WO2023132989A1 - Compositions, systèmes et procédés de traitement d'un substrat - Google Patents

Compositions, systèmes et procédés de traitement d'un substrat Download PDF

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Publication number
WO2023132989A1
WO2023132989A1 PCT/US2022/079378 US2022079378W WO2023132989A1 WO 2023132989 A1 WO2023132989 A1 WO 2023132989A1 US 2022079378 W US2022079378 W US 2022079378W WO 2023132989 A1 WO2023132989 A1 WO 2023132989A1
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ppm
pretreatment composition
composition
pretreatment
total weight
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PCT/US2022/079378
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English (en)
Inventor
Kuldeep Kumar
Kristi Maree ALLEN
Rachel Dory HARRIS
Anthony J. Notte
Elizabeth Stephenie BROWN-TSENG
Silvia BEZER
Mark William Mcmillen
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Ppg Industries Ohio, Inc.
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Publication of WO2023132989A1 publication Critical patent/WO2023132989A1/fr

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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/57—Treatment of magnesium or alloys based thereon

Definitions

  • the present disclosure relates to compositions, systems, and methods for treating a substrate.
  • a pretreatment composition comprising: a lanthanide series metal; an oxidizing agent; and a fluorometallic acid, an organophosphate compound, an organophosphonate compound, or combinations thereof.
  • a pretreatment composition comprising: a lanthanide series metal; a carboxylic acid; and an oxidizing agent in an amount of no more than 70 ppm based on total weight of the pretreatment composition.
  • a system for treating a substrate comprising: a cleaning composition; and one of the pretreatment compositions disclosed herein.
  • a method of treating a substrate comprising: contacting at least a portion of the substrate with one of the pretreatment compositions disclosed herein.
  • a substrate comprising: a surface comprising a film on at least a portion thereof, wherein the film is formed from one of the pretreatment compositions disclosed herein.
  • a substrate treated with one of the systems or methods described herein.
  • FIG. 1 is a bar graph showing the scribe creep on E-form plus panels that were pretreated in Example 1 with one of PT-2 to PT- 11 according to Process B or PT-1 according to Process A and exposed to CASS testing (10 days).
  • FIG. 2 is a bar graph showing the scribe creep on E-form plus panels that were pretreated in Example 1 with one of PT-2 to PT- 11 according to Process B or PT-1 according to Process A and exposed to ASTM G-85 A2 testing (3 weeks).
  • FIG. 3 is a bar graph showing the scribe creep on E-form plus panels that were pretreated in Example 2 with one of PT-3, PT-6, PT- 12, or PT- 13 according to Process B and exposed to CASS testing (10 days).
  • FIG. 4 is a bar graph showing the scribe creep on E-form plus panels that were pretreated in Example 2 with one of PT-3, PT-6, PT- 12, or PT- 13 according to Process B and exposed to ASTM G-85 A2 testing (3 weeks).
  • FIG. 5 is a bar graph showing the dry adhesion and wet adhesion of coatings on panels pretreated with one of PT-2, PT-4, PT-6, PT-7, PT-8, PT-9, or PT-10 according to Process B or PT-1 according to Process A in Example 3.
  • FIG. 6 is a bar graph showing the scribe creep on AA6111 panels that were pretreated in Example 4 with one of PT-2 to PT- 11 according to Process B or PT-1 according to Process A and exposed to CASS testing (20 days).
  • FIG. 7 is a bar graph showing the scribe creep on AA6111 panels that were pretreated in Example 4 with one of PT-3, PT-5, PT-6, PT-8, PT-10, or PT-11, according to Process B or PT-1 according to Process A and exposed to ASTM G-85 A2 testing (6 weeks).
  • FIG. 8 is a bar graph showing the scribe creep on AA6022 panels that were pretreated in Example 5 with one of PT-3, PT-5, PT-6, PT-8, PT- 10, or PT- 11 according to Process B or PT-1 according to Process A and exposed to CASS testing (20 days).
  • FIG. 9 is a bar graph showing the scribe creep on AA6022 panels that were pretreated in Example 5 with one of PT-3, PT-5, PT-6, PT-8, PT- 10, or PT- 11 according to Process B or PT-1 according to Process A and exposed to ASTM G-85 A2 testing (6 weeks).
  • FIG. 10 is a bar graph showing the scribe creep on HDG panels that were pretreated in Example 6 with one of PT-3, PT-5, PT-6, PT-8, PT- 10, or PT- 11 according to Process B or PT-1 according to Process A and exposed to GM14872 testing (80 cycles).
  • FIG. 11 is a bar graph showing the dry adhesion and wet adhesion of coatings on AA6111 panels pretreated with one of PT-2, PT-4, or PT-6, PT-7, PT-8, PT-9, or PT-10 according to Process B or PT-1 according to Process A in Example 7.
  • FIG. 12 shows exemplary panels for each rating 0-10 on the rating scale used in the Examples for adhesion testing.
  • each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • a closed or open-ended numerical range is described herein, all numbers, values, amounts, percentages, subranges and fractions within or encompassed by the numerical range are to be considered as being specifically included in and belonging to the original disclosure of this application as if these numbers, values, amounts, percentages, subranges and fractions had been explicitly written out in their entirety.
  • the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” mean formed, overlaid, deposited, or provided on but not necessarily in contact with the surface.
  • a coating composition “applied onto” a substrate does not preclude the presence of one or more other intervening coating layers of the same or different composition located between the coating composition and the substrate.
  • a “system” refers to a plurality of treatment compositions (including cleaners and rinses) used to treat a substrate and to produce a treated substrate.
  • the system may be part of a production line (such as a factory production line) that produces a finished substrate or a treated substrate that is suitable for use in other production lines.
  • salt refers to an ionic compound made of metal cations and non-metal anions and having an overall electrical charge of zero. Salts may be hydrated or anhydrous.
  • composition refers to a solution or dispersion and “aqueous composition” refers to a composition in a medium that comprises predominantly water.
  • the aqueous medium may comprise water in an amount of more than 50 wt.%, or more than 60 wt.%, or more than 70 wt.%, or more than 80 wt.%, or more than 90 wt.%, or more than 95 wt.% based on the total weight of the medium. That is, the aqueous medium may for example consist substantially of water.
  • the term “dispersion” refers to a two-phase transparent, translucent or opaque system in which particles, such as metal particles, are in the dispersed phase and an aqueous medium, which includes water, is in the continuous phase.
  • pretreatment composition refers to a composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a film that affords corrosion protection.
  • pretreatment bath refers to an aqueous bath containing the pretreatment composition and that may contain components that are byproducts of the process.
  • lanthanide series elements refers to elements 57-71 of the CAS version of the Periodic Table of the Elements and includes elemental version of the lanthanide series elements.
  • the lanthanide series elements may be those which have common oxidation states of +3 and +4, referred to hereinafter as +3/+4 oxidation states.
  • the term “lanthanide compound” refers to compounds that include at least one of elements 57-71 of the CASE version of the Periodic Table of the Elements.
  • Group IIIA metal and “Group IIIA element” refer to an element that is in Group IIIA of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 3 in the actual IUPAC numbering.
  • Group IIIA metal compound refers to compounds that include at least one element that is in Group IIIA of the CAS version of the Periodic Table of the Elements.
  • Group IVA metal and “Group IVA element” refer to an element that is in Group IVA of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 14 in the actual IUPAC numbering.
  • Group IVA metal compound refers to compounds that include at least one element that is in Group IVA of the CAS version of the Periodic Table of the Elements.
  • Group IVB metal and “Group IVB metal element” refer to an element that is in Group IVB of the of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Group 4 in the actual IUPAC numbering.
  • Group IVB metal compound refers to compounds that include at least one element that is in Group IVB of the CAS version of the Periodic Table of the Elements.
  • Group VIII metal and “Group VIII element” refer to an element that is in Group VIII of the CAS version of the Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983), corresponding to Groups 8-10 in the actual IUPAC numbering.
  • Group VIII metal compound refers to compounds that include at least one element that is in Group VIII of the CAS version of the Periodic Table of the Elements.
  • a “coating composition” refers to a composition, e.g., a solution, mixture, or a dispersion, that, in an at least partially dried or cured state, is capable of producing a film, layer, or the like on at least a portion of a substrate surface.
  • ambient conditions generally refer to room temperature and humidity conditions or temperature and humidity conditions that are typically found in the area in which the coating composition is being applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity, while slightly thermal conditions are temperatures that are slightly above ambient temperature.
  • the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is present only as an impurity in a trace amount of 5 ppm or less based on a total weight of the mixture or composition, respectively.
  • the term “essentially free” means that a particular material is present only in an amount of 1 ppm or less based on a total weight of the mixture or composition, respectively.
  • total composition weight refers to the total weight of all ingredients being present in the respective composition including any carriers and solvents.
  • halogen refers to any of the elements fluorine, chlorine, bromine, iodine, and astatine of the CAS version of the Periodic Table of the Elements, corresponding to Group VIIA of the periodic table.
  • halide refers to compounds that include at least one halogen.
  • mole ratio means the ratio between the amounts in moles of any two elements contained in a molecule.
  • the term “monocarboxylic acid” means a carboxylic acid that comprises one carboxyl group per molecule.
  • dicarboxylic acid means a carboxylic acid that comprises two carboxyl groups per molecule.
  • tricarboxylic acid means a carboxylic acid that comprises three carboxyl groups per molecule.
  • the present disclosure is directed to a pretreatment composition
  • a pretreatment composition comprising: a lanthanide series metal; an oxidizing agent; and a fluorometallic acid, an organophosphate compound, an organophosphonate compound, or combinations thereof.
  • the present disclosure also is directed to a pretreatment composition
  • a pretreatment composition comprising: a lanthanide series metal; a carboxylic acid; and an oxidizing agent in an amount of no more than 70 ppm based on total weight of the pretreatment composition.
  • the pretreatment composition of the present disclosure may comprise a lanthanide series metal.
  • the lanthanide series metal may, for example, comprise cerium, hafnium, praseodymium, terbium, or combinations thereof.
  • the lanthanide series metal may have an oxidation state of +3 and/or +4.
  • the lanthanide series metal may be present in the pretreatment composition as a salt.
  • the pretreatment composition may comprise more than one lanthanide series metal (i.e., a “first” lanthanide series metal and a “second” lanthanide series metal, a “third” lanthanide series metal, etc.).
  • the pretreatment composition may contain no more than one lanthanide series metal, such that the pretreatment composition may contain one lanthanide series metal and may be substantially free, essentially free, and/or completely free of more than one lanthanide series metals. That is, the pretreatment composition may be substantially free, essentially free, or completely free of a “second” lanthanide series metal, a “third” lanthanide series metal, etc.
  • the lanthanide series metal may come from more than one source, such as two or more lanthanide-containing salts or other compounds.
  • the lanthanide series metal may be present in the pretreatment composition in an amount of at least 50 ppm based on total weight of the pretreatment composition, such as at least 60 ppm, such as at least 70 ppm, such as at least 80 ppm, such as at least 90 ppm, such as at least 100 ppm, and may be present in the pretreatment composition in an amount of no more than 25,000 ppm based on total weight of the pretreatment composition, such as no more than 10,000 ppm, such as no more than 5,000 ppm, such as no more than 3,000 ppm, such as no more than 1,000 ppm, such as no more than 500 ppm.
  • the lanthanide series metal may be present in the pretreatment composition in an amount of 50 ppm to 25,000 ppm based on total weight of the pretreatment composition, such as 60 ppm to 10,000 ppm, such as 70 ppm to 5,000 ppm, such as 80 ppm to 3,000 ppm, such as 90 ppm to 1,000 ppm, such as 100 ppm to 500 ppm.
  • the pretreatment compositions may be substantially free, essentially free, or completely free of lanthanide oxide such that the bath containing the pretreatment composition is substantially free, essentially free, or completely free of lanthanide oxide.
  • the lanthanide series metal may be present in the pretreatment composition as a salt.
  • the pretreatment composition may further comprise an anion that may be suitable for forming a salt with the lanthanide series metal, such as a halogen, a nitrate, a sulfate, a phosphate, a silicate (orthosilicates and metasilicates), carbonates, hydroxides, and the like.
  • the halogen may exclude fluoride since lanthanide metal fluoride complexes are generally insoluble in water.
  • the anion may be present in the pretreatment composition, if at all, in an amount of at least 5 ppm based on total weight of the pretreatment composition, such as at least 50 ppm, such as at least 150 ppm, such as at least 300 ppm and may be present in an amount of no more than 25,000 ppm based on total weight of the pretreatment composition, such as no more than 18,000 ppm, such as no more than 5,000 ppm, such as no more than 1,000 ppm.
  • the anion may be present in the pretreatment composition, if at all, in an amount of 5 ppm to 25,000 ppm based on total weight of the pretreatment composition, such as 50 ppm to 18,000, such as 150 ppm to 5,000 ppm, such as 300 ppm to 1,000 ppm.
  • the pretreatment composition may further comprise an oxidizing agent.
  • oxidizing agent when used with respect to the pretreatment composition, refers to a chemical which is capable of oxidizing a metal present in the substrate.
  • oxidizing agent the phrase “capable of oxidizing” means capable of removing electrons from an atom or a molecule present in the substrate, thereby decreasing the number of electrons of such atom or molecule.
  • Non-limiting examples of the oxidizing agents that may be used in the pretreatment composition include but are not limited to peroxides, persulfates, perchlorates, hypochlorite, nitric acid, sparged oxygen, bromates, peroxy-benzoates, ozone, or combinations thereof.
  • the oxidizing agent may be present in an amount of at least 25 ppm, such as at least 150 ppm, such as at least 500 ppm, such as at least 750 ppm, based on total weight of the pretreatment composition, and may be present in an amount of no more than 13,000 ppm, such as no more than 10,000 ppm, such as no more than 3,000 ppm, such as no more than 2,000 ppm, such as no more than 70 ppm, such as no more than 50 ppm, such as no more than 25 ppm. based on total weight of the pretreatment composition.
  • the oxidizing agent may be present in an amount of 25 ppm to 13,000 ppm, such as 150 ppm to 10,000 ppm, such as 500 ppm to 3,000 ppm based on total weight of the pretreatment composition.
  • the pretreatment composition may comprise no more than 70 ppm of the oxidizing agent based on total weight of the pretreatment composition, such as no more than 60 ppm, such as no more than 50 ppm, such as no more than 40 ppm, such as no more than 30 ppm, such as no more than 20 ppm, such as no more than 10 ppm.
  • the pretreatment composition may be substantially free, essentially free, or completely free of oxidizing agent.
  • the pretreatment composition may comprise a fluorometallic acid.
  • the fluorometallic acid may comprise fluoride and a Group IIIA metal, Group IVA metal, Group IVB metal, a Group VI metal, and/or Group VIII metal.
  • the fluoride comprising the fluorometallic acid may have a mole ratio to the Group IIIA metal, Group IVA metal, Group IVB metal, Group VI metal, and/or Group VIII metal of more than 4. That is, for each metal atom present in the fluorometallic acid, there may be more than 4 fluoride atoms present in the fluorometallic acid.
  • Non-limiting examples of fluorometallic acids comprising fluoride having a mole ratio of more than 4 include hexafluoro silicic acid, hexafluorozirconic acid, hexafluoroferric acid, hexafluoroaluminic acid, hexafluorotitanic acid, or combinations thereof.
  • the Group IIIA metal of the fluorometallic acid may, for example, comprise aluminum and may be provided in the pretreatment composition in the form of specific compounds of the Group IIIA metal, such as their soluble acids and/or salts.
  • useful compounds include hexafluoroaluminic acid.
  • the Group IIIA metal of the fluorometallic acid may be present in the pretreatment composition comprising the fluorometallic acid in an amount of at least 10 ppm based on total weight of the pretreatment composition, such as at least 50 ppm, such as at least 100 ppm, and may be present in the pretreatment composition in an amount of no more than 1,500 ppm based on total weight of the pretreatment composition, such as no more than 1,200 ppm, such as no more than 1,000 ppm.
  • the Group IIIA metal of the fluorometallic acid may be present in the pretreatment composition in an amount of 10 ppm to 1,500 ppm based on total weight of the pretreatment composition, such as 50 ppm to 1,200 ppm, such as 100 ppm to 1,000 ppm.
  • the Group IVA metal of the fluorometallic acid may, for example, comprise silicon such as silanes, silicas, silicates, and the like.
  • the Group IVA metal may be provided in the pretreatment composition in the form of specific compounds of the metals, such as their soluble acids and/or salts. Examples of useful compounds include fluorosilicic acid, ammonium and alkali metal fluorosilicates, and the like, including by way of non-limiting example, hexafluoro silicic acid.
  • the Group IVA metal of the fluorometallic acid may be present in the pretreatment composition comprising fluorometallic acid in an amount of at least 10 ppm based on total weight of the pretreatment composition, such as at least 20 ppm, such as at least 25 ppm, such as at least 40 ppm, such as at least 50 ppm, and may be present in the pretreatment composition in an amount of no more than 1,500 ppm based on total weight of the pretreatment composition, such as no more than 1,250 ppm, such as no more than 1,000 ppm, such as no more than 750 ppm, such as no more than 500 ppm.
  • the Group IVA metal of the fluorometallic acid may be present in the pretreatment composition in an amount of 10 ppm to 1,500 ppm based on total weight of the pretreatment composition, such as 20 ppm to 1,250 ppm, such as 25 ppm to 1,000 ppm, such as 40 ppm to 750 ppm, such as 50 ppm to 500 ppm.
  • the Group IVB metal of the fluorometallic acid may comprise zirconium, titanium, hafnium, or combinations thereof.
  • the Group IVB metal used in the pretreatment composition may be a compound of zirconium, titanium, hafnium, or a mixture thereof.
  • Suitable compounds of the fluorometallic acid include, but are not limited to, hexafluorozirconic acid, zirconium tetrafluoride, fluorotitanic acid, fluoro-hafnium acid and salts thereof.
  • the Group IVB metal of the fluorometallic acid may be present in the pretreatment composition in an amount of at least 40 ppm based on total weight of the pretreatment composition, such as at least 50 ppm, such as at least 60 ppm, such as at least 70 ppm, such as at least 80 ppm.
  • the Group IVB metal of the fluorometallic acid may be present in the pretreatment composition in an amount of no more than 5,000 ppm based on total weight of the pretreatment composition, such as no more than 2,500 ppm, such as no more than 2,000 ppm such as no more than 1,500 ppm, such as no more than 1,000 ppm, such as no more than 500 ppm, such as no more than 250 ppm.
  • the Group IVB metal of the fluorometallic acid may be present in the pretreatment composition in a total amount of 40 ppm to 5,000 ppm based on total weight of the pretreatment composition, such as 50 ppm to 2,500 ppm, such as 60 ppm to 2,000 ppm, such as 60 ppm to 1,500 ppm, such as 60 ppm to 1,000 ppm, such as 60 ppm to 500 ppm, such as 60 ppm to 250 ppm, such as 70 ppm to 1,500 ppm, such as 70 ppm to 1,000 ppm, such as 70 ppm to 500 ppm, such as 70 ppm to 250 ppm, such as 80 ppm to 1,000 ppm, such as 80 ppm to 500 ppm, such as 80 ppm to 250 ppm.
  • the composition may comprise more than one type of Group IVB metal. In such instances, each type of Group IVB metal may be present in the amounts disclosed above.
  • the Group VIII metal of the fluorometallic acid may, for example, comprise iron and may be provided in the pretreatment composition in the form of specific compounds of the metals, such as their soluble acids and/or salts. Examples of useful compounds include hexafluoroferric acid.
  • the Group VIII metal if present at all, may be present in the pretreatment composition comprising fluorometallic acid in an amount of at least 100 ppm based on total weight of the pretreatment composition, such as at least 200 ppm, such as at least 500 ppm, and may be present in the pretreatment composition in an amount of no more than 3,000 ppm based on total weight of the pretreatment composition, such as no more than 2,000 ppm, such as no more than 1,000 ppm.
  • the Group VIII metal if present at all, may be present in the pretreatment composition in an amount of 100 ppm to 3,000 ppm based on total weight of the pretreatment composition, such as 200 ppm to 2,000 ppm, such as 500 ppm to 1,000 ppm.
  • the pretreatment composition may comprise a compound comprising a Group IVB metal other than the Group IVB fluorometallic acid described above.
  • the compound comprising a Group IVB metal may comprise zirconium, titanium, hafnium, or combinations thereof.
  • zirconium tetrafluoride ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconium carboxylates and zirconium hydroxy carboxylates, such as zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, zirconium basic carbonate, zirconium tetraalkaloids, and mixtures thereof.
  • suitable compounds of titanium include, but are not limited to, titanium (III) fluoride, titanium (IV) fluoride, titanium bromide, titanium chloride, titanium iodide, titanium oxysulfate, titanium isopropoxide, titanium acetate, titanyl sulfate, and titanium nitrate.
  • a suitable compound of hafnium includes, but is not limited to, hafnium nitrate.
  • the compound comprising a Group IVB metal other than the fluorometallic acid may be present in the pretreatment composition in an amount of at least 5 ppm based on total weight of the pretreatment composition, such as at least 10 ppm, such as at least 20 ppm, such as at least 50 ppm, such as at least 100 ppm, such as at least 200 ppm, such as at least 350 ppm, such as at least 500 ppm.
  • the compound comprising a Group IVB metal other than the fluorometallic acid may be present in the pretreatment composition in an amount of no more than 5,000 ppm based on total weight of the pretreatment composition, such as no more than 2,500 ppm, such as no more than 1,750 ppm, such as no more than 1,500 ppm, such as no more than 1,000 ppm, such as no more than 450 ppm, such as no more than 200 ppm.
  • the compound comprising a Group IVB metal other than the fluorometallic acid may be present in the pretreatment composition in an amount of 5 ppm to 5,000 ppm based on total weight of the pretreatment composition, such as 10 ppm to 2,500 ppm, such as 20 ppm to 1,750 ppm, such as 50 ppm to 1,500 ppm, such as 100 ppm to 1,000 ppm, such as 100 ppm to 450 ppm, such as 100 ppm to 200 ppm, such as 200 ppm to 450 ppm, such as 350 ppm to 1,000 ppm, such as 350 ppm to 450 ppm, such as 500 ppm to 5,000 ppm, such as 500 ppm to 2,500 ppm, such as 500 ppm to 1,750 ppm, such as 500 ppm to 1,500 ppm, such as 500 ppm to 1,000 ppm.
  • the pretreatment composition may comprise a halide, such as, for example, fluoride or a non-fluoride halide such as chloride or bromide.
  • Suitable sources of halide include hydrofluoric acid, hydrochloric acid, sodium hydrogen fluoride, potassium hydrogen fluoride, ammonium salts of halides, sodium chloride, sodium bromide, and/or acids or salts of tetrafluoroborate.
  • Complex fluoride-containing compounds such as fluorotitanic acid, fluorozirconic acid, potassium hexafluorotitanic acid and/or potassium hexafluorozirconic acid can also be used.
  • the total fluoride may be calculated by comparing the weight of the fluoride supplied in the pretreatment composition with the total weight of the pretreatment composition.
  • the pretreatment composition may comprise total fluoride, if present at all, in an amount of at least 50 ppm based on total weight of the pretreatment composition, such as at least 75 ppm, such as at least 100 ppm.
  • the pretreatment composition may comprise total fluoride, if present at all, in an amount of no more than 5,000 ppm based on total weight of the pretreatment composition, such as no more than 3,000 ppm, such as no more than 2,500 ppm.
  • the pretreatment composition may comprise free fluoride, if present at all, in an amount of 50 ppm to 5,000 ppm based on total weight of the pretreatment composition, such as 75 ppm to 3,000 ppm, such as 100 ppm to 2,500 ppm.
  • the composition may comprise free fluoride.
  • the free fluoride may be derived from the fluoride-containing compounds described above and/or the free fluoride may be derived from a compound or complex other than a fluorometallic compound.
  • “free fluoride” refers to fluoride present in the pretreatment composition that is not bound to metal ions or hydrogen ions, as measured in parts per million of fluoride. Free fluoride may be measured using, for example, an Orion Dual Star Dual Channel Benchtop Meter equipped with a fluoride ion selective electrode (“ISE”) available from Thermo scientific, the sympHony® Fluoride Ion Selective Combination Electrode supplied by VWR International, or similar electrodes.
  • ISE fluoride ion selective electrode
  • the fluoride ISE may be standardized by immersing the electrode into solutions of known fluoride concentration and recording the reading in millivolts, and then plotting these millivolt readings in a logarithmic graph. The millivolt reading of an unknown sample can then be compared to this calibration graph and the concentration of fluoride determined.
  • the fluoride ISE can be used with a meter that will perform the calibration calculations internally and thus, after calibration, the concentration of the unknown sample can be read directly.
  • the free fluoride may be present in the pretreatment composition in an amount of at least 10 ppm based on total weight of the pretreatment composition, such as at least 25 ppm, such as at least 35 ppm, such as at least 100 ppm, such as at least 200 ppm.
  • the free fluoride may be present in the pretreatment composition in an amount of no more than 2,500 ppm based on total weight of the pretreatment composition, such as no more than 2,000 ppm, such as no more than 1,500 ppm, such as no more than 1,000 ppm, such as no more than 600 ppm, such as no more than 200 ppm, such as no more than 100 ppm, such as no more than 75 ppm.
  • the free fluoride may be present in the pretreatment composition in an amount of 10 ppm to 2,500 ppm free fluoride based on total weight of the pretreatment composition, such as 10 ppm to 2,000 ppm, such as 10 ppm to 1,500 ppm, such as 10 ppm to 1,000 ppm, such as 10 ppm to 600 ppm, such as 10 ppm to 200 ppm, such as 10 ppm to 100 ppm, such as 10 ppm to 75 ppm, such as 25 ppm to 2,500 ppm, such as 25 ppm to 2,000 ppm, such as 25 ppm to 1,500 ppm, such as 25 ppm to 1,000 ppm, such as 25 ppm to 600 ppm, such as 25 ppm to 100 ppm, such as 25 ppm to 75 ppm, such as 35 ppm to 2,500 ppm, such as 35 ppm to 2,000 ppm, such as 35 ppm to 1,500 ppm,
  • the non-fluoride halide may be present in the pretreatment composition in amounts of at least 50 ppm based on total weight of the pretreatment, such as at least 60 ppm, such as at least 75 ppm, such as at least 100 ppm, and may be present in an amount of no more than 20,000 ppm based on total weight of the pretreatment composition, such as no more than 10,000 ppm, such as no more than 5,000 ppm, such as no more than 2,000 ppm.
  • the nonfluoride halide may be present in the pretreatment composition in amounts of 50 ppm to 20,000 ppm based on total weight of the pretreatment composition, such as 50 ppm to 10,000 ppm, such as 50 ppm to 5,000 ppm, such as 50 ppm to 2,000 ppm, such as 60 ppm to 20,000 ppm, such as 60 ppm to 10,000 ppm, such as 60 ppm to 5,000 ppm, such as 60 ppm to 2,000 ppm, such as 75 ppm to 20,000 ppm, such as 75 ppm to 10,000 ppm, such as 75 ppm to 5,000 ppm, such as 75 ppm to 2,000 ppm, such as 100 ppm to 20,000 ppm, such as 100 ppm to 10,000 ppm, such as 100 ppm to 5,000 ppm, such as 100 ppm to 2,000 ppm.
  • the amount of nonfluoride halide present in the pretreatment composition is a pretreatment
  • the pretreatment composition and/or the system may exclude fluoride, fluoride sources, non-fluoride halides and/or non-fluoride halide sources.
  • fluoride sources include monofluorides, bifluorides, fluoride complexes, and mixtures thereof known to generate fluoride ions.
  • compositions and/or a layer or coating comprising the same or a system is substantially free, essentially free, and/or completely free of fluoride, fluoride sources, non-fluoride halides and/or non-fluoride halide sources
  • fluoride ions or fluoride sources, or non-fluoride halide ions or non-fluoride halide ion sources are excluded from the composition or system, except that unintentional fluoride or non-fluoride halide that may be present in a composition or bath containing the composition as a result of, for example, carry-over from prior treatment baths in the processing line, municipal water sources (e.g., fluoride added to water supplies to prevent tooth decay), fluoride from a pretreated substrate, or the like.
  • a bath that is substantially free, essentially free, and/or completely free of fluoride or non-fluoride halide may have unintentional fluoride or non-fluoride halide, respectively, that may be derived from these external sources, even though the composition or compositions making up the system and used to make the bath prior to use on the processing line was substantially free, essentially free, and/or completely free of fluoride or non-fluoride halide, respectively.
  • the pretreatment composition may be substantially free of any fluoride sources, such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric, fluoro silicic, fluoro titanic, and fluorozirconic acids and their ammonium and alkali metal salts, and other inorganic fluorides, nonexclusive examples of which are: zinc fluoride, zinc aluminum fluoride, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride, and hydrofluoric acid, as well as other similar materials known to those skilled in the art.
  • fluoride sources such as ammonium and alkali metal fluorides, acid fluorides, fluoroboric, fluoro silicic, fluoro titanic, and fluorozirconic acids and their ammonium and alkali metal salts
  • other inorganic fluorides nonexclusive examples of which are: zinc fluoride, zinc aluminum fluoride, titanium fluoride, zi
  • the pretreatment composition may be substantially free of any nonfluoride halide sources.
  • the pretreatment composition optionally may comprise an organophosphate compound and/or an org anopho sphonate compound, such as an organophosphoric acid or an organophosphonic acid.
  • the org anopho sphonate compound may be a phosphatized epoxy resin.
  • the phosphatized epoxy resin may be a phosphoric acid ester or a phosphonic acid ester of an epoxy compound.
  • Suitable organophosphoric acids include, but are not limited to, phosphoric acid ester of bisphenol A diglycidyl ether.
  • Suitable organophosphonic acids are those having at least one group of the structure:
  • Ri comprises an alkanediyl, an aryl, an alkoxide, an ester, and/or an ether.
  • Ri may be CFh or O-CO-(CH2)2.
  • Non-limiting examples include l-hydroxyethyldiene-l,l-diphosphonic acid (HED) and/or carboxy ethyl phosphonic acid.
  • organophosphonic acids include alkyl phosphonic acids where Ri is an alkyl chain ranging from Ci to Cf> such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, and/or hexylphosphonic acid.
  • Organophosphonic acids where Ri is an aryl group such as phenylphosphonic acid may also be used.
  • alphaaminomethylene phosphonic acids which may be utilized in the reaction with an epoxy compound to prepare a compound include those comprising the structure:
  • R2 comprises an optionally substituted alkyl, an aryl, an alkoxide, an ester, and/or an ether
  • R3 comprises a hydrogen, an alkyl, an aryl, an alkoxide, an ester, an ether, and/or an epoxy.
  • R2 may comprise CH2PO3H2 and R3 may comprise hydrogen or an alkyl group such as 2-hydroxyethyl, isopropyl, n-propyl, n-butyl, n-hexyl, n-octyl, isononyl, dodecyl, or benzyl.
  • alpha- aminomethylene phosphonic acids include examples where R2 and R3 are alkyl groups, such as P- [(dimethylamino)methyl] phosphonic acid and P-[(diethylamino)methyl] phosphonic acid.
  • alpha- aminomethylene phosphonic acids with at least three phosphonic acids per molecule include: aminotris(methylenephosphonic acid) where R2 and R3 are CH2PO3H2, ethylenediaminetetrakis(methylenephosphonic acid), i.e., (H2O3PCH2)2N(CH2)2N(CH2PO3H2)2, and diethylenetriaminepentakis(methylphosphonic acid), i.e., [(H2O3PCH2)2N(CH2)2]2NCH 2 PO3H2.
  • Alpha-aminomethylene phosphonic acids are generally known compounds and can be prepared utilizing generally known methods. Many alpha-aminomethylene phosphonic acids are available commercially, for example under the Dequest product line available from Italmatch Chemicals (Genoa, Italy). One such example is aminotris(methylenephosphonic acid), which is available in an aqueous solution as Dequest 2000.
  • Suitable epoxy compounds include, but are not limited to, 1,2-epoxy compounds having an epoxy equivalence of at least 1, such as monoepoxides having a 1,2-epoxy equivalent of 1 or poly epoxides having a 1,2-epoxy equivalent of 2 or more.
  • epoxy compounds include, but are not limited to, polyglycidyl ethers of polyhydric phenols such as the polyglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, and 1 , l-bis(4- hydroxyphenyl)isobutane, monoglycidyl ethers of a monohydric phenol or alcohol such as phenyl glycidyl ether and butyl glycidyl ether, or combinations thereof.
  • polyglycidyl ethers of polyhydric phenols such as the polyglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, and 1 , l-bis(4- hydroxyphenyl)isobutane
  • monoglycidyl ethers of a monohydric phenol or alcohol such as phenyl glycidyl ether and butyl g
  • organophosphonic or organophosphoric resins include, but are not limited to, benzylaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether; carboxyethyl phosphonic acid ester of bisphenol A diglycidyl ether and of phenylglycidyl ether and of butyl glycidyl ether; carboxyethyl phosphonic acid mixed ester of bisphenol A diglycidyl ether and butylglycidyl ether; triethoxyl silyl propylaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether and cocoaminobis(methylenephosphonic) acid ester of bisphenol A diglycidyl ether.
  • the organophosphate or organophosphonate compound may be present in the pretreatment composition in an amount of at least 1 percent by weight based on total weight of the pretreatment composition, such as at least 5 percent by weight, and may be present in an amount of no more than 20 percent by weight based on total weight of the pretreatment composition, such as no more than 15 percent by weight.
  • the organophosphate or organophosphonate compound may be present in the pretreatment composition in an amount of 1 percent by weight to 20 percent by weight based on total weight of the pretreatment composition, such as 5 percent by weight to 15 percent by weight.
  • the pretreatment composition may have a solids content of at least 1.25 percent by weight based on total weight of the pretreatment composition, such as at least 2.5 percent by weight, such as at least 5 percent by weight, and may have a solids content of no more than 25 percent by weight based on total weight of the pretreatment composition, such as no more than 15 percent by weight, such as no more than 10 percent by weight.
  • the pretreatment composition may have a solids content of 1.25 percent by weight to 25 percent by weight based on total weight of the pretreatment composition, such as 2.5 percent by weight to 15 percent by weight, such as 5 percent by weight to 10 percent by weight.
  • the organophosphate or organophosphonate compound may be soluble in an aqueous medium (described below) to the extent of at least 0.03 grams per 100 grams of water at 25°C.
  • the pretreatment composition and/or the system may be substantially free, or, in some cases, essentially free, or in some cases, completely free of any Group IVB metals.
  • the present disclosure also is directed to a pretreatment composition
  • a pretreatment composition comprising, or consisting essentially of, or consisting of, a lanthanide series metal and at least one carboxylic acid.
  • the pretreatment composition may comprise an oxidizing agent in an amount of no more than 70 ppm based on total weight of the pretreatment composition, as described above.
  • the lanthanide series metal may be any of those lanthanide series metals described hereinabove and may be present in the pretreatment composition in the amounts disclosed hereinabove.
  • the carboxylic acid may be a monocarboxylic acid.
  • suitable monocarboxylic acids include, but are not limited to, propionic acid, acetic acid, and/or butyric acid.
  • the carboxylic acid may be a dicarboxylic acid.
  • suitable di-carboxylic acids include, but are not limited to, itaconic acid, fumaric acid, malic acid, and/or succinic acid.
  • the carboxylic acid may be substantially free of a tricarboxylic acid. That is, the carboxylic acid may comprise less than three carboxyl groups.
  • the carboxylic acid may be present in the composition in an amount of at least 100 ppm based on a total weight of the composition, such as at least 1,000 ppm, such as at least 10,000 ppm, such as at least 15,000 ppm.
  • the carboxylic acid may be present in the composition in an amount of no more than 50,000 ppm based on a total weight of the composition, such as no more than 40,000 ppm, such as no more than 30,000 ppm, such as no more than 20,000 ppm.
  • the carboxylic acid may be present in the composition in an amount of 100 ppm to 50,000 ppm based on total weight of the composition, such as 1,000 ppm to 40,000 ppm, such as 10,000 ppm to 30,000 ppm, such as 15,000 ppm to 20,000 ppm.
  • the pretreatment compositions may have a pH of no more than 7, such as no more than 6, such as no more than 5.5, such as no more than 5, such as no more than 4.5, such as no more than 4, such as no more than 3.5, such as no more than 3, and may have a pH of at least 1, such as at least 1.5, such as at least 2, such as at least 2.5.
  • the pretreatment compositions may have a pH of 1 to 7, such as 1 to 5, such as 1.5 to 4.5, such as 2 to 4, such as 2 to 5, such as 2 to 6, such as 2.5 to 5.5.
  • the pH of the pretreatment composition may be adjusted using, for example, any acid and/or base as is necessary.
  • the pH of the pretreatment composition may be maintained through the inclusion of an acidic material, including water soluble and/or water dispersible acids, such as nitric acid, sulfuric acid, and/or phosphonic acid.
  • the pH of the pretreatment composition may be maintained through the inclusion of a basic material, including water soluble and/or water dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as triethylamine, methylethyl amine, or mixtures thereof.
  • the pretreatment compositions may be substantially free, essentially free, and/or completely free of gelatin.
  • the pretreatment compositions optionally may be substantially free, essentially free, and/or completely free of copper.
  • the pretreatment compositions may exclude chromium or chromium-containing compounds. That is, the pretreatment composition and/or coatings or layers deposited from the pretreatment composition may be substantially free, may be essentially free, and/or may be completely free of such chromium or chromium-containing compounds.
  • chromium-containing compound refers to materials that include trivalent and/or hexavalent chromium.
  • Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium, strontium dichromate, chromium (III) sulfate, chromium (III) chloride, and chromium (III) nitrate.
  • chromium (III) sulfate chromium (III) chloride
  • chromium (III) nitrate When a pretreatment composition or a material deposited onto a substrate surface by deposition of the pretreatment composition is substantially free, essentially free, or completely free of chromium, this includes chromium in any form, such as, but not limited to, the trivalent and hexavalent chromium-containing compounds listed above.
  • the pretreatment compositions and/or material deposited on a substrate surface by deposition of the pretreatment composition may be substantially free, essentially free, and/or completely free of one or more of any of the elements or compounds in the preceding paragraph.
  • a pretreatment composition or a material deposited on a substrate surface by deposition of the pretreatment composition that is substantially free of chromium or derivates thereof means that chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment.
  • the amount of material is so small that it does not affect the properties of the pretreatment composition or deposited material; in the case of chromium, this may further include that the element or compounds thereof are not present in the pretreatment compositions and/or deposited material in such a level that it causes a burden on the environment.
  • the term “substantially free” means that the pretreatment compositions and/or deposited material contain less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph based on total weight of the composition or the layer, respectively, if any at all.
  • the term “essentially free” means that the pretreatment compositions and/or deposited material contain less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
  • the term “completely free” means that the pretreatment compositions and/or deposited material does not comprise a particular material, i.e., the mixture or composition comprises 0 ppm of such material, or that such material is below the detection limit of common analytical techniques.
  • the pretreatment compositions may, in some instances, exclude phosphate ions or phosphate-containing compounds and/or the formation of sludge, such as aluminum phosphate, iron phosphate, and/or zinc phosphate, formed in the case of using a treatment agent based on zinc phosphate. That is, the pretreatment composition and/or coatings or layers deposited from the pretreatment composition may be substantially free, essentially free, or completely free of phosphate ions or phosphate-containing compounds.
  • phosphate-containing compounds include compounds containing the element phosphorous such as ortho phosphate, pyrophosphate, metaphosphate, tripolyphosphate, organophosphonates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum and/or iron.
  • a composition and/or a material deposited on a substrate surface by deposition of the pretreatment composition is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or compounds containing phosphate in any form.
  • the pretreatment composition and/or a material deposited on a substrate surface by deposition of the pretreatment composition may be substantially free, or in some cases may be essentially free, or in some cases may be completely free, of one or more of any of the ions or compounds listed in the preceding paragraph.
  • a pretreatment composition and/or deposited material being substantially free of phosphate means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts, such as because of impurities or unavoidable contamination from the environment.
  • the amount of material is so small that it does not affect the properties of the composition; this may further include that phosphate is not present in the pretreatment compositions and/or deposited materials in such a level that they cause a burden on the environment.
  • substantially free means that the pretreatment compositions and/or deposited material contain less than 5 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph based on total weight of the composition or the deposited material, respectively, if any at all.
  • the term “essentially free” means that the pretreatment compositions and/or deposited material contain less than 1 ppm of any or all of the phosphate anions or compounds listed in the preceding paragraph.
  • the term “completely free” means that the pretreatment compositions and/or deposited material contain less than 1 ppb of any or all of the phosphate anions or compounds listed in the preceding paragraph, if any at all.
  • the pretreatment compositions optionally may be substantially free, essentially free, and/or completely free of zirconium and/or zinc.
  • the pretreatment compositions may comprise a carrier, often an aqueous medium, so that the pretreatment composition is in the form of a solution or dispersion, if a carrier is present.
  • the pretreatment compositions may be an aqueous composition.
  • the pretreatment compositions may comprise an aqueous medium and may optionally contain other materials in addition to those described above, such as nonionic surfactants and auxiliaries conventionally used in the art of pretreatment.
  • water dispersible organic solvents for example, alcohols with up to above 8 carbon atoms, such as methanol, isopropanol, l-methoxy-2-propanol, and the like, may be present; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, or propylene glycol, and the like; dimethylformamide; xylene; a base such as an amine which can partially or completely neutralize the organophosphate and/or org anopho sphonate compound to enhance the solubility of the organophosphate and/or organophosphonate compounds, such as diisopropanolamine, triethylamine, dimethylethanolamine, and 2-amino-2-methylpropano
  • water dispersible organic solvents for
  • water dispersible organic solvents are typically used in amounts up to about ten percent by volume, based on the total volume of the pretreatment, as the case may be.
  • Other optional materials include surfactants that function as defoamers or substrate wetting agents. Anionic, cationic, amphoteric, and/or nonionic surfactants may be used.
  • the pretreatment compositions may further comprise a foam depressor, including by way of non-limiting example Foam Depressor 304 CK (commercially available from PPG Industries, Inc.).
  • foam depressors may be added to cleaning and pretreatment compositions to prevent the formation of foam or to break foam already present, particularly in spray applications.
  • Defoaming surfactants may optionally be present at levels up to 1 percent by weight, such as up to 0.1 percent by weight, and wetting agents are typically present at levels up to 2 percent by weight, such as up to 0.5 percent by weight, based on the total weight of the pretreatment composition.
  • the pretreatment compositions optionally may comprise a reaction accelerator, such as nitrite ions, nitrate ions, nitro-group containing compounds, hydroxylamine sulfate, persulfate ions, sulfite ions, hyposulfite ions, peroxides, iron (III) ions, iron compounds, bromate ions, chlorate ions, and chlorite ions, as well as ascorbic acid, citric acid, tartaric acid, malonic acid, succinic acid and salts thereof.
  • a reaction accelerator such as nitrite ions, nitrate ions, nitro-group containing compounds, hydroxylamine sulfate, persulfate ions, sulfite ions, hyposulfite ions, peroxides, iron (III) ions, iron compounds, bromate ions, chlorate ions, and chlorite ions, as well as ascorbic acid, citric acid, tartaric acid, malonic acid, succinic
  • the pretreatment compositions may comprise, or consist essentially of, or consist of: a lanthanide series metal; an oxidizing agent; and a fluorometallic acid.
  • the fluorometallic acid may comprise, consist essentially of, or consist of, a Group IIIA metal, a Group IVA metal, a Group IVB metal, and/or a Group VIII metal.
  • the pretreatment composition may comprise, or consist essentially of, or consist of: a lanthanide series metal; an oxidizing agent; and an organophosphate compound, an organophosphonate compound, or combinations thereof.
  • the pretreatment composition may comprise, or consist essentially of, or consist of: a lanthanide series metal; a carboxylic acid; and an oxidizing agent in an amount of no more than 70 ppm.
  • the present disclosure also is directed to a system for treating a substrate comprising, consisting essentially of, or consisting of: a cleaning composition; and one of the pretreatment compositions disclosed herein.
  • the cleaning composition may comprise an alkaline pH.
  • the cleaning composition may have a pH of at least 10.
  • suitable alkaline cleaners include ChemkleenTM 166HP, 166M/C, 177, 181ALP, 490MX, 2010LP, and Surface Prep 1 (SP1), Ultrax 32, Ultrax 97, Ultrax 29, and Ultrax92D, each of which are commercially available from PPG Industries, Inc.
  • AMC Acid Metal Cleaner
  • the system of the present disclosure optionally may exclude any additional compositions comprising a deoxidizing agent, i.e., any additional compositions may be substantially free, essentially free, or completely free of a deoxidizing agent.
  • the system may comprise, consist essentially of, or consist of a coating composition.
  • the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin.
  • film-forming resin refers to resins that can form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal of any diluents or carriers present in the composition and/or upon curing at ambient or elevated temperature.
  • Conventional film-forming resins that may be used include, without limitation, those typically used in automotive OEM coating compositions, automotive refinish coating compositions, industrial coating compositions, architectural coating compositions, coil coating compositions, and aerospace coating compositions, among others.
  • thermosetting refers to resins that “set” irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the composition constituents often induced, for example, by heat or radiation. Curing or crosslinking reactions also may be carried out under ambient conditions. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents.
  • thermoplastic refers to resins that comprise polymeric components that are not joined by covalent bonds and thereby can undergo liquid flow upon heating and are soluble in solvents.
  • any suitable technique may be used to deposit such a coating composition onto the substrate including, for example, brushing, dipping, flow coating, spraying, and the like.
  • depositing of a coating composition may comprise an electrocoating step wherein an electrodepositable coating composition is deposited onto at least a portion of the surface of a metal substrate by electrodeposition.
  • depositing of a coating composition comprises a powder coating step.
  • the coating composition may be a liquid coating composition.
  • the present disclosure also is directed to a method of treating a substrate comprising contacting at least a portion of the substrate with any of the pretreatments of the present disclosure.
  • the solution or dispersion of the pretreatment composition may be brought into contact with the substrate by any of the techniques described herein above.
  • the solution or dispersion may be in contact with at least a portion of the substrate surface for at least 5 seconds, such as at least 45 seconds, such as at least 60 seconds, such as at least 120 seconds, such as at least 180 seconds, such as no more than 5 minutes, such as no more than 4 minutes, such as no more than 3 minutes.
  • the contacting may be for 5 seconds to 5 minutes, such as 30 seconds to 5 minutes, such as 30 seconds to 4 minutes, such as 30 seconds to 3 minutes.
  • the pretreatment composition may be maintained (during contacting) at ambient temperature or higher, such as at least 21°C (70°F), such as at least 24°C (75°F), such as at least 26°C (80°F), such as at least 32°C (90°F), such as at least 37°C (100°F), such as at least 43°C (110°F), such as at least 48°C (120°F), such as 21°C to 49°C.
  • ambient temperature or higher such as at least 21°C (70°F), such as at least 24°C (75°F), such as at least 26°C (80°F), such as at least 32°C (90°F), such as at least 37°C (100°F), such as at least 43°C (110°F), such as at least 48°C (120°F), such as 21°C to 49°C.
  • the substrate optionally may be air dried at room temperature or may be dried with hot air, for example, by using an air knife, by flashing off the water, by brief exposure of the substrate to a high temperature, such as by drying the substrate in an oven at 15°C to 200°C or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70°C, or by passing the substrate between squeegee rolls.
  • the method may comprise, or may consist essentially of, or may consist of, contacting at least a portion of a surface of the substrate with a cleaner composition; and then contacting at least a portion of the surface that was contacted with the cleaner composition with a pretreatment composition as described herein.
  • the cleaner composition may have an alkaline pH or a solvent.
  • the substrate surface may not be contacted with a surface treatment composition (excluding water rinses) prior to contacting the substrate surface with the pretreatment composition.
  • the substrate surface may not be deoxidized with a separate composition comprising a deoxidizing agent other than the pretreatment composition disclosed herein.
  • oxidizing agent to one of the pretreatment compositions disclosed herein that comprise a lanthanide series metal and a fluorometallic acid, organophosphate, and/or organophosphonate allows deoxidizing and pretreatment to occur in a single step.
  • a separate composition must be used to deoxidize the substrate surface prior to pretreatment.
  • surface treatment refers to treatment or contact of at least a portion of a substrate surface with a surface treatment composition or dispersion that comprises ingredients other than or in addition to water.
  • At least a portion of the substrate surface may be cleaned prior to contacting at least a portion of the substrate surface with one of the pretreatment compositions described herein above in order to remove grease, dirt, and/or other extraneous matter.
  • At least a portion of the surface of the substrate may be cleaned by physical and/or chemical means, such as mechanically abrading the surface and/or cleaning/degreasing the surface with commercially available alkaline cleaning agents that are well known to those skilled in the art.
  • Such cleaners are often preceded and/or followed by a water rinse, such as with tap water, distilled water, or combinations thereof.
  • the substrate optionally may be rinsed with tap water, deionized water, and/or an aqueous solution of rinsing agents in order to remove any residue.
  • the wet substrate surface may be treated with one of the pretreatment compositions described above or the substrate may be dried prior to treating the substrate surface, such as air dried, for example, by using an air knife, by flashing off the water, by brief exposure of the substrate to a high temperature, such as 15°C to 100°C, such as 20°C to 90°C, or in a heater assembly using, for example, infrared heat, such as for 10 minutes at 70°C, or by passing the substrate between squeegee rolls.
  • the method may further comprise a coating composition.
  • the coating composition may comprise, or consist essentially of, or consist of, a film-forming resin.
  • the coating composition may be deposited onto at least a portion of the surface of the substrate following its treatment with one of the pretreatment compositions described herein above. Any suitable technique may be used to deposit such a coating composition onto the substrate, including, for example, brushing, dipping, flow coating, spraying and the like.
  • depositing of a coating composition may comprise an electrocoating step wherein an electrodepositable coating composition is deposited onto a metal substrate by electrodeposition.
  • such depositing of a coating composition comprises a powder coating step.
  • the coating composition may be a liquid coating composition.
  • the coating composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin, as described herein above in reference to the system.
  • the coating composition may be an electrodepositable coating composition comprising a water-dispersible, ionic salt group-containing film-forming resin that may be deposited onto a substrate by an electrocoating step wherein the electrodepositable coating composition is deposited onto the substrate under the influence of an applied electrical potential, i.e., by electrodeposition.
  • the ionic salt group-containing filmforming polymer may comprise a cationic salt group containing film-forming polymer for use in a cationic electrodepositable coating composition.
  • the term “cationic salt group- containing film-forming polymer” refers to polymers that include at least partially neutralized cationic groups, such as sulfonium groups and ammonium groups, that impart a positive charge.
  • the cationic salt group-containing film-forming polymer may comprise active hydrogen functional groups, including, for example, hydroxyl groups, primary or secondary amino groups, and thiol groups.
  • Cationic salt group-containing film- forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, cationic salt group-containing film-forming polymers.
  • Examples of polymers that are suitable for use as the cationic salt group-containing film-forming polymer include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, among others, provided that they are functionalized with a cationic salt group.
  • the cationic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the cationic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, such as 50% to 80% by weight, such as 60% to 75% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the “resin solids” include the ionic salt group-containing film-forming polymer, curing agent (as discussed below), and any additional water-dispersible non-pigmented component(s) present in the electrodepositable coating composition.
  • the ionic salt group containing film-forming polymer may comprise an anionic salt group containing film-forming polymer for use in an anionic electrodepositable coating composition.
  • anionic salt group containing film-forming polymer refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge.
  • the anionic salt group-containing film-forming polymer may comprise active hydrogen functional groups.
  • Anionic salt group-containing film- forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, anionic salt group- containing film-forming polymers.
  • the anionic salt group-containing film- forming polymer may comprise base- solubilized, carboxylic acid group-containing film-forming polymers such as the reaction product or adduct of a drying oil or semi-drying fatty acid ester with a dicarboxylic acid or anhydride; and the reaction product of a fatty acid ester, unsaturated acid or anhydride and any additional unsaturated modifying materials which are further reacted with polyol. Also suitable are the at least partially neutralized interpolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid and at least one other ethylenically unsaturated monomer.
  • Still another suitable anionic electrodepositable resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine- aldehyde resin.
  • Another suitable anionic electrodepositable resin composition comprises mixed esters of a resinous polyol.
  • Other acid functional polymers may also be used such as phosphatized polyepoxide or phosphatized acrylic polymers. Exemplary phosphatized poly epoxides are disclosed in U.S. Patent Application Publication No. 2009-0045071 at pars. [0004]-[0015] and U.S. Patent Application Serial No. 13/232,093 at pars. [0014] -[0040], the cited portions of which being incorporated herein by reference.
  • the anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount of at least 50% by weight, such as at least 55% by weight, such as at least 60% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the anionic salt group -containing filmforming polymer may be present in the anionic electrodepositable coating composition in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the anionic salt group-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount of 50% to 90% by weight, such as 55% to 80% by weight, such as 60% to 75% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the electrodepositable coating composition may further comprise a curing agent.
  • the curing agent may comprise functional groups that are reactive with the functional groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer to effectuate cure of the coating composition to form a coating.
  • suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.
  • the curing agent may be present in the cationic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the cationic electrodepositable coating composition in an amount of no more than 60% by weight, such as no more than 50% by weight, such as no more than 40% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the cationic electrodepositable coating composition in an amount of 10% to 60% by weight, such as 20% to 50% by weight, such as 25% to 40% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the anionic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the anionic coating composition in an amount of no more than 50% by weight, such as 45% by weight, such as 40% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the curing agent may be present in the anionic electrodepositable coating composition in an amount of 10% to 50% by weight, such as 20% to 45% by weight, such as 25% to 40% by weight based on the total weight of the resin solids of the electrodepositable coating composition.
  • the electrodepositable coating composition may further comprise other optional ingredients, such as a pigment composition and, if desired, various additives such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof.
  • additives such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof.
  • the electrodepositable coating composition may comprise water and/or one or more organic solvent(s).
  • Water can, for example, be present in amounts of at least 40%, such as at least 50% based on total weight of the electrodepositable coating composition.
  • Water can be present in amounts of no more than 90% by weight, such as no more than 75% by weight based on total weight of the electrodepositable coating composition.
  • Water can be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight based on total weight of the electrodepositable coating composition.
  • the organic solvents may typically be present in an amount of less than 10% by weight, such as less than 5% by weight based on total weight of the electrodepositable coating composition.
  • the electrodepositable coating composition may in particular be provided in the form of an aqueous dispersion.
  • the total solids content of the electrodepositable coating composition may be at least 1% by weight, such as at least 5% by weight based on the total weight of the electrodepositable coating composition.
  • the total solids content of the electrodepositable coating composition may be no more than 50% by weight, such as no more than 40% by weight, such as no more than 20% by weight based on the total weight of the electrodepositable coating composition.
  • the total solids content of the electrodepositable coating composition may be from 1% to 50% by weight, such as 5% to 40% by weight, such as 5% to 20% by weight based on the total weight of the electrodepositable coating composition.
  • total solids refers to the non-volatile content of the electrodepositable coating composition, i.e., materials which will not volatilize when heated to 110°C for 15 minutes.
  • the cationic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode.
  • the anionic electrodepositable coating composition may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode.
  • An adherent film of the electrodepositable coating composition is deposited in a substantially continuous manner on the cathode or anode, respectively, when a sufficient voltage is impressed between the electrodes.
  • the applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts.
  • Current density is usually between 1.0 ampere and 15 amperes per square foot (10.8 to 161.5 amperes per square meter) and tends to decrease quickly during the electrodeposition process, indicating formation of a continuous self-insulating film.
  • the coated substrate may be heated to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate.
  • the coated substrate may be heated to a temperature ranging from 230°F to 450°F (110°C to 232.2°C), such as from 275°F to 400°F (135°C to 204.4°C), such as from 300°F to 360°F (149°C to 180°C).
  • the coated substrate may be heated to a temperature ranging from 200°F to 450°F (93°C to 232.2°C), such as from 275°F to 400°F (135°C to 204.4°C), such as from 300°F to 360°F (149°C to 180°C), such as 200°F to 210.2°F (93°C to 99°C).
  • the curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like.
  • the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes.
  • the thickness of the resultant cured electrodeposited coating may range from 10 to 50 microns.
  • a powder coating composition may then be deposited onto at least a portion of the pretreated substrate surface.
  • “powder coating composition” refers to a coating composition in the form of a co-reactable solid in particulate form which is substantially or completely free of water and/or solvent. Accordingly, the powder coating composition disclosed herein is not synonymous to waterborne and/or solvent-bome coating compositions known in the art.
  • the powder coating composition may comprise (a) a film forming polymer having a reactive functional group; and (b) a curing agent having a functional group that is reactive with the functional group of the film-forming polymer.
  • powder coating compositions examples include the polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.) or epoxy-polyester hybrid powder coating compositions.
  • Alternative examples of powder coating compositions that may be used include low temperature cure thermosetting powder coating compositions comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in U.S. Patent No. 7,470,752, assigned to PPG Industries, Inc.
  • curable powder coating compositions generally comprising (a) at least one tertiary aminourea compound, at least one tertiary aminourethane compound, or mixtures thereof, and (b) at least one film-forming epoxy-containing resin and/or at least one siloxane-containing resin (such as those described in U.S. Patent No. 7,432,333, assigned to PPG Industries, Inc. and incorporated herein by reference); and those comprising a solid particulate mixture of a reactive group-containing polymer having a T g of at least 30°C (such as those described in U.S. Patent No. 6,797,387, assigned to PPG Industries, Inc. and incorporated herein by reference).
  • T g may be calculated or measured experimentally using differential scanning calorimetry.
  • the Fox equation may be used to calculate T g : wherein Wi is the weight fraction of component 7, T gi is the glass transition temperature of the homopolymer of component/in absolute temperature units, and the summation is taken over all the components in the copolymer.
  • the powder coating compositions are often applied by spraying, electrostatic spraying, or by the use of a fluidized bed. Other standard methods for coating application of the powder coating also can be employed such as brushing, dipping or flowing. After application of the powder coating composition, the coating is often heated to cure the deposited composition.
  • the heating or curing operation is often carried out at a temperature in the range of from 130°C to 220°C, such as from 170°C to 190°C, for a period of time ranging from 10 minutes to 30 minutes, such 15 minutes to 25 minutes.
  • the thickness of the resultant film is from 50 microns to 125 microns.
  • liquid coating composition refers to a coating composition which contains a portion of water and/or solvent that may be substantially or completely removed from the composition upon drying and/or curing. Accordingly, the liquid coating composition disclosed herein is synonymous to waterborne and/or solvent-borne coating compositions known in the art.
  • the liquid coating composition may comprise, for example, (a) a film forming polymer having a reactive functional group; and (b) a curing agent having a functional group that is reactive with the functional group of the film-forming polymer.
  • the liquid coating may contain a film forming polymer that may react with oxygen in the air or coalesce into a film with the evaporation of water and/or solvents. These film- forming mechanisms may require or be accelerated by the application of heat or some type of radiation such as Ultraviolet or Infrared.
  • liquid coating compositions examples include the SPECTRACRON® line of solvent-based coating compositions, the AQUACRON® line of water-based coating compositions, and the RAYCRON® line of UV cured coatings (all commercially available from PPG Industries, Inc.).
  • Suitable film forming polymers that may be used in the liquid coating composition may comprise a (poly)ester, an alkyd, a (poly)urethane, an isocyanurate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, (poly)vinyl chloride, (poly)olefin, (poly)vinylidene fluoride, (poly) siloxane, or combinations thereof.
  • the film-forming resin may, in examples, be a primer composition and/or a topcoat composition.
  • the primer and/or topcoat compositions may be, for example, chromate- based primers and/or advanced performance topcoats.
  • the primer coat can be a conventional chromate-based primer coat, such as those available from PPG Industries, Inc. (product code 44GN072), or a chrome-free primer such as those available from PPG (DESOPRIME CA7502, DESOPRIME CA7521, Deft 02GN083, Deft 02GN084).
  • the primer coat can be a chromate-free primer coat, such as the coating compositions described in U.S. Patent Application Serial No.
  • the substrate of the present disclosure also may comprise a topcoat.
  • topcoat refers to a mixture of binder(s) which can be an organic or inorganic based polymer or a blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent.
  • a topcoat is typically the coating layer in a single or multi-layer coating system whose outer surface is exposed to the atmosphere or environment, and its inner surface is in contact with another coating layer or polymeric substrate.
  • suitable topcoats include those conforming to MIL-PRF-85285D, such as those available from PPG (Deft 03W127A and Deft 03GY292).
  • the topcoat may be an advanced performance topcoat, such as those available from PPG (Defthane® ELT.TM. 99GY001 and 99W009). However, other topcoats and advanced performance topcoats can be used as will be understood by those of skill in the art with reference to this disclosure.
  • the metal substrate also may comprise a self-priming topcoat, or an enhanced self-priming topcoat.
  • self-priming topcoat also referred to as a “direct to substrate” or “direct to metal” coating, refers to a mixture of a binder(s), which can be an organic or inorganic based polymer or blend of polymers; typically at least one pigment; can optionally contain at least one solvent or mixture of solvents; and can optionally contain at least one curing agent.
  • enhanced self-priming topcoat also referred to as an “enhanced direct to substrate coating” refers to a mixture of functionalized fluorinated binders, such as a fluoroethylene- alkyl vinyl ether in whole or in part with other binder(s), which can be an organic or inorganic based polymer or blend of polymers, typically at least one pigment, can optionally contain at least one solvent or mixture of solvents, and can optionally contain at least one curing agent.
  • binder(s) typically at least one pigment
  • self-priming topcoats include those that conform to TT-P-2756A.
  • self-priming topcoats examples include those available from PPG (03W169 and 03GY369), and examples of enhanced self-priming topcoats include Defthane® ELTTM/ESPT and product code number 97GY 121, available from PPG.
  • other self-priming topcoats and enhanced self-priming topcoats can be used in the coating system, as will be understood by those of skill in the art with reference to this disclosure.
  • the self-priming topcoat and enhanced self-priming topcoat may be applied directly to the pretreated substrate.
  • the self-priming topcoat and enhanced self-priming topcoat can optionally be applied to an organic or inorganic polymeric coating, such as a primer or paint film.
  • the self-priming topcoat layer and enhanced self-priming topcoat is typically the coating layer in a single or multi-layer coating system where the outer surface of the coating is exposed to the atmosphere or environment, and the inner surface of the coating is typically in contact with the substrate or optional polymer coating or primer.
  • the topcoat, self-priming topcoat, and enhanced self-priming topcoat can be applied to the pretreated substrate, in either a wet or “not fully cured” condition that dries or cures over time, that is, solvent evaporates and/or there is a chemical reaction.
  • the coatings can dry or cure either naturally or by accelerated means, for example, an ultraviolet light cured system, to form a film or “cured” paint.
  • a colorant and, if desired, various additives such as surfactants, wetting agents or catalyst can be included in the coating composition (electrodepositable, powder, or liquid).
  • the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition.
  • Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions.
  • the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect.
  • the coating composition may comprise the colorant in an amount of 1% by weight to 65% by weight, such as from 3% by weight to 40% by weight, such as 5% by weight to 35% by weight, based on the total weight of the coating composition.
  • the substrate may further comprise a coating composition.
  • the coating composition may comprise, or consist essentially of, or consist of, a film-forming resin.
  • the coating composition may be on at least a portion of the substrate surface that was treated with one of the pretreatment compositions described herein.
  • the coating composition may have been deposited by any suitable technique, including, for example, brushing, dipping, flow coating, spraying and the like.
  • the coating composition may be electrodeposited.
  • depositing of a coating composition comprises a powder coating step.
  • the coating composition may be a liquid coating composition.
  • Suitable substrates that may be used include metal substrates, metal alloy substrates, and/or substrates that have been metallized, such as nickel-plated plastic.
  • the metal or metal alloy can comprise or be steel, aluminum, zinc, nickel, and/or magnesium.
  • the steel substrate could be cold rolled steel, hot rolled steel, electrogalvanized steel, and/or hot dipped galvanized steel.
  • Aluminum alloys may comprise, for example, 0.01% by weight copper to 10% by weight copper.
  • Aluminum alloys which are treated may also include castings, such as IXX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g., A356.0).
  • Magnesium alloys of the AZXX (including Eform Plus), AMXX, EVXX, ZKXX, ZEXX, ZCXX, HKXX, HZXX, QEXX, QHXX, WEXX, ZEK100, or Elektron 21 series also may be used as the substrate.
  • the substrate used may also comprise titanium and/or titanium alloys, zinc and/or zinc alloys, and/or nickel and/or nickel alloys.
  • Suitable substrates for use include those that are often used in the assembly of a vehicle, such as vehicular bodies (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft), a vehicular frame, vehicular parts, motorcycles, wheels, industrial structures and components such as appliances, including washers, dryers, refrigerators, stoves, dishwashers, and the like, personal electronics, agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, heat exchangers, lawn furniture, and other articles.
  • vehicular bodies e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft
  • vehicular frames e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and/or stringers, rivets, landing gear components, and/or skins used on an aircraft
  • vehicle or variations thereof includes, but is not limited to, aircraft, including civilian, commercial and military aircraft, and/or land vehicles such as automobiles, motorcycles, and/or trucks.
  • the metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part.
  • a suitable substrate for use includes an article.
  • the substrate may be a multi-metal article.
  • multi-metal article refers to (1) an article that has at least one surface comprised of a first metal and at least one surface comprised of a second metal that is different from the first metal, (2) a first article that has at least one surface comprised of a first metal and a second article that has at least one surface comprised of a second metal that is different from the first metal, or (3) both (1) and (2).
  • the substrate may comprise a three-dimensional component formed by an additive manufacturing process such as selective laser melting, e-beam melting, directed energy deposition, binder jetting, metal extrusion, and the like.
  • the three- dimensional component may be a metal and/or resinous component.
  • a substrate to be treated with only the pretreatment composition, eliminating the separate deoxidizing step.
  • treatment of a substrate with a pretreatment composition comprising a lanthanide series metal and a fluorometallic acid, an organophosphate, an organophosphonate, or combinations thereof provides superior corrosion performance over a pretreatment composition comprising only a lanthanide series metal and an oxidizing agent.
  • a pretreatment composition comprising a lanthanide series metal, a carboxylic acid, and an oxidizing agent in an amount of no more than 70 ppm provides superior corrosion performance over a pretreatment composition comprising a lanthanide series metal, a carboxylic acid, and an oxidizing agent in amounts greater than 70 ppm.
  • Chemkleen 2010LP a phosphate-free alkaline cleaner available from PPG Industries, Inc.
  • Chemkleen 181 ALP a phosphate-free blended surfactant additive available from PPG Industries, Inc.
  • a 10-gallon solution 500 mL of Chemkleen 2010LP and 50mL of Chemkleen 181ALP were added in the DI water and the solution was heated to ⁇ 120°F using a self-constructed immersion heater.
  • the native oxide layer of the metal substrate was removed by cleaning the substrate surface with acetic acid.
  • Acetic acid (99.5%) was purchased from Thermofisher Acros Organics (Geel, Belgium).
  • To prepare the deoxidizing composition 11.11 liters of deionized water were added to a clean 3-gallon plastic bucket. Subsequently, acetic acid (0.227 liter) was added in the bath and the solution was heated to 120°F and maintained under high stirring using the immersion heater. The pH was adjusted to 2.5.
  • Potassium bifluoride (99.3%) was purchased from Sigma-Aldrich (St. Louis, MO), and hydrofluorosilicic acid (23%) and sodium hydroxide were purchased from Thermofisher Acros Organics (Geel, Belgium).
  • the pH of compositions was measured as indicated below using a pH meter (DualStar pH/ISE Dual Channel Benchtop Meter, available from ThermoFisher Scientific, Waltham, Massachusetts, USA; pH probe, Fisher Scientific Accumet pH probe (Ag/AgCl reference electrode)) by immersing the pH probe in the composition.
  • Total fluoride was calculated by estimating the stoichiometric concentration of fluoride in the pretreatment composition and converting to parts per million (ppm).
  • E-form plus magnesium substrate was provided by USAMP from POSCO (Pohang, SK). E-form plus substrates were cut from 24” by 40” to 4” by 6” using a panel cutter prior to application of the alkaline cleaner.
  • Aluminum alloy AA6111 and AA6022 substrates were purchased from ACT (Michigan, United States). Hot-dipped galvanized (HDG) substrates were purchased from ACT and Chemetall (Frankfurt, Germany).
  • Aluminum and HDG (ACT) substrates were cut from 4” by 12” to 4” by 6” using a panel cutter prior to application of the alkaline cleaner.
  • HDG (Chemetall) substrates were used in their original dimensions of 4” by 7.5.” Cut samples were treated either by Process A or Process B as listed in Table 2.
  • E-form plus control panels were treated following Process A. Panels were spray cleaned and degreased for 120 seconds at 10-15 psi in the alkaline cleaner (120°F) using Vee-jet nozzles and rinsed with deionized (DI) water by immersing in a deionized water bath (75°F) for 30 seconds followed by a deionized water spray rinse using a Melnor Rear-Trigger 7- Pattem nozzle set to shower mode (available from Home Depot). Cleaned substrates were immersed in the deoxidizer composition at 120°F for 120 seconds under high agitation and then were rinsed by a DI water spray rinse using a Melnor Rear-Trigger 7-Pattern nozzle set to shower mode for 30 seconds.
  • DI deionized
  • panels were immersed in a bath containing PT-1 for 120 seconds at room temperature. During the immersion a low agitation was maintained in the composition via manually shaking the panel holders.
  • Pretreated substrates were rinsed by a deionized water spray using a Melnor Rear-Trigger 7-Pattem nozzle set to shower mode (75°F) for 30 seconds and dried with hot air for approximately 120 seconds using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting.
  • Pretreated substrates were rinsed by a deionized water spray using a Melnor Rear-Trigger 7-Pattem nozzle set to shower mode (75°F) for 30 seconds and dried with hot air for approximately 120 seconds using a Hi-Velocity handheld blow-dryer made by Oster® (model number 078302-300-000) on high-setting.
  • a subset of electrocoated panels were X-scribed on one side of the panel.
  • panels were placed in ASTM G85 A2 testing for a minimum of one week (i.e., 21 cycles) or CASS (Copper Accelerated Acetic Acid Salt Spray) testing for a minimum of one week. After exposure, panels were dried under ambient conditions. The loose coating around the X-scribe was removed by applying a scotch filament tape (3M Industries Adhesives and Tapes Divisions, St. Paul, MN) and pulling it off. Afterwards, the width of exposed metal region along the scribe was recorded for 10-12 locations on each panel and averaged to assess the corrosion performance of the panel.
  • scotch filament tape (3M Industries Adhesives and Tapes Divisions, St. Paul, MN)
  • scribe creep refers to the area of paint loss around the scribe either through corrosion or disbondment (e.g., affected paint to affected paint).
  • corrosion or disbondment e.g., affected paint to affected paint.
  • PT-2, PT-4, PT-6, PT-8, or PT-9 (8 panels per pretreatment) according to Process B and panels were with PT-3, PT-5, PT-7, PT-10, and PT-11 (4 panels per pretreatment) according to Process B. All of the panels were then electrocoated with EPIC 200 as described above.
  • Four of the panels treated with each pretreatment composition were exposed to CASS corrosion testing (10 days) and four of the panels treated with each pretreatment composition were exposed to ASTM G85 A2 testing (21 cycles). Corrosion performance data are reported in FIGS. 1 and 2.
  • Example 1 demonstrates that E-form plus panels treated with PT-2 to PT- 10 demonstrated improved corrosion performance compared to panels treated with PT-1.
  • E-form plus panels treated with PT-2 to PT-9 and PT- 11 exhibited lower average scribe width compared to panels treated with PT-1 when subjected to CASS and G-85 corrosion testing.
  • E-form plus panels treated with PT- 10 and PT- 10 showed better corrosion performance than panels treated with PT-1 when subjected to ASTM G85 A2 testing.
  • E-form plus panels were treated with each of PT-3, PT-12, and PT-13 (4 panels per pretreatment) and 8 E-form plus panels were treated with PT-6 according to Process B. All of the panels were then electrocoated with EPIC 200 as described above. Four of the panels treated with each pretreatment composition were exposed to CASS corrosion testing (10 days) and four of the panels treated with each pretreatment composition were exposed to ASTM G85 A2 testing (21 cycles). Corrosion performance data are reported in FIGS. 3 and 4.
  • Example 2 demonstrates that removal of hydrogen peroxide from a composition comprising acetic acid either improves corrosion performance of E-form plus substrates (as suggested by CASS corrosion testing) or provides comparable corrosion performance (as suggested by ASTM G85 A2 testing).
  • Example 3 demonstrates that E-form plus panels treated with PT-2, PT-4, or PT-6 to PT- 10 demonstrate improved dry adhesion performance compared to panels treated with PT-1. Additionally, E-form plus panels treated with PT-4 or PT-6 exhibited improved wet adhesion performance compared to panels treated with PT-1.
  • Example 4
  • AA6111 alloy substrates were treated with PT-2 (2 panels), PT-3 (4 panels), PT-4
  • AA6111 alloy substrates were treated with PT-1 (6 panels) according to Process A. Panels were then electrocoated with EPIC 200 as described above. A subset of electrocoated panels were then exposed to CASS testing (20 days) as follows: PT-1 (4 panels), PT-2 to PT-5 (2 panels), PT-6 (4 panels), PT-7 (2 panels), PT- 8 (6 panels), PT-9 (2 panels), PT-10 (6 panels), or PT-11 (2 panels).
  • Example 4 demonstrates that AA 6111 panels treated with one of PT-2 to PT-8 or PT- 10 exhibit comparable or smaller average scribe creep when subjected to CASS testing compared to panels treated with PT-1.
  • AA6111 panels treated with PT-8 exhibited superior corrosion performance when subjected to ASTM G85 A2 testing compared to panels treated with PT-1.
  • AA6111 panels treated with PT-3, PT-5, PT-6, PT-10, or PT-11 exhibit comparable scribe creep compared to panels treated with PT-1.
  • AA6022 panels were treated with PT-3 (4 panels), PT-5 (4 panels), PT-6 (4 panels), PT-8 (4 panels), PT-10 (4 panels), or PT-11 (4 panels) according to Process B or PT-1 (4 panels) according to Process A (Table 2). Panels were then electrocoated with EPIC 200 as described above. Half of the panels treated with each pretreatment composition were exposed to CASS testing (20 days) and the other half were exposed to ASTM G85 A2 testing (42 cycles) and corrosion performance was evaluated. Corrosion performance data are reported in FIGS. 8 and 9.
  • Example 5 demonstrates that AA6022 panels treated with PT-3, PT-5, PT-8, PT- 10, or PT- 11 exhibit a smaller average scribe creep compared to panels treated with PT-1 when subjected to CASS testing and ASTM G85 A2 testing. AA6022 panels treated with PT-6 exhibit a comparable scribe creep compared to panels treated with PT-1 when subjected to CASS testing.
  • HDG panels were treated with one of PT-3, PT-5, PT-6, PT-8, PT- 10, or PT-11 (2 panels per treatment) according to Process B and 2 panels were treated with PT-1 according to Process A. Panels were then electrocoated with EPIC 200 as described above. Panels were subjected to GM 14872 testing (80 cycles) and then evaluated for corrosion performance. Data are reported in FIG. 10.
  • Example 6 demonstrates that HDG panels treated with PT-3, PT-5, PT-6, PT- 10, or PT-11 exhibit a comparable corrosion performance compared to PT-1.
  • AA6111 panels were treated with each of PT-2, PT-4, or PT-6 to PT-10 (2 panels per treatment) according to Process B and 2 panels were treated with PT-1 according to Process A. Panels were then electrocoated with EPIC 200 and top coated with a standard primer, basecoat, and a clearcoat as described above. Adhesion performance was evaluated by cross hatch analysis. Data are reported in FIG. 11.
  • Example 7 demonstrates that AA6111 panels treated with PT-2, PT-4, or PT-6 to PT-10 exhibit an improved dry adhesion performance compared to panels treated with PT-1.
  • AA6111 panels treated with PT-2, PT-4, PT-6, PT-7, PT-9, or PT-10 exhibit either comparable or improved wet adhesion performance compared to panels treated with PT-1.

Abstract

L'invention divulgue une composition de prétraitement comprenant un métal de la série des lanthanides ; un oxydant ; et un acide fluorométallique, un composé organophosphate, un composé organophosphonate, ou des combinaisons de ceux-ci. L'invention divulgue également une composition de prétraitement comprenant un métal de la série des lanthanides ; un acide carboxylique ; et un oxydant dans une quantité inférieure ou égale à 70 ppm sur la base du poids total de la composition de prétraitement. L'invention divulgue aussi un système de traitement d'un substrat comprenant une composition de nettoyage et l'une des compositions de prétraitement de l'invention. L'invention divulgue par ailleurs des procédés de traitement d'un substrat comprenant la mise en contact d'au moins une partie du substrat avec l'une des compositions de prétraitement selon l'invention. L'invention divulgue de même des substrats comprenant une surface ayant un film sur au moins une partie de celui-ci, le film étant formé à partir de l'une des compositions de prétraitement de l'invention. L'invention divulgue en outre des substrats traités avec l'un quelconque des systèmes ou procédés de l'invention.
PCT/US2022/079378 2022-01-06 2022-11-07 Compositions, systèmes et procédés de traitement d'un substrat WO2023132989A1 (fr)

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Citations (5)

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WO2003093532A2 (fr) * 2002-04-29 2003-11-13 Ppg Industries Ohio, Inc. Revetements de conversion comprenant des complexes alcalino-terreux de fluorure metallique
US6797387B2 (en) 2000-09-21 2004-09-28 Ppg Industries Ohio Inc. Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers
US20070272900A1 (en) * 2004-12-08 2007-11-29 Masayuki Yoshida Composition for Metal Surface Treatment, Treating Liquid for Surface Treatment, Method of Surface Treatment, and Surface-Treated Metal Material
US7432333B2 (en) 2002-05-31 2008-10-07 Ppg Industries Ohio, Inc. Powder coating of amino-urea or urethane catalyst and epoxy/hydroxy and/or siloxane resin
US20090045071A1 (en) 2007-08-15 2009-02-19 Ppg Industries Ohio, Inc. Electrodeposition coatings for use over aluminum substrates

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US6797387B2 (en) 2000-09-21 2004-09-28 Ppg Industries Ohio Inc. Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers
WO2003093532A2 (fr) * 2002-04-29 2003-11-13 Ppg Industries Ohio, Inc. Revetements de conversion comprenant des complexes alcalino-terreux de fluorure metallique
US7432333B2 (en) 2002-05-31 2008-10-07 Ppg Industries Ohio, Inc. Powder coating of amino-urea or urethane catalyst and epoxy/hydroxy and/or siloxane resin
US7470752B2 (en) 2002-05-31 2008-12-30 Ppg Industries Ohio, Inc. Powder coating of amino-urea or urethane catalyst and epoxy and/or siloxane resin
US20070272900A1 (en) * 2004-12-08 2007-11-29 Masayuki Yoshida Composition for Metal Surface Treatment, Treating Liquid for Surface Treatment, Method of Surface Treatment, and Surface-Treated Metal Material
US20090045071A1 (en) 2007-08-15 2009-02-19 Ppg Industries Ohio, Inc. Electrodeposition coatings for use over aluminum substrates

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