Status (6)

Country Link
EP (1) EP0209143B1 (enExample)
JP (1) JPS6220880A (enExample)
AU (1) AU6008486A (enExample)
BR (1) BR8603404A (enExample)
DE (2) DE3624101A1 (enExample)
GB (1) GB2178065B (enExample)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987001397A1 (fr) * 1985-08-29 1987-03-12 Nisshin Steel Co., Ltd. Tole d'acier galvanise a chaud et son procede de fabrication
JPH08983B2 (ja) * 1987-03-05 1996-01-10 新日本製鐵株式会社 耐食性に優れたクロメ−ト処理方法
JPH03226584A (ja) * 1990-01-30 1991-10-07 Nippon Parkerizing Co Ltd 亜鉛系めっき鋼板用表面処理液及び表面処理方法
JP2697485B2 (ja) * 1992-05-27 1998-01-14 住友金属工業株式会社 高耐食性合金化溶融亜鉛めっき鋼板の製造法
FR2701754B1 (fr) * 1993-02-18 1995-04-07 Pont A Mousson Elément de tuyauterie pour canalisation enterrée, canalisation enterrée correspondante, et procédé de protection d'un tel élément de tuyauterie.
LT3218B (en) 1993-03-27 1995-04-25 Chemijos Inst Method for coating zinc alloy by chromium plating
JP3983386B2 (ja) 1998-04-03 2007-09-26 日本ペイント株式会社 クロメート防錆処理剤
AU2002301945B2 (en) * 2001-11-21 2008-07-17 Chiyoda Chemical Co., Ltd Surface treatment method of metal member, and metal goods
ES2428290T3 (es) * 2011-03-22 2013-11-06 Henkel Ag & Co. Kgaa Tratamiento anticorrosivo de varios pasos para componentes metálicos, que por lo menos parcialmente presentan superficies de cinc o de aleaciones de cinc
EP2631333A1 (de) * 2012-02-24 2013-08-28 Henkel AG & Co. KGaA Vorbehandlung von Zinkoberflächen vor einer Passivierung

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE316668B (enExample) * 1963-09-23 1969-10-27 Parker Ste Continentale
GB1234181A (enExample) * 1967-06-14 1971-06-03
FR1596007A (enExample) * 1968-04-18 1970-06-15
JPS49135836A (enExample) * 1973-05-04 1974-12-27
JPS5392339A (en) * 1977-01-25 1978-08-14 Nippon Paint Co Ltd Metal surface treatment agent
US4227946A (en) * 1979-02-09 1980-10-14 Oakite Products, Inc. No-rinse pre-paint coating composition and method
JPS5745833A (en) * 1980-09-01 1982-03-16 Taeko Nakagawa Stomack camera
JPH0647741B2 (ja) * 1983-04-26 1994-06-22 日本ペイント株式会社 塗膜密着性に優れた耐食性金属表面処理用組成物
FR2560894B1 (fr) * 1984-03-07 1988-11-18 Parker Ste Continentale Procede de preparation de surfaces de zinc, d'alliages de zinc et d'acier recouvert de ces materiaux, destinees a recevoir des peintures ou des vernis
JPS6126784A (ja) * 1984-07-16 1986-02-06 Nippon Paint Co Ltd 化成処理されたアルミニウム含有亜鉛めつき合金鋼板

Also Published As

Publication number Publication date
GB2178065B (en) 1989-07-19
JPH0351797B2 (enExample) 1991-08-07
EP0209143A3 (en) 1988-10-26
GB8617211D0 (en) 1986-08-20
BR8603404A (pt) 1987-02-24
EP0209143A2 (de) 1987-01-21
AU6008486A (en) 1987-01-22
DE3624101A1 (de) 1987-01-22
JPS6220880A (ja) 1987-01-29
DE3679866D1 (de) 1991-07-25
GB2178065A (en) 1987-02-04

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