US20160160355A1 - Pretreatment of metal surfaces with a calcium-containing aqueous agent - Google Patents

Pretreatment of metal surfaces with a calcium-containing aqueous agent Download PDF

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US20160160355A1
US20160160355A1 US14/962,375 US201514962375A US2016160355A1 US 20160160355 A1 US20160160355 A1 US 20160160355A1 US 201514962375 A US201514962375 A US 201514962375A US 2016160355 A1 US2016160355 A1 US 2016160355A1
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calcium
metal surface
pretreatment
coating
ppm
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Liangliang LI
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Novelis Inc Canada
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    • 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
    • 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention relates to the fields of material science, material chemistry, surface chemistry, metal manufacturing, aluminum alloys, aluminum manufacturing and related fields.
  • the present invention provides novel compositions and processes for surface pretreatment of metals, for example, aluminum alloys, in order to improve their corrosion resistance.
  • the compositions, processes and uses described herein can be employed in various industries to produce articles or materials comprising metal surfaces, such as aluminum alloy surfaces, including, but not limited to, motor vehicle parts or panels, construction or architectural parts or panels, electronic housings, composite and bonded materials and articles, and other products and parts comprising metal surfaces.
  • Filiform corrosion typically refers to a type of corrosion occurring at the interface between metal surfaces and thin films or coatings, including organic and inorganic films and coatings. Filiform corrosion has an appearance of randomly or semi-randomly distributed filaments emanating from one or more sources (“heads”) under bulging and/or cracking coating. These filaments are channels or crevices comprised of corrosion products, such as metal salts.
  • Filiform corrosion is initiated by atmospheric water and oxygen supplied to the initial site (which forms a “head”) by osmosis and propagates under the film forming the filaments, which can be referred to as “tails.”
  • the damage to a metal surface caused by filiform corrosion may not be extensive, it detrimentally affects the coating, including its appearance, functional properties and bond with the surface.
  • filiform corrosion of a painted or aluminum alloy surface may lead to a surface riddled with channels filled with white aluminum hydroxide precipitate.
  • filiform corrosion may lead to interfacial failure of a metal/adhesive or metal/bonding compound interface, which, in turn, may lead to a structural failure of an article containing such an interface.
  • Filiform corrosion is associated with exposure to high humidity and also with the occurrence of various ions on the metal surface.
  • a number of approaches have been employed to reduce filiform corrosion at a metal surface under a film or coating.
  • One of these approaches is the use of the so-called pretreatment coatings or primers.
  • Pretreatment coatings provide a stable metal oxide surface that resists filiform corrosion and promotes adhesion of the film or coating to the aluminum alloy surface.
  • One class of pretreatment coatings are pretreatment coatings containing combinations of metal ions, such as Ti/Zr pretreatment coatings, which tie up oxygen at the metal surface in stable oxides that function as an oxygen diffusion barrier.
  • Ti/Zr pretreatment involves the hydrolysis of hexafluorotitanate and hexafluorozirconate to form Ti/Zr oxides, which produces free fluoride ions as a byproduct.
  • oxide layer provides a degree of protection from filiform corrosion and improves the bonding between the aluminum alloy surface and the coating, it is believed that the byproduct-free (non-complexed with Ti, Zr or other metal) fluoride ions lead to filiform corrosion propagation.
  • the fluoride ions can easily incorporate into the Al oxide layers between the pretreatment coating and the alloy substrate and replace the oxygen in the Al oxide matrix, which eventually causes the dissolution of Al and leads to the corrosion of the alloy surface.
  • the pretreatment coating is typically rinsed after application with deionized water.
  • This method requires large amounts of deionized water to lower fluoride ion levels.
  • Production of the deionized water and treatment of the spent rinse solution to remove dissolved compounds prior to discharge both add to the costs of the above process and may create significant amounts of hazardous waste.
  • improved bonding between aluminum alloy surfaces and various coatings would be beneficial for various industries and fields. Accordingly, improved processes and compositions for pretreatment of aluminum alloy surfaces are desired.
  • the present invention provides solutions to problems associated with filiform corrosion of metal surfaces, such as aluminum alloy surfaces, surfaces covered with organic or inorganic films or coatings, and, more generally, with the adhesion of coatings or films (for example, paint or adhesive adhesion).
  • the present invention may be used to improve the adhesion between metal surfaces, such as aluminum alloy surfaces, and the films or coatings. It may also be used to improve adhesion between metal surfaces and other metal or non-metal surfaces bonded or glued together with bonding compounds or adhesives.
  • the present invention addresses these problems by providing anti-corrosion pretreatment on a metal surface, such as an aluminum alloy surface, in which a pretreatment coating containing metal and fluoride ions, such as a Ti/Zr pretreatment coating, after its application to the metal surface, such as the aluminum alloy surface, is contacted with an aqueous agent containing calcium ions.
  • a pretreatment coating containing metal and fluoride ions such as a Ti/Zr pretreatment coating
  • the improved processes described herein can possess various advantages. For example, they can be less costly than conventional pretreatments, use less water, and produce less hazardous waste than the conventional pretreatments, such as those employing deionized water rinses.
  • Some embodiments of the present invention are processes for anti-corrosion pretreatment of aluminum alloys that utilize calcium-containing aqueous agents. Compositions of matter related to calcium-containing aqueous agents as well as uses of a calcium-containing aqueous agent in the process of anticorrosion pretreatment are also included within the embodiments of the present invention.
  • Some other embodiments of the present invention are processes of producing or manufacturing articles that comprise coated aluminum alloy surfaces treated by the improved surface pretreatment.
  • the present invention also encompasses articles manufactured according to the above processes, including materials containing aluminum alloy surfaces.
  • One exemplary embodiment of the present invention is a method for treating a metal surface coated with a pretreatment coating comprising fluoride ions.
  • the method includes a step of contacting the metal surface one or more times with an aqueous agent comprising at least 7 ppm calcium ions.
  • Another exemplary embodiment of the present invention is a method for pretreatment of a metal surface, which includes the steps of: coating the metal surface with a pretreatment coating; and, contacting the metal surface coated with the pretreatment coating with an aqueous agent comprising at least 7 ppm calcium ions.
  • One more exemplary embodiment of the present invention is a method of improving corrosion resistance of a metal surface, which includes the steps of coating the metal surface with a pretreatment coating and contacting the metal surface coated with the pretreatment coating with an aqueous agent comprising at least 7 ppm calcium ions.
  • the metal surface can be an aluminum alloy surface, for example, a surface of a 2xxx, 3xxx, 5xxx, 6xxx or 7xxx aluminum alloy.
  • the pretreatment coating can be a Ti/Zr or Zr/Cr coating.
  • the pretreatment coating can be hexafluorotitanate, hexafluorozirconate or chromium sulfate coating.
  • the aqueous agent can be a solution of a calcium salt, for example, a calcium carbonate, a calcium phosphate, a calcium nitrate or a calcium sulfate.
  • the aqueous agent can contain calcium (Ca 2+ ) ions in an amount of at least about 7 ppm (about 7 ppm or above), for example, at least about 7.5 ppm, at least about 8.0 ppm, at least about 8.5 ppm, at least about 9 ppm, or at least about 9.5 ppm.
  • the aqueous agent can contain calcium ions in an amount of from about 7.5 ppm to about 500 ppm, (e.g., from about 8 ppm to about 450 ppm, from about 8.5 ppm to about 400 ppm, from about 9.0 ppm to about 350 ppm, from about 9.5 ppm to about 300 ppm, from about 10 ppm to about 250 ppm, from about 20 ppm to about 200 ppm, from about 50 ppm to about 100 ppm, or from about 10 ppm to about 50 ppm).
  • the aqueous agent can contain calcium ions in a range of from about 7.5-9.8 ppm.
  • the aqueous agent can contain calcium ions at about 7.5 ppm. In some other embodiments, the aqueous agent can contain calcium ions at saturation. In some exemplary embodiments, the aqueous agent is a saturated solution of calcium carbonate.
  • the step of contacting the metal surface with the aqueous agent in the processes according to the embodiments of the present invention can include one or more of immersing the metal surface in the agent, rinsing the metal surface with the agent, rolling the agent onto the metal surface, or spraying the metal surface with the agent.
  • the fluoride ion content can be reduced in the pretreatment coating, and/or calcium ion content can be increased in the pretreatment coating.
  • the metal surface is rinsed with the aqueous agent in the contacting step, and the weight of the pretreatment coating after the contacting step is greater in comparison to a metal surface coated with the pretreatment coating rinsed with deionized water.
  • the embodiments of the present invention can include, after the contacting step, a step of applying to the metal surface one or more of a paint, a lacquer, an adhesive, a glue or a bonding compound.
  • the embodiments of the present invention include articles of manufacture comprising a metal surface treated by the methods according to the embodiments of the present invention.
  • Some examples of such articles of manufacture are an aluminum alloy sheet, a motor vehicle panel, an automotive panel, an electronics panel, an architectural panel or a material comprising an aluminum alloy surface.
  • Processes of manufacturing the articles of manufacture which include the methods according to the embodiments of the present invention are also encompassed by the embodiments of the present invention.
  • Other embodiments, objects and advantages of the present invention will be apparent from the following detailed description of embodiments of the invention.
  • FIG. 1A shows a line plot illustrating depth profiling x-ray photoelectron spectroscopy (XPS) data for Ti after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • XPS x-ray photoelectron spectroscopy
  • FIG. 1B shows a line plot illustrating depth profiling x-ray photoelectron spectroscopy (XPS) data for Zr after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • XPS x-ray photoelectron spectroscopy
  • FIG. 2A shows a line plot illustrating depth profiling XPS data for Si after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • FIG. 2B shows a line plot illustrating depth profiling XPS data for O after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • FIG. 3A shows a line plot illustrating depth profiling XPS data for Ca after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • FIG. 3B shows a line plot illustrating depth profiling XPS data for F after rinsing pretreated aluminum alloy samples with deionized water, tap water and calcium carbonate solution.
  • pretreatment compositions and improved methods of pretreating aluminum alloy surfaces which also can be applied to the pretreatment of other metal surfaces.
  • the improved pretreatment lowers the concentration of free fluoride ions at the surface of a metal, such as an aluminum alloy surface, coated with the pretreatment coating, as well as in the pretreatment coating.
  • the improved pretreatment reduces and/or inhibits propagation of filiform corrosion on a metal surface.
  • the improved anticorrosion pretreatment generally improves the bond between a film or coating (for example, paint or adhesive) and the metal surface.
  • the improved anticorrosion pretreatment leads to improved bond durability when adhesive compounds are used to bond metal surfaces with other metal or non-metal surfaces. In some other exemplary embodiments, the improved anticorrosion pretreatment leads to more durable and stable bonds between a metal surface and a coating applied on the metal surface, such as a coating or paint.
  • the embodiments of the present invention include methods for treating metal surfaces, such as aluminum alloy surfaces. The methods are performed with the goal of inhibiting corrosion, such as filiform corrosion, of the metal surfaces, such as aluminum alloy surfaces, covered with an organic or inorganic coating or film, including protective and/or decorative coatings, such as lacquers or paints, adhesive or bonding compounds, such as glues or resins, or other types of films, coatings or compounds.
  • the methods of the present invention can therefore be referred to as anticorrosion pretreatment or methods to improve corrosion resistance or other related terms.
  • the methods according to some embodiments of the present invention can also be described as surface pretreatment methods, methods of treating aluminum alloy surfaces, methods of treating metal surfaces or other related terms.
  • the methods of the invention comprise one or more steps of contacting a metal surface, such as an aluminum alloy surface, which has been treated by a pretreatment agent comprising metal ions and fluoride ions, such as Zr, Ti, Cr, Ce, or V-based agents, with an aqueous agent comprising calcium ions (Ca 2+ ).
  • aqueous agent used in the methods of the present invention may contain at least 7 ppm Ca 2+ ions in an aqueous solution, and can be referred to as a calcium-containing agent.
  • the exposure of the pretreatment coating layer to the calcium-containing agent leads to formation of ionic bonds between calcium ions originating in the calcium-containing agent and free fluoride ions (F) found in the pretreatment coating layer.
  • fluoride ions leach out to the surface of the pretreatment coating, while calcium ions from the agent migrate into the pretreatment coating layer, sequestering fluoride ions remaining in the layer in ionic complexes, such as CaF 2 complexes, which are poorly soluble.
  • the amount of free fluoride ions found in the pretreatment coating layer is thereby reduced, which alleviates filiform corrosion propagation under the film coating applied onto the metal surface. Additional phenomena may be involved, which also inhibit filiform corrosion.
  • the presence of calcium ions at the metal surface may increase the pH at the surface. Higher pH, particularly in the alkaline range, inhibits propagation of filiform corrosion.
  • the phenomenon of filiform corrosion described above is intended to aid in the description and the understanding of the embodiments of the present invention.
  • the pretreatment processes according the embodiments of the present invention may alleviate filiform corrosion
  • the advantages of using the methods of the present invention are not limited to reducing, inhibiting, or alleviating filiform corrosion or its propagation.
  • a contact with a calcium-containing agent may increase the weight of the pretreatment coat on a metal surface, improving bond durability with the final coating.
  • the pretreatment processes according to the embodiments of the present invention improve durability of the coatings applied onto metal surfaces and/or improve durability between the coating and the metal surface.
  • the pretreatment processes according to the embodiments of the present invention also improve the stability of the interface between a metal surface and an organic or inorganic film or coating applied onto it and/or improve the bond between metal surfaces and other metal or non-metal components bonded to such surfaces with bonding compounds or adhesives, which leads to reduced failure of the above interfaces. Furthermore, the pretreatment processes according to the embodiments of the present invention improve adhesion between a film or coating and a metal surface, and reduce the possibility of adhesion failure between metal surfaces and other metal or non-metal components bonded to them with bonding or adhesive compounds metal or non-metal surfaces.
  • the metal surfaces suitable for pretreatment according to the embodiments of the present invention include surfaces of various alloyed and non-alloyed metals, for example, iron, magnesium, zinc, copper, brass and aluminum and their alloys.
  • the aluminum alloy surfaces suitable for pretreatment according to the embodiments of the present invention include surfaces comprised of aluminum alloyed with various elements, such as Fe, Mn, Si, Mg, Cu, etc. as well as surfaces comprised of substantially pure aluminum.
  • the term “aluminum alloy surface” is not intended to be limited by the type of an aluminum, alloyed or unalloyed.
  • aluminum alloys suitable for the pretreatment according to the embodiments of the present invention are 2xxx, 3xxx, 5xxx, 6xxx or 7xxx aluminum alloys (according to Aluminum Association (AA) Designation).
  • the term “surface” as used herein generally means an outer part of a quantity of a metal, such as an aluminum alloy. In some cases, a surface may be an outer part when subjected to the pretreatment, but later may be on the inside of an object or a material.
  • a multilayer composite comprising one or more metal layers may contain, on the inside, surfaces treated according to the processes of the present invention and subsequently bonded with other metal or non-metal surfaces.
  • the methods according to some embodiments of the present invention involve a metal surface, such as an aluminum alloy surface, that has been subjected to pretreatment coating (“pretreated”) with a pretreatment coating or agent comprising metal ions and fluoride ions.
  • pretreatment coatings include Ti/Zr and Zr/Cr coatings.
  • the pretreatment coatings are hexafluorotitanate, hexafluorozirconate and chromium sulfate coatings, conversion coatings based on chromium (chromium sulfate or chromate—Cr(VI)—e.g., K 2 CrO 4 ), cerium (cerium chloride/hydroxide, cerium nitrate) coatings, vanadate (vanadate sulfate) coatings, or manganese (for example, manganese phosphate) coatings.
  • chromium chromium sulfate or chromate—Cr(VI)—e.g., K 2 CrO 4
  • cerium cerium chloride/hydroxide, cerium nitrate
  • vanadate vanadate sulfate
  • manganese for example, manganese phosphate
  • Pretreatment coatings are applied to aluminum alloy surfaces using appropriate processes, such as etching, pretreating, rinsing, and curing.
  • a pretreatment coatings may be characterized by the content of constituent elements, such as Ti, Zr, etc.
  • Pretreatment coating forms a pretreatment film upon application, but the terms “coating” and “film” can be used interchangeably in this context.
  • a pretreatment coating can be characterized by a thickness of the film formed by the pretreatment coating, for example, it can be about 20 nm to about 10 ⁇ m thick (e.g., about 25 nm to about 8 ⁇ m, about 50 nm to about 6 ⁇ m, about 75 nm to about 4 ⁇ m, about 100 nm to about 2 ⁇ m, about 125 nm to about 1 ⁇ m, about 150 nm to about 800 nm, about 175 nm to about 600 nm, about 200 nm to about 575 nm, about 225 to about 550 nm, about 250 nm to about 500 nm, about 275 nm to about 475 nm, about 300 nm to about 450 nm, about 325 nm to about 425 nm, or about 350 nm to about 400 nm).
  • a thickness of the film formed by the pretreatment coating for example, it can be about 20 nm to about 10 ⁇ m thick
  • the film formed by the pretreatment coating can be about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, about 100 nm, about 200 nm, about 300 nm, about 400 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 ⁇ m, about 2 ⁇ m, about 3 ⁇ m, about 4 ⁇ m, about 5 ⁇ m, about 6 ⁇ m, about 7 ⁇ m, about 8 ⁇ m, about 9 ⁇ m, or about 10 ⁇ m.
  • the processes of the present invention may improve the performance of the pretreatment coating, for example, by (1) reducing free fluoride ion content in the film (2) stabilizing the free fluoride ions remaining in the coating and (3) increasing the coat weight constituent elements in the film, for example, Ti and Zr.
  • the pretreatment coating on an aluminum alloy surface may contain detectable levels of calcium, for example 7-500 ppm or 10-50 ppm.
  • one or more steps e.g., two or more steps, three or more steps, four or more steps, etc.
  • steps e.g., two or more steps, three or more steps, four or more steps, etc.
  • types of pretreatment coating e.g., two or more types of pretreatment coating, three or more types of pretreatment coating, four or more types of pretreatment coating, etc.
  • the processes according to the embodiments of the present invention involve one or more steps of contacting the aluminum alloy surface coated with a pretreatment coating with an aqueous calcium-containing agent.
  • An aqueous calcium-containing agent contains calcium (Ca 2+ ) ions in an amount of at least about 7 ppm (7 ppm or above, which can also be expressed as >7 ppm), for example, at least about 7.5 ppm, at least about 8.0 ppm, at least about 8.5 ppm, at least about 9 ppm, or at least about 9.5 ppm.
  • the aqueous agent can contain calcium ions in an amount of from about 7.5 ppm to about 500 ppm, from example, from about 8 ppm to about 450 ppm, from about 8.5 ppm to about 400 ppm, from about 9.0 ppm to about 350 ppm, from about 9.5 ppm to about 300 ppm, from about 10 ppm to about 250 ppm, from about 20 ppm to about 200 ppm, from about 50 ppm to about 100 ppm, or from about 10 ppm to about 50 ppm.
  • the aqueous agent can contain calcium ions in a range of from about 7.5-9.8 ppm.
  • the aqueous calcium-containing agent can contain calcium ions at about 7.5 ppm.
  • an aqueous calcium-containing agent contains calcium ions at saturation.
  • aqueous agents examples include an aqueous solution, a sol, or a gel.
  • An aqueous agent used in the pretreatment methods of the present invention may contain calcium salts, such as calcium carbonate, calcium nitrate, calcium sulfate, calcium phosphate, etc.
  • an aqueous agent may contain other metal ions or salts, as well as other components.
  • an aqueous agent is a saturated solution of a calcium salt, such as CaCO 3 .
  • Another example is an aqueous solution containing calcium ions and detectable levels of one or more of Al, Mg, Si, and Mn.
  • Embodiments of the present invention encompass aqueous agents described herein as well as their uses in the processes of the present invention.
  • a calcium-containing aqueous agent with a pretreated metal surface, such as an aluminum alloy surface.
  • Bringing the metal surface, such as the aluminum alloy surface, and the calcium-containing aqueous agent into contact may also be described as exposing the surface to the aqueous agent, or applying the aqueous agent.
  • Examples of methods that may be used to bring the metal surface, such as the aluminum alloy surface, and the calcium-containing agent into contact include, but are not limited to, immersing (for example, by immersion of the surface into a bath or other type of vessel containing the calcium-containing agent), rinsing or spraying, or rolling the agent onto the surface.
  • Suitable methods and conditions are selected and optimized based on various considerations, such as the desired extent of calcium penetration into the pretreatment coating, the extent of fluoride ion reduction in the pretreatment coating, the type of the agent used and/or the type of the surface being treated.
  • One or more contacting steps may be employed. For example, one, two, three, four, five or more steps are possible.
  • more than one step of applying a pretreatment coating may be included, in which case, a calcium-containing agent may be applied one or more times after each step of the pretreatment coating or after some (one or more) of the steps.
  • Contact of the pretreated aluminum alloy surface with the calcium-containing agent may be conducted at various temperatures, for example at a temperature from approximately 15° C. to 85° C.
  • the duration of the contact of the pretreated metal surface, such as the pretreated aluminum alloy surface, with the calcium-containing agent may also vary.
  • the contact duration can range from several seconds (e.g., two or more seconds, three or more seconds, four or more seconds, five or more seconds, six or more seconds, seven or more seconds, eight or more seconds, nine or more seconds, 10 or more seconds, 15 or more seconds, 20 or more seconds, 25 or more seconds, or 30 or more seconds) to one or more minutes (e.g., two or more minutes, three or more minutes, four or more minutes, five or more minutes, six or more minutes, seven or more minutes, eight or more minutes, nine or more minutes, 10 or more minutes, 11 or more minutes, 12 or more minutes, 13 or more minutes, 14 or more minutes, 15 or more minutes, 16 or more minutes, 17 or more minutes, 18 or more minutes, 19 or more minutes, or 20 or more minutes).
  • seconds e.g., two or more seconds, three or more seconds, four or more seconds, five or more seconds, six or more seconds, seven or more seconds, eight or more seconds, nine or more seconds, 10 or more seconds, 15 or more seconds, 20 or more seconds, 25 or more
  • the duration of the contact of the pretreated metal surface with the calcium-containing agent can range from about 2 seconds to 20 minutes, from about 10 seconds to about 15 minutes, from about 30 seconds to about 10 minutes, or from about 1 minute to 5 minutes.
  • the selected duration which may also be referred to as “dwell time,” may depend on various factors, such as the type of the pretreatment coating, concentration of the pretreatment agent or the method of application.
  • the processes of the present invention may further contain one or more steps (two or more, three or more, four or more, etc.) of applying one or more films or coatings.
  • the embodiments of the present invention are applicable to either organic and inorganic films or coatings.
  • inorganic coatings are zinc phosphate, zirconium oxide, and E-coat.
  • organic coatings are films (such as protective or decorative films), paints, lacquers, adhesives, bonding compounds, glues and resins, or primers. It is to be understood that more than one type of coating (e.g., one or more, two or more, three or more, etc.) may be employed.
  • Embodiments of the present invention include processes of producing or manufacturing articles that comprise coated metal surface(s), such as aluminum alloy surface(s), treated by the surface pretreatment processes discussed above.
  • the processes may be employed in various industries, including motor vehicle, aircraft or electronics manufacturing, automotive industry, transportation industry, or more generally, in any industry where adhesive bonds of metal parts, such as aluminum alloy parts, are used.
  • the present invention also encompasses articles and materials manufactured by the above processes described herein.
  • the articles include motor vehicle parts or panels, ship or aircraft parts or panels, construction or architectural parts or panels and electronic housing parts.
  • Other examples of materials include composite and bonded materials, including metals, such as aluminum alloys, layered composites or laminates including aluminum layers adhered or bonded to aluminum or other types of layers, and clad or monolithic aluminum alloy sheets, such as those containing, for example, 2xxx, 3xxx, 5xxx, 6xxx and 7xxx aluminum alloys.
  • the present invention encompasses articles and materials that are manufactured by the processes described herein and include coated or bonded metal surfaces, such as aluminum alloy surfaces, or articles and other products or parts comprising coated or bonded metal surfaces, such as aluminum alloy surfaces.
  • Advantages afforded by the embodiments of the present invention include those discussed above. Further advantages of the embodiments of the present invention include improved methods producing a coated metal article, such as an aluminum article, with at least the same durability and corrosion resistance as the conventional processes, while reducing the costs and the hazardous waste.
  • a coated metal article such as an aluminum article
  • a significant reduction of water usage may be achieved, because less rinsing agent is required to achieve at least a comparable reduction in fluoride levels.
  • tap water may be employed as a calcium-containing rinse agent.
  • ICP inductively coupled plasma
  • the aluminum alloy samples were prepared as follows. Mill-finished AA5754 and AA6111 samples were subjected to the following sequential steps: (1) acidic etching in a solution of ferric sulfate and sulfuric acid, (7%) at 40-80° C. for 5-30 seconds; (2) rinsing in DI water at 65° C. for 8 seconds; (3) pretreatment in the pretreatment solution at 40-80° C. for 4-30 seconds; (4) air drying for 5-30 seconds at room temperature; (5) final rinsing by immersing each sample in one of the three different rinses at 40-80° C. for 4-30 seconds; and (6) air drying with clean compressed air.
  • the titanium coat weight for each sample was determined by X-ray fluorescence (XRF).
  • XRF X-ray fluorescence
  • Elemental depth profiling of AA6111 alloy samples was performed using x-ray photoelectron spectrometry (XPS).
  • XPS x-ray photoelectron spectrometry
  • a description of XPS protocols is provided, for example, in “Axis Ultra. Operators Manual” published in 1998 by Kratos Analytical (UK).
  • the results are illustrated in FIGS. 1A, 1B, 2A, 2B, 3A, and 3B .
  • the greatest signal for Ti and Zr at the Ti/Zr-pretreated sample surface was registered after the calcium rinse, which is consistent with greater coat weight registered with the XRF determination.
  • FIGS. 1A and 1B the greatest signal for Ti and Zr at the Ti/Zr-pretreated sample surface was registered after the calcium rinse, which is consistent with greater coat weight registered with the XRF determination.
  • the samples rinsed with the calcium rinse also showed stronger signals of both Si and O, in comparison with DI-rinsed samples, which indicates that a greater pretreatment coat weight was present on the samples rinsed with the calcium rinse.
  • a much stronger signal of calcium was detected on the Ti/Zr-pretreated AA6111 after the calcium rinse than on the other two samples. No calcium was detected on the DI water-rinsed sample.
  • fluoride tended to be rinsed out of the coating and then enriched at the Ti/Zr surface; in contrast, fluoride in the sample rinsed with the calcium rinse was stable and distributed through the coating.
  • Titanium coat weight for each sample was determined by X-ray fluorescence (XRF) and the polymer coat weight was determined by UV-visible spectroscopy (UV/vis).
  • XRF X-ray fluorescence
  • UV/vis UV-visible spectroscopy
  • Table 3 shows the dependence of the stress durability results for the AA6111 samples on the calcium-containing agents used in the final rinse step.
  • the joints were in vertical position during the stress durability testing, and numbered 1 through 6, top to bottom.
  • the samples rinsed with Ca(HCO 3 ) 2 and Ca(NO 3 ) 2 -based rinses failed after 8-10 cycles, while the rest of the samples passed 25 cycles.
  • the stress durability testing showed that the choice of salt employed in the rinse solution influences bond durability.
  • a stress durability test was used to assess the effect of the pretreatment and adhesive on bond durability.
  • the study was conducted using a sample of an AA6111 aluminum alloy including a Ti/Zr-based pretreatment film.
  • the aluminum alloy samples were etched and pretreated as described in Example 1. Different rinses were used on the pretreated samples for rinse times of 10 seconds.
  • Three types of rinses were tested, including deionized (DI) water, Georgia tap water, and artificially prepared calcium-containing rinses, which were prepared as solutions of Ca(HCO 3 ) 2 , Ca(NO 3 ) 2 , Ca(H 2 PO 4 ) 2 , Ca(NO 2 ) 2 , and CaSO 4 , in deionized water at 65° C. Each solution had a Ca 2+ concentration of 200 ppm.
  • Table 4 shows that the final rinse performed with different calcium salts exhibits varying bond durability performance.
  • the bonds rinsed with CaSO 4 -enriched water and Georgia tap water provided the highest mean cycle to failure and only one broken bond.
  • Ca(NO 2 ) 2 and DI water each resulted in two broken bonds.
  • Ca(HCO 3 ) 2 , Ca(NO 3 ) 2 , and Ca(H 2 PO 4 ) 2 each resulted in three broken bonds and did not complete the nominal requirement of 45 cycles.
  • the results show that tap water as the final rinse maintains or improves the pretreatment performance, as compared to DI water.
  • the particular anions of the Ca 2+ salts affect the bond durability performance.

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CN113201731A (zh) * 2021-05-08 2021-08-03 东北大学 一种汽车用高强钢表面锆化膜快速成膜的方法
CN113584468A (zh) * 2021-07-02 2021-11-02 武汉钢铁有限公司 一种预处理剂及其制备方法与应用
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EP4570947A1 (fr) * 2023-12-15 2025-06-18 Henkel AG & Co. KGaA Procédé en plusieurs étapes pour le traitement anticorrosion de composants à surfaces en acier

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