+

US20030172998A1 - Composition and process for the treatment of metal surfaces - Google Patents

Composition and process for the treatment of metal surfaces Download PDF

Info

Publication number
US20030172998A1
US20030172998A1 US10/099,769 US9976902A US2003172998A1 US 20030172998 A1 US20030172998 A1 US 20030172998A1 US 9976902 A US9976902 A US 9976902A US 2003172998 A1 US2003172998 A1 US 2003172998A1
Authority
US
United States
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.)
Abandoned
Application number
US10/099,769
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
Individual
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 Individual filed Critical Individual
Priority to US10/099,769 priority Critical patent/US20030172998A1/en
Assigned to MACDERMID, INCORPORATED reassignment MACDERMID, INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAUER, RICHARD, BERRY, ROBERT, GIRARD, JUSTIN, WOJCIK, GERALD
Priority to EP03708992A priority patent/EP1492902A4/en
Priority to AU2003212949A priority patent/AU2003212949A1/en
Priority to CNB038058278A priority patent/CN100378246C/en
Priority to PCT/US2003/003610 priority patent/WO2003078682A1/en
Priority to JP2003576672A priority patent/JP2005520047A/en
Priority to TW092102988A priority patent/TWI255863B/en
Publication of US20030172998A1 publication Critical patent/US20030172998A1/en
Abandoned 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 best 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. Pat. 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.
  • composition and process for the treatment of metal surfaces with a composition comprising:
  • the source of tungstate ions includes all tungstates but most specifically all ortho-tungstates, meta-tungstates and para-tungstates, epolytungstates, 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/l to about 10 g/l, preferably from about 0.1 g/l to about 1.5 g/l and is most preferably about 1.0 g/l.
  • 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/l to about 2.0 g/l, most preferably from about 0.05 g/l to about 0.5 g/l.
  • 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.
  • Optional ingredients may be added to the treatment composition, including surfactants, accelerators, dyes, organic polymers, buffering agents and pH adjusting agents.
  • 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.
  • Table 1 provides several examples of working bath concentrations of solutions that are usable in the present invention.
  • TABLE 1 Suitable Bath Concentrations of Solutions of the Invention Component Formulation A Formulation B Formulation C Tungstic acid, 3.0 g/l 2.5 g/l 3.5 g/l hexaamonium salt Dihydrogen 3.0 g/l 2.5 g/l 3.5 g/l hexafluorozirconate Water Diluted to Diluted to Diluted to 1 liter 1 liter 1 liter
  • 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.
  • 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 ti prior to painting.
  • the treated (or bare aluminum) panels were spray painted with a primer, and then painted.

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)

Abstract

A method of forming a conversion layer on a metallic surface and a composition usable in the method are provided. The composition is an aqueous solution comprising a source of tungstate ions and a soluble material comprising zirconium. The method provides a conversion coating on a surface that can then be painted or otherwise treated. The conversion coatings of the present invention are minimally affected by heating and/or baking, unlike chromate conversion coatings of the prior art.

Description

    FIELD OF THE INVENTION
  • 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. In addition, 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. [0001]
    • BACKGROUND OF THE INVENTION
  • Various 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. [0002]
  • 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. [0003]
  • 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 best 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. Pat. 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. [0004]
  • It is therefore an object of this invention to provide a composition and process which can produce a conversion coating on metallic surfaces, which coating will provide excellent corrosion resistance and adhesion to siccative organic coatings but is free of chromium content. In addition, it is an object of this invention to provide a conversion coating on metallic surfaces that is minimally affected by subsequent heating and/or baking. It is a further object of this invention to provide a composition and method for treating metal surfaces, especially the surfaces of zinc, zinc alloys, aluminum and aluminum alloys. [0005]
    • SUMMARY OF THE INVENTION
  • These and other objects of the present invention can be achieved by treating metal surfaces with a composition comprising: [0006]
  • (1) a source of tungstate ions; and [0007]
  • (2) a soluble material comprising zirconium; and thereafter drying or baking the metal surfaces. [0008]
  • 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. Preferably the treatment composition is free of chromium ions. [0009]
    • DETAILED DESCRIPTION OF THE INVENTION
  • The inventors herein propose a composition and process for the treatment of metal surfaces with a composition comprising: [0010]
  • (1) a source of tungstate ions; and [0011]
  • (2) a soluble material comprising zirconium; and thereafter drying or baking the metal surfaces. [0012]
  • The source of tungstate ions includes all tungstates but most specifically all ortho-tungstates, meta-tungstates and para-tungstates, epolytungstates, 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. The concentration of tungstate (measured as tungsten) in the composition should range from about 0.01 g/l to about 10 g/l, preferably from about 0.1 g/l to about 1.5 g/l and is most preferably about 1.0 g/l. [0013]
  • The composition also includes a soluble compound containing zirconium and preferably, fluoride. Examples of 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/l to about 2.0 g/l, most preferably from about 0.05 g/l to about 0.5 g/l. [0014]
  • 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. [0015]
  • 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. [0016]
  • 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. [0017]
  • To that end, 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. [0018]
  • Typically, parts to be treated with the composition of this invention are cleaned to remove soils and other surface contamination. Preferably 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. [0019]
  • Optional ingredients may be added to the treatment composition, including surfactants, accelerators, dyes, organic polymers, buffering agents and pH adjusting agents. [0020]
  • This invention is further described by the following examples, which should be taken as illustrative only and not limiting in any regard.[0021]
    • EXAMPLE 1
  • 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. In this example, 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. Next, 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. Finally, the parts may be painted or otherwise processed. Table 1 provides several examples of working bath concentrations of solutions that are usable in the present invention. [0022]
    TABLE 1
    Suitable Bath Concentrations of Solutions of the Invention
    Component Formulation A Formulation B Formulation C
    Tungstic acid, 3.0 g/l 2.5 g/l 3.5 g/l
    hexaamonium salt
    Dihydrogen 3.0 g/l 2.5 g/l 3.5 g/l
    hexafluorozirconate
    Water Diluted to Diluted to Diluted to
    1 liter 1 liter 1 liter
    • EXAMPLE 2
  • The effect of heat treating on neutral salt spray test results for panels treated in a five minute immersion of the compositions of example 1 was investigated by baking sample panels at various temperatures for 10 minute each and comparing the results to that of panels coated with a chromate conversion coating. The results are shown in [0023]
    TABLE 2
    Comparison of Effect of Heat-Treating on Neutral Salt
    Spray Results for Tungstate Zirconium Coatings and
    Chromate Coatings
    Temperature Hours to Failure
    ° C. Tungstate-Zirconium Coating Chromate Coating
    150 168 hours <24 hours
    200 144 hours <24 hours
    250 144 hours <24 hours
    300 312 hours <24 hours
    350 312 hours <24 hours
  • As is readily seen, 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. [0024]
    • 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. For comparison purposes, 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. As expected, the bare aluminum panels resulted in consistent adhesion failures. On the other hand, the zirconium tungstate coated panels provided adhesion promotion that equaled or exceeded that of the chromate coated panels. [0025]
    • EXAMPLE 4
  • 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. [0026]
  • In this example, 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 ti prior to painting. The treated (or bare aluminum) panels were spray painted with a primer, and then painted. [0027]
  • The panels were then subjected to a 2 mm cross-hatch/tape-pull test in accordance with ASTM D 3359-87 Method B. The results demonstrated that the adhesion promotion of the tungstate zirconium treated panels far exceeded that of the bare aluminum panels or the chromate coated panels. [0028]

Claims (43)

What is claimed is:
1. A method of forming a conversion layer on a metallic surface comprising the steps of:
treating the metallic surface with an aqueous treating solution comprising:
(a) a source of tungstate ions; and
(b) a soluble material comprising zirconium; and
thereafter drying and/or baking the treated metal surface.
2. A method according to claim 1, wherein the aqueous treating solution further comprises ammonium hydroxide.
3. A method according to claim 1, wherein the source of tungstate ions is selected from the group consisting of ortho-tungstates, meta-tungstates and para-tungstates, polytungstates, heteropolytungstates, isopolytungstates, peroxytungstates, and combinations thereof.
4. A method according to claim 3, wherein the source of tungstate ions is meta-tunstate or para-tungstate.
5. A method according to claim 3, wherein the source of tungstate ions is selected from the group consisting of sodium, potassium, lithium, calcium, cerium, barium, magnesium, strontium, hydrogen and ammonium tungstate salts.
6. A method according to claim 3, wherein the source of tungstate ions is tangstic acid, hexaamonium salt.
7. A method according to claim 1, wherein the concentration of tungstate ions, measured as tungsten, in treating solution is about 0.01 g/l to about 10.0 g/l.
8. A method according to claim 7, wherein the concentration of tungstate ions, measured as tungsten, in the treating solution is about 0.1 g/l to about 1.5 g/l.
9. A method according to claim 8, wherein the concentration of tungstate ions, measured as tungsten, in the treating solution is 1.0 g/l.
10. A method according to claim 1, wherein the soluble material comprising zirconium is selected from the group consisting of zirconium ammonium fluoride, dihydrogen hexafluorozirconate, potassium hexafluorozirconate, zirconium sulfate, zirconium carbonate, zirconium nitrate, and zirconium phosphate.
11. A method according to claim 10, wherein the soluble material comprising zirconium is dihydrogen hexafluorozirconate.
12. A method according to claim 1, wherein the concentration of the soluble material comprising zirconium in the treating solution is about 0.01 g/l to about 2.0 g/l.
13. A method according to claim 12, wherein the concentration of the soluble material comprising zirconium in the treating solution is about 0.05 g/l to about 0.5 g/l.
14. A method according to claim 1, wherein the aqueous treating solution further comprises a soluble aluminum salt.
15. A method according to claim 14, wherein the concentration of the soluble aluminum salt is between 5 and 500 parts per million as aluminum.
16. A method according to claim 1, wherein the temperature of the treating solution is within the range of about 55° F. to about 180° F.
17. A method according to claim 16, wherein the temperature of the treating solution is about 70° F. to about 120° F.
18. A method according to claim 1, wherein the pH of the treating solution is maintained from about 2.8 to about 7.0.
19. A method according to claim 1, wherein the parts are cleaned prior to treating the metallic surface with the treating solution.
20. A method according to claim 19, wherein the metallic surface is deoxidized after cleaning and prior to treating with the treating solution.
21. A method according to claim 1, wherein the treating solution is free of chromium.
22. A method according to claim 1, wherein the treating solution is applied by immersion or by spraying.
23. A method according to claim 1, wherein the treating solution further comprises at least one of a surfactant, an accelerator, a dye, an organic polymer, a buffering agent, and a pH adjusting agent.
24. An aqueous conversion coating composition comprising a source of tungstate ions and a soluble material comprising zirconium.
25. A composition according to claim 24, wherein the aqueous treating solution further comprises ammonium hydroxide.
26. A composition according to claim 24, wherein the source of tungstate ions is selected from the group consisting of ortho-tungstates, meta-tungstates and para-tungstates, polytungstates, heteropolytungstates, isopolytungstates, peroxytungstates, and combinations thereof.
27. A composition according to claim 26, wherein the source of tungstate ions is meta-tungstate or para-tungstate.
28. A composition according to claim 26, wherein the source of tungstate ions is selected from the group consisting of sodium, potassium, lithium, calcium, cerium, barium, magnesium, strontium, hydrogen and ammonium tungstate salts.
29. A composition according to claim 26, wherein the source of tungstate ions is tungstic acid, hexaamonium salt.
30. A composition according to claim 24, wherein the concentration of tungstate ions, measured as tungsten, in treating solution is about 0.01 g/l to about 10.0 g/l.
31. A composition according to claim 30, wherein the concentration of tungstate ions, measured as tungsten, in the treating solution is about 0.1 g/l to about 1.5 g/l.
32. A composition according to claim 31, wherein the concentration of tungstate ions, measured as tungsten, in the treating solution is 1.0 g/l.
33. A composition according to claim 24, wherein the soluble material comprising zirconium is selected from the group consisting of zirconium ammonium fluoride, dihydrogen hexafluorozirconate, potassium hexafluorozirconate, zirconium sulfate, zirconium carbonate, zirconium nitrate, and zirconium phosphate.
34. A composition according to claim 33, wherein the soluble material comprising zirconium is dihydrogen hexafluorozirconate.
35. A composition according to claim 24, wherein the concentration of the soluble material comprising zirconium in the treating solution is about 0.01 g/l to about 2.0 g/l.
36. A composition according to claim 35, wherein the concentration of the soluble material comprising zirconium in the treating solution is about 0.05 g/l to about 0.5 g/l.
37. A composition according to claim 24, wherein the aqueous treating solution further comprises a soluble aluminum salt.
38. A composition according to claim 37, wherein the concentration of the soluble aluminum salt is between 5 and 500 parts per million as aluminum.
39. A composition according to claim 24, wherein the temperature of the treating solution is within the range of about 55° F. to about 180° F.
40. A composition according to claim 39, wherein the temperature of the treating solution is about 70° F. to about 120° F.
41. A composition according to claim 24, wherein the pH of the treating solution is maintained from about 2.8 to about 7.0.
42. A composition according to claim 24, wherein the treating solution is free of chromium.
43. A composition according to claim 24, wherein the treating solution further comprises at least one of a surfactant, an accelerator, a dye, an organic polymer, a buffering agent, and a pH adjusting agent.
US10/099,769 2002-03-14 2002-03-14 Composition and process for the treatment of metal surfaces Abandoned US20030172998A1 (en)

Priority Applications (7)

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
EP03708992A EP1492902A4 (en) 2002-03-14 2003-02-07 Composition and process for the treatment of metal surfaces
AU2003212949A AU2003212949A1 (en) 2002-03-14 2003-02-07 Composition and process for the treatment of metal surfaces
CNB038058278A CN100378246C (en) 2002-03-14 2003-02-07 Composition and process for the treatment of metal surfaces
PCT/US2003/003610 WO2003078682A1 (en) 2002-03-14 2003-02-07 Composition and process for the treatment of metal surfaces
JP2003576672A JP2005520047A (en) 2002-03-14 2003-02-07 Aqueous surface treating agent and film forming method for metal surface treatment
TW092102988A TWI255863B (en) 2002-03-14 2003-02-13 Composition and process for the treatment of metal surfaces

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
US20030172998A1 true US20030172998A1 (en) 2003-09-18

Family

ID=28039680

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/099,769 Abandoned US20030172998A1 (en) 2002-03-14 2002-03-14 Composition and process for the treatment of metal surfaces

Country Status (7)

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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090242081A1 (en) * 2008-03-26 2009-10-01 Richard Bauer Aluminum Treatment Composition
US20100243506A1 (en) * 2006-09-19 2010-09-30 Valspar Sourcing, Inc. Food and Beverage Containers and Methods of Coating
US20100243108A1 (en) * 2009-03-31 2010-09-30 Ppg Industries Ohio, Inc. Method for treating and/or coating a substrate with non-chrome materials
WO2014025484A1 (en) * 2012-08-07 2014-02-13 Macdermid Acumen, Inc. Steel-pre-paint treatment composition
US9347134B2 (en) 2010-06-04 2016-05-24 Prc-Desoto International, Inc. Corrosion resistant metallate compositions
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
CN114836745A (en) * 2022-03-21 2022-08-02 华南理工大学 Aluminum alloy neutral zirconium-tungsten conversion solution and preparation method of zirconium-tungsten conversion film on surface of aluminum alloy

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008174807A (en) 2007-01-19 2008-07-31 Nippon Hyomen Kagaku Kk Chromium-free metal surface treatment liquid
US20090123656A1 (en) * 2007-11-13 2009-05-14 Ernest Long Composition and method for controlling galvanic corrosion in printed circuit boards
CN102312233B (en) * 2010-06-29 2013-10-30 株式会社神户制钢所 Aluminum alloy plate after surface treatment and manufacturing method thereof
CN102529202B (en) * 2010-10-18 2015-02-25 株式会社神户制钢所 Aluminium alloy plate, bonded body using the same and vehicular member
CN102586730A (en) 2011-01-17 2012-07-18 鸿富锦精密工业（深圳）有限公司 Film-coated part and preparation method thereof
TWI426153B (en) * 2011-01-19 2014-02-11 Hon Hai Prec Ind Co Ltd Coated article and method for making the same
JP6143431B2 (en) * 2012-09-20 2017-06-07 株式会社神戸製鋼所 Aluminum alloy plate, joined body and automobile member using the same
ITMI20122229A1 (en) * 2012-12-21 2014-06-22 Campagnolo Srl BICYCLE COMPONENT INCLUDING AN ALUMINUM BODY AND A COMPOSITE BODY, AND METHOD OF MANUFACTURING SUCH A COMPONENT
CN109317382B (en) * 2018-11-22 2021-10-19 安徽安铝铝业有限公司 Surface treatment process for aluminum alloy section

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963568A (en) * 1973-05-30 1976-06-15 Kansai Paint Company, Ltd. Process for coating aluminum or aluminum alloy
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
US5902767A (en) * 1993-08-03 1999-05-11 Mobil Oil Corporation Catalyst having an acidic solid oxide component and a group IB metal or metal oxide component
US6419731B2 (en) * 2000-04-20 2002-07-16 Nippon Paint Co., Ltd. Nonchromate rust preventive agent for aluminum, method of rust prevention and rust-preventive aluminum products

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2905535A1 (en) * 1979-02-14 1980-09-04 Metallgesellschaft Ag METHOD FOR SURFACE TREATMENT OF METALS
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
JPH05214266A (en) * 1992-01-31 1993-08-24 Nippon Parkerizing Co Ltd Autodeposition aqueous coating composition
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
DE4417965A1 (en) * 1994-05-21 1995-11-23 Henkel Kgaa Iron phosphating using substituted monocarboxylic acids
US6193815B1 (en) * 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals
US6027580A (en) * 1995-12-13 2000-02-22 Henkel Corporation Hydrophilicizing post-treatment over chromate conversion coating
US6083309A (en) * 1996-10-09 2000-07-04 Natural Coating Systems, Llc Group IV-A protective films for solid surfaces
JP3860697B2 (en) * 1999-12-27 2006-12-20 日本パーカライジング株式会社 Metal surface treatment agent, surface treatment method of metal material, and surface treatment metal material
WO2001086016A2 (en) * 2000-05-11 2001-11-15 Henkel Corporation Metal surface treatment agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963568A (en) * 1973-05-30 1976-06-15 Kansai Paint Company, Ltd. Process for coating aluminum or aluminum alloy
US5902767A (en) * 1993-08-03 1999-05-11 Mobil Oil Corporation Catalyst having an acidic solid oxide component and a group IB metal or metal oxide component
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
US6419731B2 (en) * 2000-04-20 2002-07-16 Nippon Paint Co., Ltd. Nonchromate rust preventive agent for aluminum, method of rust prevention and rust-preventive aluminum products

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100243506A1 (en) * 2006-09-19 2010-09-30 Valspar Sourcing, Inc. Food and Beverage Containers and Methods of Coating
US8168276B2 (en) 2006-09-19 2012-05-01 Valspar Sourcing, Inc. Food and beverage containers and methods of coating
US20090242081A1 (en) * 2008-03-26 2009-10-01 Richard Bauer Aluminum Treatment Composition
WO2009120431A1 (en) * 2008-03-26 2009-10-01 Macdermid, Incorporated Aluminum treatment composition
CN102144042A (en) * 2008-03-26 2011-08-03 麦克德米德股份有限公司 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
WO2014025484A1 (en) * 2012-08-07 2014-02-13 Macdermid Acumen, Inc. Steel-pre-paint treatment composition
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions
US12104272B2 (en) 2015-10-12 2024-10-01 Prc-Desoto International, Inc. Treated substrates
CN114836745A (en) * 2022-03-21 2022-08-02 华南理工大学 Aluminum alloy neutral zirconium-tungsten conversion solution and preparation method of zirconium-tungsten conversion film on surface of aluminum alloy

Also Published As

Publication number Publication date
WO2003078682A1 (en) 2003-09-25
TW200303934A (en) 2003-09-16
JP2005520047A (en) 2005-07-07
EP1492902A1 (en) 2005-01-05
AU2003212949A1 (en) 2003-09-29
TWI255863B (en) 2006-06-01
CN100378246C (en) 2008-04-02
EP1492902A4 (en) 2005-06-15
CN1643181A (en) 2005-07-20

Similar Documents

Publication Publication Date Title
EP1404894B1 (en) Corrosion resistant coatings for aluminum and aluminum alloys
US20030172998A1 (en) Composition and process for the treatment of metal surfaces
EP0896641B1 (en) Zinc phosphate tungsten-containing coating compositions using accelerators
EP1433876B1 (en) Chemical conversion coating agent and surface-treated metal
EP1433875B1 (en) Chemical conversion coating agent and surface-treated metal
JP4427332B2 (en) Treatment liquid for surface treatment of aluminum or magnesium metal and surface treatment method
US3895970A (en) Sealing rinse for phosphate coatings of metal
EP2044239B1 (en) Method for making a corrosion resistant coating on metal surfaces using an improved trivalent chromium-containing composition
JP2680618B2 (en) Metal phosphate treatment method
JP6281990B2 (en) Improved trivalent chromium-containing composition for aluminum and aluminum alloys
CA2186025A1 (en) Composition and process for treating the surface of aluminiferous metals
JP3333611B2 (en) Hexavalent chromium-free chemical conversion surface treatment agent for aluminum and aluminum alloys
US4306917A (en) Conversion coating solutions for treating metallic surfaces
US6755918B2 (en) Method for treating magnesium alloy by chemical conversion
KR20040058040A (en) Chemical conversion coating agent and surface-treated metal
JPS63157879A (en) Method forming phosphate film to surface of metal
CA2190991A1 (en) Iron phosphatisation using substituted monocarboxilic acids
US3720547A (en) Permanganate final rinse for metal coatings
US4220486A (en) Conversion coating solution for treating metallic surfaces
JPH04128384A (en) Treatment of metallic surface, treating bath and treating agent
CA1197674A (en) Composition and process for the treatment of phosphatized metal surfaces
JP3286583B2 (en) Chemical conversion treatment composition for magnesium-containing metal, surface treatment method and surface treatment product
EP3137652B1 (en) Non chromate colored conversion coating for aluminum
US20100032060A1 (en) Process for preparing chromium conversion coatings for magnesium alloys
US3615890A (en) Method of applying phosphate conversion coating by reverse roller technique

Legal Events

Date Code Title Description
AS Assignment

Owner name: MACDERMID, INCORPORATED, CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WOJCIK, GERALD;GIRARD, JUSTIN;BERRY, ROBERT;AND OTHERS;REEL/FRAME:012727/0021

Effective date: 20020301

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载