EP0214571B1 - Procédé pour la formation de couches de conversion sur du zinc et/ou sur des alliages de zinc - Google Patents

Procédé pour la formation de couches de conversion sur du zinc et/ou sur des alliages de zinc Download PDF

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Publication number
EP0214571B1
EP0214571B1 EP86111976A EP86111976A EP0214571B1 EP 0214571 B1 EP0214571 B1 EP 0214571B1 EP 86111976 A EP86111976 A EP 86111976A EP 86111976 A EP86111976 A EP 86111976A EP 0214571 B1 EP0214571 B1 EP 0214571B1
Authority
EP
European Patent Office
Prior art keywords
solution
zinc
chromium
contact
chromating
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
EP86111976A
Other languages
German (de)
English (en)
Other versions
EP0214571A1 (fr
Inventor
Kenshi Saeki
Kazuyuki Oyama
Iwao Kawasaki
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 EP0214571A1 publication Critical patent/EP0214571A1/fr
Application granted granted Critical
Publication of EP0214571B1 publication Critical patent/EP0214571B1/fr
Expired 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
    • C23C22/06—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
    • C23C22/37—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 hexavalent chromium compounds
    • C23C22/38—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 hexavalent chromium compounds containing also phosphates

Definitions

  • the invention relates to a var procedure for producing conversion layers on surfaces made of zinc or zinc alloys by means of aqueous acidic chromating solutions which contain chromium VI, chromium III and phosphate.
  • drying processes i.e. Processes in which the chromating solution is dried without rinsing water at ambient temperature or in particular at an elevated temperature are becoming increasingly important.
  • the advantage of such methods is, in particular, that no rinsing water is produced and that the conversion layers obtained in this way impart excellent corrosion resistance.
  • Another advantage is that the treatment solutions e.g. by adding zinc or reducing chromium VI to chromium III less than those in which the conversion layer is in constant contact with the solution.
  • the object of the invention is to provide a method for producing conversion layers on surfaces made of zinc or zinc alloys, the chromating solution of which has a longer service life, which leads to excellent conversion layers with regard to corrosion protection and adhesion promotion for a possibly subsequently applied lacquer and which is nevertheless simple to carry out .
  • the method is suitable for the treatment of workpieces coated with solid zinc or solid zinc alloys, e.g. galvanized steel sheet or strip.
  • chromic acid is introduced as such in the simplest way.
  • the chromium-III ions can be added using suitable salts, but particularly advantageously by reducing chromium-VI using e.g. Oxalic acid, tannic acid, starch, alcohol, hydrazine or citric acid can be added.
  • the phosphate content can be adjusted by adding phosphoric acid, ammonium phosphate and the like.
  • the fluorozirconate content can be measured by adding ammonium hexafluorozirconate or the free acid.
  • the concentrations of the active constituents of the chromating solution are critical insofar as the conversion layers produced do not have the required quality at a chromic acid concentration below 10 g / l, and at a concentration above 100 g / l the paint adhesion decreases due to an excessively high layer weight. In the case of chromium concentrations below 1 g / 1, the corrosion protection in particular decreases. It should also be noted that only certain varnishes can then be applied, i.e. the otherwise universal type of painting is partially lost. At concentrations above 21 g / 1, it is difficult to avoid the formation of precipitates in the chromating solution.
  • the phosphate. that is built into the conversion layer is responsible in particular for the uniform appearance of the conversion layer and the excellent adhesion for a subsequently applied lacquer. If its concentration is below 0.1 g / l, the aforementioned effects are only present to a small extent. At concentrations above 4 g / l, the proportion of phosphate in the conversion layer increases sharply, which is associated with reduced corrosion resistance. The fluorozirconate ion intensifies the pickling attack on the zinc surface. Its ability to complexly bind metal ions is likely to be decisive for increasing the service life of the chromating solution or for its ability to form conversion layers of excellent quality over a longer period of time.
  • the chromium VI chromium III weight ratio also determines the uniformity of the conversion layers produced, but is also responsible for the long service life of the chromating solution and the universal type of coating. When leaving the area, these advantages no longer exist. Even the weight ratios of chrome Acid: fluorozirconate and phosphate: fluorozirconate are critical insofar as the favorable results with regard to corrosion resistance, adhesion promotion and universal paintability are lost when the design rule is left.
  • the metal surface is brought into contact with a chromating solution in which the weight ratio of chromic acid: fluorozirconate is set to (10 to 40): 1.
  • the corrosion resistance and the adhesion promotion of the conversion layer produced by the method according to the invention can be further improved if, according to a preferred embodiment of the invention, the surface is brought into contact with a chromating solution which additionally contains 0.1 to 200 g / l of silicate or silica. With lower contents, the improvement achieved is only very slight, with higher contents, the layer weight increases considerably, which reduces the paint adhesion. The best results are achieved if, according to a further advantageous embodiment of the invention, the metal surface is brought into contact with a chromating solution in which the weight ratio of chromic acid: silica is set to (10 to 0.5): 1.
  • the chromating solution is usually used at a temperature that ranges from ambient to 50 ° C.
  • the contact with the surface consisting of zinc or a zinc alloy is best done by roller application, spraying or dipping. Any excess chromating solution should be removed as soon as possible, for example using pinch rollers. In this way, it can be achieved in a particularly simple manner that a specific and constant layer weight results.
  • a particularly favorable embodiment of the invention provides for the metal surface to be brought into contact with the phosphating solution in such a way that, after drying, a layer weight of 10 to 200 mg / m 2 , preferably 15 to 100 mg / m 2 (calculated as Cr) , results.
  • Excess chromating solution removed using squeeze rollers can be returned to the treatment bath and thereby reused.
  • drying is carried out without intermediate rinsing. This can be done at ambient temperature or at elevated temperature, e.g. in a convection oven.
  • the service life of the chromating solution is practically unlimited and the conversion layers produced are of excellent quality.
  • meaningful means, within the usual process sequence, degreasing / cleaning, rinsing water, applying the chromating solution and drying by thorough rinsing to ensure that as little contamination as possible gets into the chromating solution.
  • a certain enrichment, particularly of zinc ions cannot be avoided, an excess can be removed by known ion exchange processes.
  • Oiled sheets of hot-dip galvanized steel were treated after the process step alkaline degreasing, water rinsing, squeezing with rollers, roller application of the chromating solution at room temperature and drying.
  • the compositions of the chromating solutions used for this are given in Table 1 below.
  • the layer weights produced with all chromating solutions were 20 to 25 mglm 2 (calculated as Cr).
  • the coating is first scratched with a cutter at a distance of 1 mm to the metal surface, so that a grid with several scratch marks lying at an angle of 90 ° is created.
  • the test sheet is first dented slowly by pressing in a ball until a bulge with a height of 7 mm is created.
  • a falling body with a weight of 1 kg and a punch diameter of 12.7 mm is dropped on the test sheet from a height of 30 cm. The top and back of the deformed area are evaluated.

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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (6)

1. Procédé de production de couches de conversion sur des surfaces der zinc ou d'alliages de zinc au moyen de solutions de chromatage acides aqueuses qui contiennent du chrome-VI, du chrome-III et du phosphate, caractérisé en ce qu'on amène la surface en contact avec une solution de chromatage qui contient
10 à 100 g/I d'acide chromique (calc. en Cr03)
1 à 21 g/I d'ions chrome (calc. en Cr)
0,1 à 4 g/l d'ions phosphate (calc. en P04) et
0,1 à 4 g/I d'ions fluorozirconate (calc. en ZrF6),

dans laquelle on ajuste le rapport pondéral
du chrome-VI au chrome-III à (1,5 à 5) : 1
de l'acide chromique
au fluorozirconate à (5 à 100) : 1 et
du phosphate au fluorozirconate à (0,5 à 2) : 1

puis on sèche la solution de chromatage.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on amène la surface en contact avec une solution de chromatage dans laquelle le rapport pondéral acide chromique : fluorozirconate est ajusté à (10 à 40) : 1.
3. Procédé suivant les revendications 1 ou 2, caractérisé en ce qu'on amène la surface en contact avec une solution de chromatage qui contient en outre 0,1 à 200 g/I de silicate ou d'acide silicique.
4. Procédé suivant la revendication 3, caractérisé en ce qu'on amène la surface en contact avec une solution de chromatage dans laquelle le rapport pondéral acide chromique : acide silicique est de (10 : 0,5) : 1.
5. Procédé suivant une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on amène la surface en contact avec une solution de chromatage dont le pH est dans le domaine de 0,6 à 4.
6. Procédé suivant une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on amène la surface métallique en contact avec la solution de chromatage de telle sorte qu'il en résulte après séchage un poids de couche de 10 à 200 mg/m2, de préférence de 15 à 100 mg/m2 (calc. en Cr).
EP86111976A 1985-09-05 1986-08-29 Procédé pour la formation de couches de conversion sur du zinc et/ou sur des alliages de zinc Expired EP0214571B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP194940/85 1985-09-05
JP60194940A JPS6256580A (ja) 1985-09-05 1985-09-05 亜鉛系メツキ鋼板のクロメ−ト塗布液

Publications (2)

Publication Number Publication Date
EP0214571A1 EP0214571A1 (fr) 1987-03-18
EP0214571B1 true EP0214571B1 (fr) 1989-01-18

Family

ID=16332863

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86111976A Expired EP0214571B1 (fr) 1985-09-05 1986-08-29 Procédé pour la formation de couches de conversion sur du zinc et/ou sur des alliages de zinc

Country Status (9)

Country Link
US (1) US4749418A (fr)
EP (1) EP0214571B1 (fr)
JP (1) JPS6256580A (fr)
AU (1) AU584454B2 (fr)
CA (1) CA1274156A (fr)
DE (2) DE3629382A1 (fr)
GB (1) GB2180263B (fr)
NZ (1) NZ217245A (fr)
ZA (1) ZA866712B (fr)

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JPS6352338A (ja) * 1987-05-29 1988-03-05 Mitsubishi Electric Corp ディスク再生装置
GB2215740B (en) * 1988-02-08 1992-06-03 Brent Chemicals Int Composition and process for treating metal surfaces
JPH01249331A (ja) * 1988-03-31 1989-10-04 Toyo Kohan Co Ltd 加工性に優れたポリエステル樹脂被覆金属板の製造方法
JPH0735587B2 (ja) * 1988-06-30 1995-04-19 日本鋼管株式会社 高耐食性表面処理鋼板の製造方法
JPH0230771A (ja) * 1988-07-19 1990-02-01 Nkk Corp 高耐食性表面処理鋼板の製造方法
JPH02243772A (ja) * 1989-03-17 1990-09-27 Nisshin Steel Co Ltd 亜鉛めっき鋼板の高耐食クロメート処理液および処理方法
JP2879344B2 (ja) * 1989-04-07 1999-04-05 富山化学工業株式会社 ３―ホルミルアミノ―７―メチルスルホニルアミノ―６―フェノキシ―４ｈ―１―ベンゾピラン―４―オンまたはその塩を含有する抗炎症製剤
JPH0753911B2 (ja) * 1989-04-07 1995-06-07 日本パーカライジング株式会社 亜鉛系めっき鋼板のクロメート処理方法
JPH07100873B2 (ja) * 1989-09-27 1995-11-01 日本パーカライジング株式会社 亜鉛系メッキ鋼板のクロメート塗布液
CA2019861C (fr) * 1990-06-26 1995-10-17 Hiroaki Kawamura Feuille d'acier etame a double couche de chrome et pellicule de resine de copolyester, et methode de fabrication
JP2628782B2 (ja) * 1990-10-08 1997-07-09 日本パーカライジング株式会社 亜鉛系めっき鋼板のクロメート処理方法
LT3218B (en) 1993-03-27 1995-04-25 Chemijos Inst Method for coating zinc alloy by chromium plating
JP3288152B2 (ja) * 1993-08-14 2002-06-04 日本パーカライジング株式会社 耐黒変性及び耐白錆性に優れた亜鉛系めっき鋼板の製造方法
US6149735A (en) * 1995-11-30 2000-11-21 Henkel Corporation Chromate treatment bath composition and process for application to metals
JPH09157864A (ja) * 1995-11-30 1997-06-17 Nippon Parkerizing Co Ltd 金属材料用クロメート処理液組成物、および処理方法
US7314671B1 (en) 1996-04-19 2008-01-01 Surtec International Gmbh Chromium(VI)-free conversion layer and method for producing it
DE19615664A1 (de) 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
WO1997041277A1 (fr) * 1996-04-26 1997-11-06 Henkel Corporation Passivation de chromate et solutions concentrees stables au stockage utilisees a cet effet
DE69832086T2 (de) 1997-08-21 2006-12-14 Henkel Kgaa Verfahren zum beschichten und/oder nachbessern von beschichtungen auf metalloberflächen
DE19740248A1 (de) * 1997-09-12 1999-03-18 Henkel Kgaa Chromatierung oder Nachpassivierung mit stabilisierten Cr(III)/Cr(VI)-haltigen Lösungen
KR100370472B1 (ko) * 1998-12-02 2003-04-10 주식회사 포스코 강판의내식성및표면외관을향상시키는3가크롬용액
US6375726B1 (en) * 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
US6527841B2 (en) * 2000-10-31 2003-03-04 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
DE102004032561B3 (de) * 2004-07-05 2006-02-09 Heraeus Electro-Nite International N.V. Behälter für Metallschmelze sowie Verwendung des Behälters
US20060240191A1 (en) * 2005-04-21 2006-10-26 The U.S. Of America As Represented By The Secretary Of The Navy Composition and process for preparing chromium-zirconium coatings on metal substrates
CN102066611B (zh) * 2008-04-25 2013-09-18 汉高股份及两合公司 用于处理镀锌钢的三价铬钝化剂
US8273190B2 (en) 2009-05-29 2012-09-25 Bulk Chemicals, Inc. Method for making and using chromium III salts
US20110070429A1 (en) * 2009-09-18 2011-03-24 Thomas H. Rochester Corrosion-resistant coating for active metals
US8425692B2 (en) 2010-05-27 2013-04-23 Bulk Chemicals, Inc. Process and composition for treating metal surfaces
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JPS6039169A (ja) * 1983-08-12 1985-02-28 Nippon Light Metal Co Ltd 親水性金属表面処理剤

Also Published As

Publication number Publication date
AU584454B2 (en) 1989-05-25
ZA866712B (en) 1987-11-25
CA1274156A (fr) 1990-09-18
AU6181586A (en) 1987-03-12
EP0214571A1 (fr) 1987-03-18
GB2180263A (en) 1987-03-25
DE3661845D1 (en) 1989-02-23
JPH0419313B2 (fr) 1992-03-30
GB2180263B (en) 1989-08-16
DE3629382A1 (de) 1987-03-05
NZ217245A (en) 1988-10-28
JPS6256580A (ja) 1987-03-12
GB8621414D0 (en) 1986-10-15
US4749418A (en) 1988-06-07

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