WO2023102284A1 - Systèmes et procédés de traitement d'un substrat - Google Patents

Systèmes et procédés de traitement d'un substrat Download PDF

Info

Publication number
WO2023102284A1
WO2023102284A1 PCT/US2022/077333 US2022077333W WO2023102284A1 WO 2023102284 A1 WO2023102284 A1 WO 2023102284A1 US 2022077333 W US2022077333 W US 2022077333W WO 2023102284 A1 WO2023102284 A1 WO 2023102284A1
Authority
WO
WIPO (PCT)
Prior art keywords
ppm
pretreatment composition
composition
substrate
pretreatment
Prior art date
Application number
PCT/US2022/077333
Other languages
English (en)
Inventor
Kristi Maree ALLEN
Rachel Dory HARRIS
Abdulrahman Dawoud IBRAHIM
Silvia BEZER
Lyanne VALDEZ
Original Assignee
Ppg Industries Ohio, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Publication of WO2023102284A1 publication Critical patent/WO2023102284A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/20—Orthophosphates containing aluminium cations
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the present disclosure relates to compositions, systems, and methods for treating a substrate.
  • a pretreatment composition comprising at least 25 ppm of a phosphonate based on total weight of the pretreatment composition; at least 6 ppm of zinc based on total weight of the pretreatment composition; and a pH of 6.0 or less.
  • a system for treating a substrate comprising a cleaning composition; and one of the pretreatment compositions disclosed herein.
  • FIG. 1 shows FIB-EDS-TEM of an Eform Plus magnesium substrate treated with Pretreatment 1 (PT 1) followed by an alkaline cleaner according to Example 2.
  • FIG. 1A shows a high-angle annular diffraction TEM micrograph.
  • FIGS. IB - IE are TEM micrographs overlaid with elemental maps (IB, magnesium; 1C, oxygen, ID, phosphorous; IE, zinc) as determined by EDS.
  • FIG. 2 shows FIB-EDS-TEM of an Eform Plus magnesium substrate treated with an alkaline cleaner and no pretreatment according to Example 2.
  • FIGS. 2B - 2E show TEM micrographs overlaid with elemental maps (2B, magnesium; 2C, oxygen; 2D, phosphorous, 2E, zinc) as determined by EDS.
  • FIG. 3 shows an XPS depth profile of Eform Plus magnesium substrates treated with (3A) alkaline cleaner and no pretreatment, (3B) alkaline cleaner and PT 1 (ZnO + HEDP), (3C) alkaline cleaner and PT 7 (ZnO), and (3D) alkaline cleaner and PT 2 (HEDP) as a function of atomic percent.
  • FIG. 4 shows a bar graph showing the deposition of phosphorous and zinc (counts) measured using X-ray fluorescence (XRF) on Eform Plus magnesium panels treated with alkaline cleaner alone, alkaline cleaner and PT 2 (HEDP), alkaline cleaner and PT 7 (ZnO), and alkaline cleaner and PT 1 (ZnO + HEDP).
  • XRF X-ray fluorescence
  • 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.
  • a “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 predominately water.
  • aqueous medium may comprise water in an amount of more than 50 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 a discontinuous phase, e.g., metal particles, are dispersed in a continuous phase such as an aqueous medium, which includes water.
  • derivative refers to a compound that may arise from another compound if one atom or group of atoms is replaced with another atom or group of atoms.
  • a derivative of etidronic acid may arise from replacing a hydroxide group with an alkoxide group.
  • 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.
  • a “coating composition” refers to a composition, e.g., a solution, a 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 a composition is being applied to a substrate, e.g., at 10°C to 32°C and 5% to 80% relative humidity, while slightly thermal conditions are temperatures that are slightly above ambient temperature (e.g., greater than 32°C to 40°C).
  • the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is only present 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 only present in an amount of 1 ppm or less based on a total weight of the mixture or composition, respectively.
  • the term “completely free” means that a mixture or composition, respectively, does not comprise a particular material, i.e., the mixture or composition comprises 1 ppb or less of such material based on a total weight of the mixture or composition, or that such material is below the detection limit of common analytical techniques.
  • total composition weight refers to the total weight of all ingredients being present in the respective composition including any solvents.
  • phosphonates are compounds comprising C-PO(OR)2 groups, wherein R may independently be an alkyl group, an aryl group, or an H.
  • phosphonic acids are compounds comprising C-PO(OH)2 or C- PO(OR)2 groups, wherein R may be an H, an alkyl group, or an aryl group, wherein at least one R comprises an H.
  • monopho sphonic acid means a compound that has one phosphonic acid moiety.
  • diphosphonic acid means a compound that has two phosphonic acid moieties.
  • polypho sphonic acid means a compound having more than two phosphonic acid moieties.
  • organic compounds means compounds that comprise at least one covalent bond between a carbon and another element, such as another carbon, hydrogen, oxygen, and/or nitrogen.
  • organic compounds other than phosphonates or phosphonic acids means an organic compound that is not a phosphonate or a phosphonic acid, compound comprising C-PO(OR)2 groups, wherein R may be an alkyl group, an aryl group, or an H and/or phosphonic acids comprising C-PO(OH)2 or C-PO(OR)2 groups, wherein R may be an H, an alkyl group, or an aryl group, wherein at least one R comprises an H.
  • alkaline means a composition comprising a pH greater than 7.0.
  • the present disclosure is directed to a pretreatment composition, the pretreatment composition comprising, consisting essentially of, or consisting of at least 25 ppm of a phosphonate based on total weight of the pretreatment composition; 6 ppm of zinc based on total weight of the pretreatment composition; and a pH of 6.0 or less.
  • the pretreatment composition may comprise a phosphonate.
  • the molecular weight (Mw) of the phosphonate may be at least 100 g/mol, such as at least 200 g/mol, such as at least 1,000 g/mol, such as at least 1,500 g/mol, such as at least 10,000 g/mol, such as at least 15,000 g/mol.
  • the Mw of the phosphonate may be no more than 50,000 g/mol, such as no more than 40,000 g/mol, such as no more than 30,000 g/mol, such as no more than 1,000 g/mol, such as no more than 600 g/mol.
  • the Mw of the phosphonate may be 100 g/mol to 50,000 g/mol, such as 100 g/mol to 1,000 g/mol, such as 100 g/mol to 600 g/mol, such as 200 g/mol to 1,000 g/mol, such as 200 g/mol to 600 g/mol, such as 1,000 g/mol to 40,000 g/mol, such as 1,500 g/mol to 50,000 g/mol, such as 1,500 g/mol to 30,000 g/mol, such as 10,000 g/mol to 50,000 g/mol, such as 15,000 g/mol to 40,000 g/mol.
  • Mw refers to the weight average molecular weight as determined by Gel Permeation Chromatography using Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), using polystyrene standards, tetrahydrofuran (THF) as the eluent at a flow rate of 1 ml min 1 , and two PL Gel Mixed C columns for separation.
  • RI detector Waters 410 differential refractometer
  • the phosphonate may comprise at least 1 carbon atom, such as at least 5 carbon atoms, such as at least 25 carbon atoms, such as at least 150 carbon atoms, such as at least 200 carbon atoms.
  • the phosphonate may comprise no more than 1,000 carbon atoms, such as no more than 750 carbon atoms, such as no more than 50 carbon atoms, such as no more than 15 carbon atoms.
  • the phosphonate may comprise 1 to 1,000 carbon atoms, such as 1 to 15 carbon atoms, such as 5 to 50 carbon atoms, such as 25 to 1,000 carbon atoms, such as 150 to 1,000 carbon atoms, such as 200 to 750 carbon atoms.
  • the phosphonate may comprise a phosphonic aid.
  • the phosphonic acid may comprise a mononphosphonic acid, a diphosphonic acid, a polyphosphonic acid, or combinations thereof.
  • the diphosphonic acid may comprise etidronic acid or derivatives thereof.
  • Suitable phosphonic acids may comprise ethylenediamine tetra(methylenephosphonic) acid (EDTMP), diethylenetriaminepenta(methylene-phosphonic acid) (DTPMPA), iminodi(methylphosphonic acid), N-(phosphonomethyl)iminodiacetic acid hydrate, (aminomethyl)phosphonic acid, glyphosate, methylenediphosphonic acid, N,N- bis(phosphonomethyl)glycine, glyphosine, 2-phosphono 1,2,4-butane tricarboxylic acid (PBTC), aminotris(methylenephosphonic acid) (ATMP aminotris), polyvinylphosphonic acid (PVPA), or combinations thereof.
  • ETMP ethylenediamine tetra(methylenephosphonic) acid
  • DTPMPA diethylenetriaminepenta(methylene-phosphonic acid)
  • iminodi(methylphosphonic acid) N-(phosphonomethyl)iminodiacetic acid hydrate
  • the pretreatment composition may comprise the phosphonate in an amount of at least 25 ppm based on total weight of the pretreatment composition, such as at least 30 ppm, such as at least 40 ppm, such as at least 500 ppm, such as at least 2,000 ppm, such as at least 4,000 ppm.
  • the pretreatment composition may comprise the phosphonate in an amount of no more than 60,000 ppm based on total weight of the pretreatment composition, such as no more than 55,000 ppm, such as no more than 50,000 ppm.
  • the pretreatment composition may comprise the phosphonate in an amount of 25 ppm to 60,000 ppm based on total weight of the pretreatment composition, such as 30 ppm to 55,000 ppm, such as 40 ppm to 50,000 ppm, such as 500 ppm to 55,000 ppm, such as 2,000 ppm to 55,000 ppm, such as 4,000 ppm to 55,000 ppm, such as 500 ppm to 50,000 ppm, such as 2,000 ppm to 50,000 ppm, such as 4,000 ppm to 50,000 ppm.
  • the pretreatment composition may comprise zinc.
  • the zinc may be provided in the form of a compound comprising zinc or a salt comprising zinc, or a combination thereof.
  • Suitable compounds of zinc include, but are not limited to, zinc oxide, zinc hydroxide, zinc nitrate, zinc sulfate, zinc chloride, zinc chlorate, or combinations thereof.
  • the pretreatment composition may comprise zinc in an amount of at least 6 ppm based on total weight of the pretreatment composition, such as at least 100 ppm, such as at least 500 ppm, such as at least 1,000 ppm, such as at least 1,500 ppm.
  • the pretreatment composition may comprise zinc in an amount of no more than 15,000 ppm based on total weight of the pretreatment composition, such as no more than 12,000 ppm, such as no more than 10,000 ppm, such as no more than 7,500 ppm.
  • the pretreatment composition may comprise zinc in an amount of 6 ppm to 15,000 ppm based on total weight of the pretreatment composition, such as 100 ppm to 15,000 ppm, such as 100 ppm to 12,000 ppm, such as 100 ppm to 10,000 ppm, such as 100 ppm to 7,500 ppm, such as 500 ppm to 12,000 ppm, such as 500 ppm to 10,000 ppm, such as 750 ppm to 7,500 ppm, such as 1,000 ppm to 10,000 ppm, such as 1,500 ppm to 7,500 ppm.
  • the pretreatment composition may comprise free fluoride.
  • 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 Thermoscientific, the symphony® Fluoride Ion Selective Combination Electrode supplied by VWR International, or similar electrodes. See, e.g., Light and Cappuccino, Determination of fluoride in toothpaste using an ion-selective electrode, J. Chem.
  • 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 may be read directly.
  • Examples of compounds to be added to adjust the fluoride level include, but are not limited to, ammonium bifluoride, potassium hydrogen fluoride, and yttrium nitrate.
  • the pretreatment composition may comprise free fluoride in an amount of at least 15 ppm based on a total weight of the pretreatment composition, such as at least 50 ppm, such as at least 100 ppm, such as at least 150 ppm, such as at least 200 ppm.
  • the pretreatment composition may comprise free fluoride in an amount of no more than 750 ppm based on a total weight of the pretreatment composition, such as no more than 700 ppm, such as no more than 650 ppm, such as no more than 600 ppm, such as no more than 550 ppm.
  • the pretreatment composition may comprise free fluoride in an amount of 15 ppm to 750 ppm free fluoride based on a total weight of the pretreatment composition, such as 50 ppm to 700 ppm, such as 100 ppm to 650 ppm, such as 150 ppm to 600 ppm, such as 200 ppm to 550 ppm.
  • pretreatment composition may comprise a pH of 6.0 or less, such as 5.0 or less, such as 4.0 or less.
  • the pretreatment composition may comprise a pH of at least 0.3, such as at least 0.5, such as at least 0.8, such as at least 0.9, such as at least 1.0, such as at least 1.5, such as at least 2.0.
  • the pretreatment composition may comprise a pH of 0.3 to 6.0, such as 0.3 to 5.0, such as 0.3 to 4.0, such as 0.5 to 6.0, such as 0.5 to 5.0, such as 0.5 to 4.0, such as 0.8 to 6.0, such as 0.8 to 5.0, such as 0.8 to 4.0, such as 1.0 to 6.0, such as 1.0 to 5.0, such as 1.0 to 4.0, such as 1.5 to 4.0, such as 2.0 to 4.0.
  • the pH may be adjusted using, for example, any acid/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 phosphoric acid.
  • the pH of the 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 diisopropanolamine, triethylamine, dimethyethanolamine, 2-amino-2methylpropanol, methylethyl amine, or combinations thereof.
  • bases such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines such as diisopropanolamine, triethylamine, dimethyethanolamine, 2-amino-2methylpropanol, methylethyl amine, or combinations thereof.
  • the base can partially or completely neutralize the phosphonate compounds to enhance the solubility of the phosphonate compounds.
  • the pretreatment composition 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 compounds 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 from the pretreatment composition may be substantially free, may be essentially free, and/or may be completely free of one or more of any of the elements or compounds in the preceding paragraph.
  • material formed on a substrate surface from the pretreatment composition may be substantially free of chromium or derivates thereof meaning 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.
  • essentially free when used with respect to chromium, means that the pretreatment compositions and/or deposited material contains less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any at all.
  • completely free when used with respect to chromium, means that the pretreatment composition comprises 0 ppm of such material or that such material is below the detection limit of common analytical techniques.
  • the pretreatment composition may be substantially free, essentially free, or completely free of organic compounds other than phosphonates or phosphonic acids.
  • the pretreatment composition may comprise a carrier, often an aqueous medium, so that the pretreatment composition is in the form of a solution or dispersion.
  • the pretreatment composition may be an aqueous composition.
  • the pretreatment composition may optionally contain other materials in addition to those described above, such as surfactants and other auxiliaries conventionally used in the art of pretreatment.
  • water-soluble 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; and combinations thereof.
  • 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 composition 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, citric acid 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, citric acid iron compounds, bromate ions, chlorate ions, and chlorite ions, as well as ascorbic acid, citric acid, tartaric acid, malonic
  • Suitable resins include reaction products of one or more alkanolamines and an epoxy-functional material containing at least two epoxy groups, such as those disclosed in United States Patent No. 5,653,823, incorporated herein by reference.
  • such resins contain beta hydroxy ester, imide, or sulfide functionality, incorporated by using dimethylolpropionic acid, phthalimide, or mercaptoglycerine as an additional reactant in the preparation of the resin.
  • the reaction product is that of the diglycidyl ether of Bisphenol A (commercially available from Shell Chemical Company as EPON 880), dimethylol propionic acid, and diethanolamine in a 0.6 to 5.0:0.05 to 5.5:1 mole ratio.
  • Suitable resinous binders include water soluble and water dispersible polyacrylic acids as disclosed in United States Patent Nos. 3,912,548 and 5,328,525, disclosed herein by reference; phenol formaldehyde resins as described in United States Patent No. 5,662,746, disclosed herein by reference; water soluble polyamides such as those disclosed in WO 95/33869, disclosed herein by reference; copolymers of maleic or acrylic acid with allyl ether as described in Canadian patent application 2,087,352, disclosed herein by reference; and water soluble and dispersible resins including epoxy resins, aminoplasts, phenol-formaldehyde resins, tannins, and polyvinyl phenols as discussed in United States Patent No. 5,449,415, disclosed herein by reference.
  • the pretreatment composition may comprise the resinous binder in an amount of 0.005 percent to 30 percent by weight, such as 0.5 to 3 percent by weight, based on the total weight of the pretreatment composition.
  • the pretreatment composition may be substantially free or, in some cases, completely free of any resinous binder.
  • substantially free when used in reference to the absence of resinous binder in the pretreatment composition, means that any resinous binder is present in the pretreatment composition in a trace amount of less than 0.005 percent by weight.
  • completely free means that there is no resinous binder in the pretreatment composition at all.
  • the present disclosure also is directed to a system for treating a substrate.
  • the system may comprise, or may consist essentially of, or may consist of, a cleaning composition and a pretreatment composition disclosed herein.
  • the pretreatment composition can be any pretreatment composition as described herein.
  • the system may comprise, or may consist essentially of, or may consist of a cleaning composition; and a pretreatment composition comprising, or consisting essentially of, or consisting of, at least 25 ppm of a phosphonate based on total weight of the pretreatment composition, at least 6 ppm of zinc based on total weight of the pretreatment composition, and a pH of 6.0 or less.
  • the cleaning composition may be an alkaline cleaning composition.
  • 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. (Cleveland, OH), and any of the DFM Series, RECC 1001, and 88X1002 cleaners (commercially available from PRC-DeSoto International, Sylmar, CA), and Turco 4215-NCLT and Ridolene (commercially available from Henkel Technologies, Madison Heights, MI).
  • the cleaning composition may comprise a pH of at least 10.0, such as at least 10.5.
  • the system of the present disclosure may further comprise, or may consist essentially of, or may consist of, a film-forming composition.
  • the film-forming composition may comprise, or may consist essentially of, or may consist of, a coating composition.
  • the coating composition may comprise, or consist essentially of, or consist of, a film-forming resin. 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.
  • 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.
  • 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 the substrate by an electrocoating step wherein the electrodepositable coating composition is deposited onto the metal 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.
  • 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 Unites States Patent Application Publication No. 2009/0045071 at [0004]-[0015] and United States Patent Application Serial No. 13/232,093 at [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 50% to 90%, such as 55% to 80%, such as 60% to 75% 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 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 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 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 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), 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 minutes 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.
  • 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 United States Patent No. 7,470,752, assigned to PPG Industries, Inc.
  • 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 as 15 minutes to 25 minutes.
  • the thickness of the resultant film is typically 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-bome 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 or 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 isocyanate, a (poly)urea, a (poly)epoxy, an anhydride, an acrylic, a (poly)ether, a (poly)sulfide, a (poly)amine, a (poly)amide, a (poly)vinyl chloride, a (poly)olefin, a (poly)vinylidene fluoride, a (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 topcoats can be any of the described herein below.
  • 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 United States Patent Application Serial No.
  • the present disclosure also is directed to a method for treating a substrate.
  • the method may comprise, or may consist essentially of, or may consist of, contacting at least a portion of the substrate surface with a pretreatment composition disclosed herein.
  • the solution or dispersion of the pretreatment composition may be spontaneously applied or contacted to the substrate surface.
  • the solution or dispersion of the pretreatment composition may be brought into contact with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or roll-coating.
  • 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.
  • 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 (70°F) to 48°C (120°F).
  • spontaneous when used with respect to a pretreatment composition, refers to a pretreatment composition that is capable of reacting with and chemically altering the substrate surface and binding to it to form a protective layer in the absence of an externally applied voltage.
  • the method may further comprise contacting at least a portion of the substrate surface with a cleaning composition prior to contacting with the pretreatment composition disclosed herein.
  • the cleaning composition can be any cleaning composition as discussed above in the context of the system disclosed herein.
  • 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 cleaning composition; and then contacting at least a portion of the surface with a pretreatment composition.
  • the cleaning composition may comprise an alkaline pH.
  • 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.
  • a surface treatment composition excluding water rinses
  • surface treatment refers to treatment or contact 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 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, or may consist essentially of, or may consist of contacting at least a portion of the surface of the substrate with a coating composition following the contacting with the pretreatment composition.
  • the coating composition can be any coating composition as discussed above in the context of the system disclosed herein.
  • the coating composition may comprise, or may consist essentially of, or may consist of a film-forming resin.
  • the coating composition may, for example, be applied by electrodeposition, as detailed above.
  • the present disclosure also may be directed to a substrate comprising a film on at least a portion thereof formed from a pretreatment composition disclosed herein.
  • the substrate may comprise a film on at least a portion thereof formed from a pretreatment composition disclosed herein for example by making use of the system and/or method disclosed herein.
  • Suitable substrates that may be used include metal substrates, metal alloy substrates, substrates that have been metallized, such as nickel-plated plastic, and/or combinations thereof.
  • 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 of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys also may be used as the substrate.
  • 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 1XX.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 in the present disclosure include those that are often used in the assembly of vehicle 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, personal electronics, agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles.
  • vehicle or variations thereof includes, but is not limited to, civilian, commercial and military aircraft, and/or land vehicles such as cars, 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.
  • 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.
  • the treated substrate may optionally further comprise a coating formed from a coating composition.
  • the coating composition from which the coating is formed may comprise a film-forming resin.
  • the coating composition may comprise an electrodepositable coating composition, a powder coating composition, and/or a liquid coating composition.
  • the coating may be applied to at least a portion of the substrate by electrodeposition of the coating deposition, as described above.
  • the coated substrate of the present disclosure may for example 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. Examples of 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® ELTTM 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 “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) 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.
  • 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 97GY121, available from PPG Industries Ohio, Inc.
  • 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 catalysts 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.
  • DCMA Dry Color Manufacturers Association
  • the colorant can be present in the coating composition in any amount sufficient to impart the desired visual and/or color effect.
  • the colorant may comprise 1% to 65% by weight based on the total weight of the composition, such as 3% to 49% by weight, such as 5% to 35% by weight.
  • An alkaline cleaner solution was prepared by adding 10 gallons of deionized water to a rectangular stainless- steel tank with a total volume of 37 gallons, equipped with spray nozzles. To this was added 500 mL of Chemkleen 2010LP (a phosphate-free alkaline cleaner available from PPG Industries, Inc.) and 50 mL of Chemkleen 181 ALP (a phosphate-free blended surfactant additive available from PPG Industries, Inc.). The solution temperature was raised to 120°F.
  • 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 mL sample of the alkaline cleaner was titrated with 0.100 N sulfuric acid to measure the free and total alkalinity.
  • the free alkalinity was 5.2 mL as measured using a phenolphthalein end point (pink to colorless color change) and the total alkalinity was 6.4 mL as measured to a bromocresol green end point (blue to yellow color change).
  • PT 1-14 Fourteen different pretreatment compositions (PT 1-14) were prepared for testing. The compositions are listed in Table 1, below. Zinc was supplied by adding zinc oxide, available from Fisher Scientific (Fair Lawn, NJ); etidronic acid was supplied by adding hydroxyl ethylidene (1, 1 -dipho sphonic acid) (58 wt%), available from Italmatch (Manchester, UK) for pretreatments 1-3, 6-8, and 10 and hydroxyl ethylidene (1, 1-diphosphonic acid) (58 wt%), available from PPG Industries, Inc.
  • Zinc was supplied by adding zinc oxide, available from Fisher Scientific (Fair Lawn, NJ); etidronic acid was supplied by adding hydroxyl ethylidene (1, 1 -dipho sphonic acid) (58 wt%), available from Italmatch (Manchester, UK) for pretreatments 1-3, 6-8, and 10 and hydroxyl ethylidene (1, 1-
  • compositions were prepared in DI water and maintained at 75°F with an immersion heater (Polyscience Sous Vide Professional, Model # 7306AC1B5, available from Polyscience, Niles, Illinois). Baths containing pretreatment were set to low agitation mode during immersion of panels to circulate and heat the composition contained therein.
  • immersion heater Polyscience Sous Vide Professional, Model # 7306AC1B5, available from Polyscience, Niles, Illinois. Baths containing pretreatment were set to low agitation mode during immersion of panels to circulate and heat the composition contained therein.
  • pH was measured using a pH meter (interface, DualStar pH/ISE Dual Channel Benchtop Meter, available from ThermoFisher Scientific, Waitham, Massachusetts, USA; pH probe, Fisher Scientific Accumet pH probe (Ag/AgCl reference electrode)) by immersing the pH probe in the pretreatment solution.
  • Free fluoride was measured using a DualStar pH/ISE Dual Channel Benchtop Meter (ThermoFisher Scientific) equipped with a fluoride selective electrode (Orion ISE Fluoride Electrode, solid state, available from ThermoFisher Scientific) by immersing the ISE in the pretreatment solution and allowing the measurement to equilibrate.
  • Chemfil buffer an alkaline buffering solution, commercially available from PPG Industries, Inc.
  • Chemfos AFL a partially neutralized aqueous ammonium bifluoride solution, commercially available from PPG Industries, Inc and prepared according to supplier instructions.
  • Aluminum etidronate derivative was prepared by adding 13.36 g of anhydrous aluminum chloride portion-wise to a 58 wt% solution of etidronic acid in a clean 500 mL round bottom flask. The reaction vigorously exothermed upon addition of the aluminum salt. A charge of 15.28 g of deionized water was then added to the reaction and the resultant mixture was stirred at room temperature for approximately 43 hours using a Thermolyne Nuova SP 18425 stir plate and a magnetic stir bar. The volatiles were then removed under reduced pressure on a BUCHI RE-111 rotary evaporator for 4 hours. The remaining viscous liquid was dissolved in deionized water to produce the aluminum etidronate derivative at 56.69% total solids.
  • AZ21 magnesium alloy (known commercially as “Eform Plus” or abbreviated “EFP”) supplied by USAMP from POSCO (Pohang, SK) was evaluated. Substrates were cut to 4” by 6” using a panel cutter prior to application of the alkaline cleaner.
  • Eform Plus or abbreviated “EFP” supplied by USAMP from POSCO (Pohang, SK) was evaluated. Substrates were cut to 4” by 6” using a panel cutter prior to application of the alkaline cleaner.
  • Panels were treated using either Treatment Method A or B, outlined in Tables 2 and 3, respectively, below.
  • Treatment Method 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 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).
  • All panels were immersed in one of PT 1 through PT 10 for 120 seconds (75°F), rinsed by a deionized water spray rinse using a Melnor Rear-Trigger 7-Pattern nozzle set to shower mode (75°F) for 30 seconds, and dried with hot air (140°F) for 120 seconds using a Hi- Velocity handheld blow dryer made by Oster® (model number 078302-300-000) on high setting.
  • EPIC 200 a cationic electrocoat with components commercially available from PPG and prepared in accordance with manufacturer’s instructions.
  • the electrocoat paint was ultrafiltered removing 25% of the material, which was replenished with fresh deionized water.
  • the rectifier Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XG 300-5 6, Ameteck, Berwyn, Pennsylvania
  • the electrocoat application conditions were a voltage set point of 170V-180V, a ramp time of 30s, and a current density of 1.6 mA/cm2.
  • the electrocoat composition was maintained at 92°F using a heating coil.
  • the film thickness was coulomb controlled to deposit a target film thickness of 0.75 ⁇ 0.2 mils for EPIC.
  • the DFT was controlled by changing the amount of charge (coulombs) that passed through the panels. Following deposition of the electrocoat, panels were baked in an oven (Despatch Model EFD-1- 42) at 177°C for 25 minutes.
  • Electrocoated panels were vertically or X- scribed on one side of the panel down to the metal substrate.
  • EFP panels were placed in ASTM G85 A2 testing for a minimum of 3 weeks (i.e., 21 cycles). After the exposure, corroded panels were dried under ambient conditions until dry to the touch.
  • the loose coating around the 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 5-12 locations and averaged to assess the corrosion performance of the panel.
  • scribe creep refers to the area of paint loss around the scribe either through corrosion or disbondment (e.g., effected paint to effected paint).
  • Panels for PT 2 and PT 3 were run in duplicate, panels for PT 4, PT 5, and PT 9 were run in quadruplicates, and panels for PT 1, PT 6, PT 7, PT 8, and PT 10 were run in octuplicates.
  • Elemental testing was performed using X-Ray Fluorescence spectroscopy (XRF), XPS depth profiling, and FIB/TEM/EDX.
  • FIB/TEM/EDX was performed using a FEI Helios NanoEab 660.
  • a protective layer of carbon and a protective layer of gold was deposited on the sample before the focused ion beam (FIB) preparation.
  • the focused ion beam (FIB) lift-out method was used.
  • High-angle annular dark- field scanning transmission electron microscopy (HAADF STEM) and energy dispersive x-ray spectroscopy (EDX) analysis was performed at Penn State University’s Materials Research Institute on the FEI Talos TEM (200kV).
  • HAADF STEM high-angle annular dark- field scanning transmission electron microscopy
  • EDX energy dispersive x-ray spectroscopy
  • AZ21 panels were treated according to Treatment Method A (Table 2). Panels were then electrocoated with EPIC 200 according to the parameters described above. Panels were scribed and subjected to G-85 cyclic corrosion testing as specified in Table 4.
  • This example shows that AZ21 panels treated with PT 1 had better corrosion performance in comparison to panels treated with PT 2, PT 3, or PT 7 as demonstrated by an average scribe creep of 1.43 mm following exposure to 42 cycles of G-85 cyclic corrosion testing and an average scribe creep of 0.034 mm/cycle of G-85 cyclic corrosion testing.
  • PT 2, PT 3, and PT 7 were not extended to 42 cycles because their corrosion performance at 21 cycles was so poor that 42 cycles would likely result in extensive corrosion that could not be measured or differentiated from the other pretreatments in the same set.
  • AZ21 panels were treated according to either Treatment Method A or B (Table 2 and 3). Panels were then electrocoated with EPIC 200 according to the parameters described above. Panels were scribed and subjected to G-85 cyclic corrosion testing as specified in Table 5.
  • Treatment Method B This example shows that AZ21 panels treated with PT 1 have comparably better corrosion performance to PT 8 on AZ21 and performs considerably better than the alkaline clean only comparative control, or Treatment Method B, as demonstrated by an average scribe creep of 1.43 mm following exposure to 42 cycles of salt spray testing and an average scribe creep of 0.034 mm/cycle of salt spray testing. Treatment Method B was not run to 42 cycles because the corrosion performance was so poor that 42 cycles would likely show result in extensive corrosion that could not be measured or differentiated from the other pretreatments in the same set.
  • AZ21 panels were treated according to Treatment Method A (Table 2). Panels were then electrocoated with EPIC 200 according to the parameters described above. Panels were scribed and subjected to G-85 cyclic corrosion testing as specified in Table 6.
  • This example shows that AZ21 panels treated with PT 1 had better corrosion performance than AZ21 panels treated with PT 4, PT 5, PT 6, or PT 9 as demonstrated by an average scribe creep of 1.43 mm following exposure to 42 cycles of salt spray testing and an average scribe creep of 0.034 mm/cycle of salt spray testing.
  • This example also shows that AZ21 panels treated with PT 5, PT 6, and PT 9, which demonstrate different operating ranges of zinc and etidronic acid, give noticeably better corrosion performance on AZ21 in comparison to PT 4. This is demonstrated by an average scribe creep after 42 cycles of G-85 corrosion testing of 4.44 mm, 8.59 mm, and 3.02 mm for PT 5, PT 6, and PT 9, respectively, versus an average scribe creep of 13.86 mm for PT 4.
  • AZ21 panels were treated according to Treatment Method A (Table 2). Panels were then electrocoated with EPIC 200 according to the parameters described above. Panels were scribed and subjected to G-85 cyclic corrosion testing as specified in Table 7. Table 7. Average G-85 scribe creep results for Example 4
  • Example 5 pH and free fluoride measured for PT 11, PT 12, PT 13, and PT 14
  • PT 11, PT 12, PT 13, and PT 14 were prepared as described above.
  • the pH and free fluoride of each pretreatment were measured as described above and recorded in Table 8. This example confirms the pH and free fluoride ranges for PT 2, PT 4, PT 7, and PT 10.

Abstract

L'invention divulgue des compositions de prétraitement comprenant au moins 25 ppm d'un phosphonate sur la base du poids total de la composition de prétraitement ; au moins 6 ppm de zinc sur la base du poids total de la composition de prétraitement ; et un pH de 6,0 ou moins. L'invention divulgue également des systèmes et des procédés de traitement d'un substrat avec l'une des compositions de prétraitement divulguées ici. L'invention divulgue également des substrats qui ont été traités avec l'une des compositions de prétraitement divulguées ici.
PCT/US2022/077333 2021-12-03 2022-09-30 Systèmes et procédés de traitement d'un substrat WO2023102284A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163285738P 2021-12-03 2021-12-03
US63/285,738 2021-12-03

Publications (1)

Publication Number Publication Date
WO2023102284A1 true WO2023102284A1 (fr) 2023-06-08

Family

ID=83899812

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/077333 WO2023102284A1 (fr) 2021-12-03 2022-09-30 Systèmes et procédés de traitement d'un substrat

Country Status (1)

Country Link
WO (1) WO2023102284A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912548A (en) 1973-07-13 1975-10-14 Amchem Prod Method for treating metal surfaces with compositions comprising zirconium and a polymer
CA2087352A1 (fr) 1992-07-01 1994-01-02 David W. Reichgott Procede et composition pour le traitement d'acier galvanise
US5328525A (en) 1993-01-05 1994-07-12 Betz Laboratories, Inc. Method and composition for treatment of metals
US5449415A (en) 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
WO1995033869A1 (fr) 1994-06-03 1995-12-14 Henkel Corporation Composition et procede de traitement de la surface de metaux alumineux
US5653823A (en) 1995-10-20 1997-08-05 Ppg Industries, Inc. Non-chrome post-rinse composition for phosphated metal substrates
US5662746A (en) 1996-02-23 1997-09-02 Brent America, Inc. Composition and method for treatment of phosphated metal surfaces
WO2002024975A1 (fr) * 2000-09-22 2002-03-28 Henkel Kommanditgesellschaft Auf Aktien Composition et procede de traitement de metaux
US6797387B2 (en) 2000-09-21 2004-09-28 Ppg Industries Ohio Inc. Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers
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
US20110008645A1 (en) * 2008-03-11 2011-01-13 Mark Andre Schneider Process for coating metallic surfaces with a passivating agent, the passivating agent and its use

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912548A (en) 1973-07-13 1975-10-14 Amchem Prod Method for treating metal surfaces with compositions comprising zirconium and a polymer
CA2087352A1 (fr) 1992-07-01 1994-01-02 David W. Reichgott Procede et composition pour le traitement d'acier galvanise
US5328525A (en) 1993-01-05 1994-07-12 Betz Laboratories, Inc. Method and composition for treatment of metals
US5449415A (en) 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
WO1995033869A1 (fr) 1994-06-03 1995-12-14 Henkel Corporation Composition et procede de traitement de la surface de metaux alumineux
US5653823A (en) 1995-10-20 1997-08-05 Ppg Industries, Inc. Non-chrome post-rinse composition for phosphated metal substrates
US5662746A (en) 1996-02-23 1997-09-02 Brent America, Inc. Composition and method for treatment of phosphated metal surfaces
US6797387B2 (en) 2000-09-21 2004-09-28 Ppg Industries Ohio Inc. Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers
WO2002024975A1 (fr) * 2000-09-22 2002-03-28 Henkel Kommanditgesellschaft Auf Aktien Composition et procede de traitement de metaux
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
US20110008645A1 (en) * 2008-03-11 2011-01-13 Mark Andre Schneider Process for coating metallic surfaces with a passivating agent, the passivating agent and its use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIGHTCAPPUCCINO: "Determination of fluoride in toothpaste using an ion-selective electrode", J. CHEM. EDUC., vol. 52, no. 4, April 1975 (1975-04-01), pages 247 - 50

Similar Documents

Publication Publication Date Title
KR102255735B1 (ko) 박막 전처리 및 밀봉 조성물을 통한 금속 기판 처리를 위한 시스템 및 방법
KR102650929B1 (ko) 2-단계 전처리 시스템 및 방법
US10113070B2 (en) Pretreatment compositions and methods of treating a substrate
WO2018031981A1 (fr) Système et procédé de prétraitement à deux étapes
CN115087761A (zh) 用于金属预处理应用的铋组合物
US20240050983A1 (en) Systems and methods for treating a substrate
US20240076781A1 (en) Systems and methods for treating a metal substrate
WO2023102284A1 (fr) Systèmes et procédés de traitement d'un substrat
WO2023015060A1 (fr) Systèmes et procédé de traitement d'un substrat
WO2023132989A1 (fr) Compositions, systèmes et procédés de traitement d'un substrat
WO2022197357A1 (fr) Systèmes et procédés de traitement d'un substrat
WO2022197358A1 (fr) Systèmes et procédés de traitement d'un substrat
EP3497265A1 (fr) Préparation d'une composition de traitement et système et procédé de maintien d'un bain de traitement formé à partir de la préparation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22793086

Country of ref document: EP

Kind code of ref document: A1