EP1492902A1 - Composition et procede de traitement de surfaces metalliques - Google Patents

Composition et procede de traitement de surfaces metalliques

Info

Publication number
EP1492902A1
EP1492902A1 EP03708992A EP03708992A EP1492902A1 EP 1492902 A1 EP1492902 A1 EP 1492902A1 EP 03708992 A EP03708992 A EP 03708992A EP 03708992 A EP03708992 A EP 03708992A EP 1492902 A1 EP1492902 A1 EP 1492902A1
Authority
EP
European Patent Office
Prior art keywords
treating solution
zirconium
composition according
tungstate
concentration
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.)
Withdrawn
Application number
EP03708992A
Other languages
German (de)
English (en)
Other versions
EP1492902A4 (fr
Inventor
Gerald Wojcik
Justin Girard
Robert Berry
Richard Bauer
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.)
MacDermid Inc
Original Assignee
MacDermid Inc
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 MacDermid Inc filed Critical MacDermid Inc
Publication of EP1492902A1 publication Critical patent/EP1492902A1/fr
Publication of EP1492902A4 publication Critical patent/EP1492902A4/fr
Withdrawn legal-status Critical Current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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates

Definitions

  • the present invention is directed to a composition and method for producing a conversion coating on metallic surfaces.
  • the conversion coatings of this invention are generally chromium free and improve the corrosion resistance of the treated surfaces as well as the adhesion of siccative organic finishes to those treated surfaces.
  • the conversion coatings of the present invention are minimally affected by subsequent heating and/or baking steps.
  • This invention is particularly suited to treating zinc, zinc alloys, aluminum and aluminum alloys, although steel and other metals may be treated.
  • conversion coatings for metal surfaces have been suggested in the prior art for the purpose of forming a coating, to protect the metal against corrosion and also serve as a base for improving the adhesion of subsequently applied siccative organic finishes.
  • Such conversion coatings are created by treatment of the metal surface with solutions of various chemicals, which react with the surface to form the desired coating.
  • Commonly used conversion coating compositions generally include phosphates and chromates.
  • Phosphate conversion coatings have long been used, particularly on steel.
  • the simplest phosphating solutions comprise aqueous solutions of alkali metal phosphates that can react with iron, aluminum, and/or zinc to form the phosphate conversion coating. While phosphate conversion coatings do increase the corrosion resistance of the treated surface and the adhesion of subsequently applied siccative organic coatings, in many applications, better results are required.
  • Chromate conversion coatings generally produce much better corrosion resistance and adhesion than phosphate coatings. However, chromate conversion coatings generally do not provide good corrosion resistance and adhesion at elevated temperatures. Chromate solutions generally comprise aqueous solutions of hexavalent and/or trivalent chromium along with other additives. Historically, hexavalent chromium has produced the hest performing chromate conversion coatings. However, recent improvements in trivalent chromate technology have allowed trivalent chromates to rival the performance of hexavalent chromates. Typical chromate compositions and processes are revealed in U.S. Patent Nos. 5,407,749 and 4,349,392, the teachings of each of which are incorporated by reference herein in their entirety. In any case, chromium has been determined to be a relatively toxic metal and is heavily regulated. As a result, significant efforts have been expended to replace chromate coatings with chrome free coatings.
  • the invention is particularly suited to the treatment of zinc and zinc alloy surfaces as well as surfaces of aluminum and aluminum alloys.
  • the inventors have found that it is preferable to adjust the pH of the treatment composition to between 2.0 and 7.0.
  • the treatment composition is free of chromium ions.
  • compositions and processes for the treatment of metal surfaces with a composition comprising: (1) a source of tungstate ions; and
  • the source of tungstate ions includes all tungstates but most specifically all ortho-tungstates, meta-tungstates and para-tungstates, polytungstates, hetero- polytungstates, isopolytungstates, peroxytungstates, and combinations thereof.
  • a source of meta- or para-tungstate is preferred.
  • Suitable sources of tungstate ions include sodium, potassium, lithium, calcium, cerium, barium, magnesium, strontium, hydrogen and ammonium tungstate salts, ammonium metatungstate, potassium metatungstate, sodium metatungstate, tungstic acid, sodium tungstate, potassium tungstate and ammonium tungstate.
  • a soluble tungstate salt such as ammonium or potassium tungstate, is most preferred for use in both the liquid concentrate and in the treatment solution.
  • concentration of tungstate (measured as tungsten) in the composition should range from about 0.01 g/1 to about 10 g/1, preferably from about 0.1 g/1 to about 1.5 g/1 and is most preferably about 1.0 g/1.
  • the composition also includes a soluble compound containing zirconium and preferably, fluoride.
  • suitable zirconium comprising materials include, but are not limited to, zirconium ammonium fluoride, dihydrogen hexafluorozirconate, potassium hexafluorozirconate, zirconium sulfate, zirconium carbonate, zirconium nitrate, and zirconium phosphate.
  • Dihydrogen hexafluorozirconate is the most preferred zirconium comprising compound.
  • the concentration of the zirconium comprising compound in the composition should preferably range from about 0.01 g/1 to about 2.0 g/1, most preferably from about 0.05 g/1 to about 0.5 g/1.
  • the inventors have determined that the pH of the treatment composition should preferably be maintained from about 2.0 to about 7.0, more preferably between 2.8 and 7.0.
  • the inventors have discovered that the corrosion protection afforded while operating outside of the foregoing range (2.0-7.0) is substantially inferior and that the stability of the aqueous solution of the treatment composition outside of the preferred range is less than desired.
  • the treating bath preferably comprises ammonium hydroxide as a neutralization agent for the concentrate and the treatment solution made from the concentrate. Ammonium hydroxide is necessary in order to adjust the pH of the liquid concentrate to an elevated pH so that the concentrate will not become unstable.
  • the inventors have also discovered that the build-up of aluminum in the treatment composition bath may increase the ability of the bath to produce excellent corrosion resistance as compared to a fresh bath.
  • the inventors have achieved 1,000 hours of salt spray resistance on panels that have been processed in old treatment baths.
  • a soluble aluminum salt may be added to the treatment composition of the present invention.
  • Soluble aluminum salts that are usable in the invention include aluminum ammonium chloride, aluminum ammonium sulfate, aluminum nitrate, aluminum potassium sulfate and aluminum sulfate. If used, the aluminum salt should generally be present in the bath at a concentration of between 5 and 500 parts per million (ppm) as aluminum, with a preferred concentration of between 10 and 200 ppm as aluminum.
  • parts to be treated with the composition of this invention are cleaned to remove soils and other surface contamination.
  • the parts are then deoxidized in an acid solution, which is capable of removing surface oxides, and then rinsed.
  • a suitable acid solution for wrought alloys is a 50% nitric acid solution, although other acid solutions may also be used.
  • the parts are then contacted with the zirconium tungstate composition of this invention by either immersion or by spraying for a period ranging from about 30 seconds to about 10 minutes.
  • the treatment composition is preferably maintained at temperatures ranging from about 55°F to about 180°F, most preferably from about 70°F to about 120°F.
  • the parts are then dried and/or baked, prior to painting or other processing.
  • Metal parts are first cleaned to remove surface contamination, by soaking the parts in an alkaline cleaning solution, at 170°F for 10-15 minutes.
  • the alkaline cleaning solution used is MacDermid TS 40A, at a concentration of 6 oz/gal, although other alkaline cleaning solutions may also be used.
  • the parts are rinsed for a period of about 2 minutes.
  • the parts are deoxidized in a 50% nitric acid solution at ambient temperature for a period of about 1 minute, and are then subjected to a second rinsing.
  • the parts are subjected to a conversion coating of the present invention for a period of 2 to 10 minutes at a temperature ranging from room temperature to about 125°F.
  • the parts are then rinsed for a final time and are dried and/or baked.
  • the panels treated with the composition of the instant invention provide much greater corrosion protection than similar panels coated with a chromate conversion coating at elevated temperatures.
  • Example 3 Panels treated with the zirconium and tungsten solution were tested side by side with panels treated with a chromate conversion coating conforming to MIL-C-81706 and MIL-C-5541.
  • bare aluminum panels were included in the test.
  • the treated (or bare aluminum) panels were sprayed with primer and/or paint or were powder coated.
  • the treated (or bare aluminum) panels were then subjected to a 2 mm cross-hatch/tape-pull test in accordance with ASTM D 3359-87 Method B, the standard test method for measuring adhesion with tape.
  • ASTM D 3359-87 Method B the standard test method for measuring adhesion with tape.
  • the bare aluminum panels resulted in consistent adhesion failures.
  • the zirconium tungstate coated panels provided adhesion promotion that equaled or exceeded that of the chromate coated panels.
  • the zirconium tungstate coated panels of the present invention were next tested side by side with panels treated with panels treated with the MIL-C-81706/MIL-C-5541 chromate and, for comparison purposes, bare aluminum panels after the panels had been heated or baked at elevated temperatures.
  • the treated (or bare aluminum) panels were heated to temperatures of 150°C, 200°C, 250°C, 300°C, and 350°C for a 20-minute time period prior to painting.
  • the treated (or bare aluminum) panels were spray painted with a primer, and then painted.

Abstract

L'invention concerne un procédé de formage d'une couche de conversion sur une surface métallique, et une composition pouvant être utilisée dans ce procédé. La composition est une solution aqueuse comprenant une source d'ions tungstates et un matériau soluble comprenant du zirconium. Le procédé permet d'obtenir un revêtement de conversion sur une surface qui peut alors être peinte ou traitée de toute autre façon. Les revêtements de conversion selon l'invention ne sont affectés que de façon minime par le chauffage et/ou la cuisson, contrairement aux revêtements de conversion au chromate de la technique antérieure.
EP03708992A 2002-03-14 2003-02-07 Composition et procede de traitement de surfaces metalliques Withdrawn EP1492902A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/099,769 US20030172998A1 (en) 2002-03-14 2002-03-14 Composition and process for the treatment of metal surfaces
US99769 2002-03-14
PCT/US2003/003610 WO2003078682A1 (fr) 2002-03-14 2003-02-07 Composition et procede de traitement de surfaces metalliques

Publications (2)

Publication Number Publication Date
EP1492902A1 true EP1492902A1 (fr) 2005-01-05
EP1492902A4 EP1492902A4 (fr) 2005-06-15

Family

ID=28039680

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03708992A Withdrawn EP1492902A4 (fr) 2002-03-14 2003-02-07 Composition et procede de traitement de surfaces metalliques

Country Status (7)

Country Link
US (1) US20030172998A1 (fr)
EP (1) EP1492902A4 (fr)
JP (1) JP2005520047A (fr)
CN (1) CN100378246C (fr)
AU (1) AU2003212949A1 (fr)
TW (1) TWI255863B (fr)
WO (1) WO2003078682A1 (fr)

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MX2009002697A (es) * 2006-09-19 2009-03-24 Valspar Sourcing Inc Recipientes para alimentos y bebidas y metodos de revestimiento.
JP2008174807A (ja) 2007-01-19 2008-07-31 Nippon Hyomen Kagaku Kk クロムを含まない金属表面処理液
US20090123656A1 (en) * 2007-11-13 2009-05-14 Ernest Long Composition and method for controlling galvanic corrosion in printed circuit boards
US20090242081A1 (en) * 2008-03-26 2009-10-01 Richard Bauer Aluminum Treatment Composition
US20100243108A1 (en) * 2009-03-31 2010-09-30 Ppg Industries Ohio, Inc. Method for treating and/or coating a substrate with non-chrome materials
US9347134B2 (en) 2010-06-04 2016-05-24 Prc-Desoto International, Inc. Corrosion resistant metallate compositions
CN102312233B (zh) * 2010-06-29 2013-10-30 株式会社神户制钢所 经表面处理的铝合金板及其制造方法
CN102529202B (zh) * 2010-10-18 2015-02-25 株式会社神户制钢所 铝合金板、使用其的接合体及汽车用部件
CN102586730A (zh) 2011-01-17 2012-07-18 鸿富锦精密工业（深圳）有限公司 镀膜件及其制备方法
TWI426153B (zh) * 2011-01-19 2014-02-11 Hon Hai Prec Ind Co Ltd 鍍膜件及其製備方法
US20140041764A1 (en) * 2012-08-07 2014-02-13 Roberto Zoboli Steel Pre-Paint Treatment Composition
JP6143431B2 (ja) * 2012-09-20 2017-06-07 株式会社神戸製鋼所 アルミニウム合金板、これを用いた接合体および自動車用部材
ITMI20122229A1 (it) * 2012-12-21 2014-06-22 Campagnolo Srl Componente di bicicletta comprendente un corpo in alluminio ed un corpo in materiale composito, e metodo di fabbricazione di tale componente
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
CN109317382B (zh) * 2018-11-22 2021-10-19 安徽安铝铝业有限公司 铝合金型材表面处理工艺
CN114836745A (zh) * 2022-03-21 2022-08-02 华南理工大学 一种铝合金中性锆钨转化液及铝合金表面的锆钨转化膜的制备方法

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US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
WO1993015154A1 (fr) * 1992-01-31 1993-08-05 Henkel Corporation Composition de revetement a auto-depot
US5919318A (en) * 1994-05-21 1999-07-06 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating using substituted monocarboxylic acids
WO2001048264A1 (fr) * 1999-12-27 2001-07-05 Henkel Corporation Composition et procede de traitement de surface metallique et article resultant
WO2001086016A2 (fr) * 2000-05-11 2001-11-15 Henkel Corporation Agent de traitement de surface metallique

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US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
WO1993015154A1 (fr) * 1992-01-31 1993-08-05 Henkel Corporation Composition de revetement a auto-depot
US5919318A (en) * 1994-05-21 1999-07-06 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating using substituted monocarboxylic acids
WO2001048264A1 (fr) * 1999-12-27 2001-07-05 Henkel Corporation Composition et procede de traitement de surface metallique et article resultant
WO2001086016A2 (fr) * 2000-05-11 2001-11-15 Henkel Corporation Agent de traitement de surface metallique

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Title
See also references of WO03078682A1 *

Also Published As

Publication number Publication date
EP1492902A4 (fr) 2005-06-15
WO2003078682A1 (fr) 2003-09-25
TWI255863B (en) 2006-06-01
CN100378246C (zh) 2008-04-02
US20030172998A1 (en) 2003-09-18
AU2003212949A1 (en) 2003-09-29
CN1643181A (zh) 2005-07-20
TW200303934A (en) 2003-09-16
JP2005520047A (ja) 2005-07-07

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