WO2004046421A1 - Composition et procede de passivation pour surfaces zinciferes et aluniferes - Google Patents

Composition et procede de passivation pour surfaces zinciferes et aluniferes Download PDF

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WO2004046421A1
WO2004046421A1 PCT/US2003/035882 US0335882W WO2004046421A1 WO 2004046421 A1 WO2004046421 A1 WO 2004046421A1 US 0335882 W US0335882 W US 0335882W WO 2004046421 A1 WO2004046421 A1 WO 2004046421A1
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composition
fluorometallate
solution
total weight
amount
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PCT/US2003/035882
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English (en)
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Jasdeep Sohi
Timm L. Kelly
Kevin K. Meagher
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2003290716A priority Critical patent/AU2003290716A1/en
Publication of WO2004046421A1 publication Critical patent/WO2004046421A1/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
    • C23C22/34—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
    • C23C22/361—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 titanium, zirconium or hafnium compounds
    • 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
    • C23C22/73—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 characterised by the process

Definitions

  • the present invention relates to compositions and processes for passivating, i.e. , fo ⁇ ning a corrosion protective surface layer, on metal surfaces that consist predominantly of aluminum and/or zinc.
  • passivating i.e. , fo ⁇ ning a corrosion protective surface layer
  • metal surfaces that consist predominantly of aluminum and/or zinc.
  • a wide variety of such surfaces are in normal use, including many kinds of galvanized and/or aluminized steel, and the invention is applicable to such surfaces which differ from the underlying metal, as well as to solid alloys of aluminum and/or zinc.
  • Zinc (zinciferous) and zinc alloy (such as almriiniferous) coatings are frequently used to protect steel from corrosion.
  • Two common types of metal-coated steel typically used are galvanized steel (zinc) and Galvalume ® (55% Al, 43.5% Zn, 1.5% Si). Both galvanized steel and Galvalume ® have long service lifetimes as a result of galvanic and/or sacrificial corrosion protection afforded by the coatings. While the underlying steel is protected, the zinc coating is sometimes susceptible to corrosion that can result in surface staining and white corrosion.
  • an entirely or substantially chromium-free composition and process for passivating is provided that provides adequate corrosion resistance in comparison with previously used chromate containing passivating agents.
  • a passivating aqueous liquid composition that comprises, preferably consists essentially of, or more preferably consists of, water and:
  • composition may optionally further comprises one or more of the following:
  • Various embodiments of the invention include working compositions for direct use in treating metals, make-up concentrates from which such working compositions can be prepared by dilution with water, replenisher concentrates suitable for maintaining optimum performance of working compositions according to the invention, processes for treating metals with a composition according to the invention, and extended processes including additional steps that are conventional per se, such as cleaning, rinsing, and subsequent painting or some similar overcoating process that puts into place an organic binder-containing protective coating over the metal surface treated according to a narrower embodiment of the invention.
  • Articles of manufacture including surfaces treated according to a process of the invention are also within the scope of the invention.
  • compositions according to the invention as defined above should be substantially free from many ingredients used in compositions for similar purposes in the prior art.
  • these compositions contain no more than 25, 15, 9, 5, 3, 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.001, or 0.0002 percent of each of the following constituents: nitrite; halates and perhalates (i.e., perchlorate, chlorate, iodate, etc.); hydroxylamine and salts and complexes of hydroxylamine; chloride; bromide; iodide; organic compounds containing nitro groups; hexavalent chromium; ferricyanide; ferrocyanide; and pyrazole compounds. Components such as these may not be harmful in
  • the dissolved phosphate ions that constitute necessary component (A) may be obtained from a variety of sources as known in the art. Normally much of the phosphate content will be supplied by phosphoric acid added to the composition, and the stoichiometric equivalent as phosphate ions of all undissociated phosphoric acid and all its anionic ionization products in solution, along with the stoichiometric equivalent as phosphate ions of any dihydrogen phosphate, monohydrogen phosphate, or completely neutralized phosphate ions added to the composition in salt form, are to be understood as forming part of phosphate ions component (A), irrespective of the actual degree of ionization and/or reaction to produce some other chemical species that exists in the composition.
  • component (A) If any metaphosphoric acid, other condensed phosphoric acids, or salts of any of these acids are present in the compositions, their stoichiometric equivalent as phosphate is also considered part of component (A). Generally, however, it is preferred, at least partly for reasons of economy, to utilize orthophosphoric acid and its salts as the initial source for component (A).
  • the concentration of phosphate ions and/or their stoichiometric equivalents as noted above preferably is at least, with increasing preference in the order given, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 9.0, 10.0, 12.0, 13.0, 14.0, 15.0, 16.0 or 17.0 grams per liter (hereinafter usually abbreviated as "g/L") of total composition and independently preferably is not more than, with increasing preference in the order given, 400, 200, 100, 90, 80, 75, 70, 60, 50, 45, 40 or 34 g/L.
  • the dissolved fluorometallate anions that constitute necessary component (B) preferably are selected from the group consisting of TiF 6 "2 , ZrF 6 "2 , HfF 6 - 2 , SiF 6 - 2 , A1F 6 '3 , GeF 6 "2 , SnF 6 "2 , BF 4 ' , and mixtures thereof, with the first two being more preferred and fmorotitanate being the most preferred.
  • Such anions may be introduced into a treatment composition according to the invention as acids or salts, with the acids usually preferred for economy and because a net acidity of the compositions is preferable as considered f rther below, and the entire stoichiometric equivalent as any of the above recited fluorometallate ions in any source material as dissolved in a composition according to the invention or a precursor composition for it is to be considered as part of the fluorometallate component, irrespective of the actual degree of ionization that may occur.
  • the total concentration of the fluorometallate anions dissolved in a working treatment composition according to the invention preferably is at least, with increasing preference in the order given, 0.5, 1.0, 2.0, 2.5, 3.0, 4.0, 5.0, 6.0, 7.5, 8.5, 10.0, 11.0, 12.0 or 13.0 g/L and independently, primarily for reasons of economy, preferably is not more than, with increasing preference in the order given, 400, 200, 100, 90, 80, 75, 65, 50, 45, 38, 37.5, 35.0, 32.5 30.0, 28.0, 27.0 or 26.0 g/L.
  • the concentrations of fluorometallate anions (B) and phosphate ions (A) preferably are such that the ratio between them, in working compositions and concentrated solutions used to prepare working concentrations, is at least, with increasing preference in the order given, 0.10: 1.0, 0.15:1.0, 0.25: 1.0, 0.35:1.0, 0.45:1.0, 0.50: 1.0, 0.55:1.0, 0.60: 1.0, 0.65:1.0, or 0.75:1.0 and independently preferably is not more than, with increasing preference in the order given, 5: 1.0, 4:1.0, 3.5: 1.0, 3.2: 1.0, 2.0:1.0, 1.5:1.0, 1.0: 1.0, or 0.9:1.0.
  • composition of the present invention also optionally includes an amino-phenolic polymer component (C).
  • Suitable examples of such polymers include Mannich adducts of secondary amines containing a carbon chain with at least one hydroxy group, formaldehyde, and a polyphenolic resin.
  • Certain preferred polymers are Mannich adducts of poly vinyl phenol that are described in more detail in U.S. Patent Nos.
  • the polymer component (C) is the Mannich adduct of polyhydroxystyrene with N-methylglucamine.
  • Polymer (C) in some embodiments, can also be added as a solution of the polymer component with an acid, such as fluorotitanic acid, phosphoric acid, and fluorozirconic acid.
  • the concentrations of polymer (C) and the acid in the polymer (C)/acid solution preferably are such that the ratio between them is at least, with increasing preference in the order given, 1.0:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 5.0:1.0 or 6.5:1.0, and independently preferably is not more than, with increasing preference in the order given, 50: 1.0, 40: 1.0, 30:1.0, 25: 1.0, 15: 1.0, 10: 1.0, 9.0: 1.0, 8.0: 1.0 or 7.5:1.0.
  • the total concentration of the polymer (C) dissolved in a working treatment composition according to the invention preferably is at least, with increasing preference in the order given, 0.1, 0.25, 0.50, 0.75, 1.0, 1.25, 1.50 or 1.70 g/L of total composition and independently preferably not more than, with increasing preference in the order given, 150, 100, 75, 50, 25, 15 or 13 g/L.
  • the optimal amount of polymer (C) depends in large part on the desired end property of the coating.
  • the concentrations of polymer (C) and phosphate anions (A) preferably are such that the ratio between them, in working compositions and concentrated solutions used to prepare working concentrations, is at least, with increasing preference in the order given, 0.005: 1.0, 0.01: 1.0, 0.015:1.0, 0.02:1.0, 0.025:1.0, 0.03:1.0, 0.035:1.0, 0.04:1.0, 0.045: 1.0 or 0.05:1.0, and independently preferably is not more than, with increasing preference in the order given, 1.2:1.0, 1.0:1.0, 0.90:1.0, 0.75:1.0, 0.60: 1.0, 0.50:1.0, 0.45: 1.0, 0.35:1.0, 0.25:1.0, 0.20:1.0, 0.10:1.0 or 0.07:1.0.
  • the pH of the treatment bath should be from 1.0 to 4.0, more preferably 1.2 to 2.5, and most preferably from 1.5 to 2.0.
  • a j?H below 1.0 may result in an overly strong etch and scanty coating formation.
  • the solution may have a pronounced tendency to form precipitates, which can result in a shortened bath life.
  • the pH can be adjusted using a p ⁇ adjusting component (D) such as an acid such as phosphoric acid, or nitric acid, or a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or ammonium hydroxide, with ammonium hydroxide being the most preferred.
  • the total concentration of p ⁇ adjusting component (D) dissolved in a working treatment composition according to the invention preferably is at least, with increasing preference in the order given, 1.0, 5, 10, 15, 20, 25, 30, or 32.5 g/L of total composition, and independently preferably not more than, with increasing preference in the order given, 100, 90, 80, 75, 70, 60, 50, or 45 g/L.
  • the composition of the present invention also optionally includes a wetting agent (E).
  • the wetting agent (E) is particularly useful for wetting surfaces that are known to be somewhat difficult to wet, such as Galvalume ® . Wetting agents that improve coating wetting without increasing water sensitivity of the composition and that are soluble and stable in strong acidic solutions are preferred. Examples of suitable wetting agents include, but are not limited to, phosphate esters. Preferred phosphate esters include, but are not limited to, substituted phosphate esters, and more preferably substituted carboxylated phosphate esters.
  • a particularly preferred wetting agent (E) is PHOSPHOTERICTM TC-6. PHOSPHOTERICTM TC-6 is reported by its supplier, Uniqema of New Castle, Delaware, to have an "R" moiety according to chemical formula (II):
  • R 1 and R 3 are carboxyethyl or salt thereof and the other is carboxyethyl, salt thereof, or hydrogen, and R 2 is coconut oil alkyl, in chemical formula (III):
  • u is 1 or 2
  • y (4-u)
  • M is hydrogen or sodium cation, except that at least one M must be sodium cation.
  • the total concentration of wetting agent (E) dissolved in a working composition according to the invention preferably is at least, with increasing preference in the order given, 0.10, 0.20, 0.25, 0.30, 0.40, 0.50, 0.55, 0.60 or 0.65 g/L of total composition and independently preferably not more than, with increasing preference in the order given, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.90, 0.80 or 0.75 g/L.
  • the concentrations of wetting agent (E) and phosphate anions (A) preferably are such that the ratio between them, in working compositions and concentrated solutions used to prepare working compositions, is at least, with increasing preference in the order given, 0.010:1.0, 0.015:1.0, 0.020: 1.0 or 0.025:1.0 and independently preferably is not more than, with increasing preference in the order given, 0.20: 1.0, 0.15:1.0, 0.10:1.0, 0.090:1.0, 0.075: 1.0, 0.060:1.0, 0.050:1.0, 0.045:1.0, 0.040: 1.0 or 0.035:1.0.
  • composition of the present invention can be prepared by combining the components in any order.
  • TD-1355-DE is an aqueous solution containing about 1.2 wt. % hexafluorotitanic acid and about 8.6 wt. % of a Mannich adduct of polyhydroxystyrene, N-methylglucamine, and formaldehyde prepared in accordance with U.S. Patent No. 5,891,952.
  • Some preferred concentrated compositions, in accordance with the present invention, comprise:
  • compositions in accordance with the present invention, comprise:
  • the concentrated composition is typically diluted, with water, to about 2-50 wt. %, more preferably 3.5-30 wt. %, and most preferably about 5-20 wt. % .
  • compositions in accordance with the present invention, comprise:
  • weight percents in the three preceding tables are on a wet basis and that the components referred to in those tables have percent solids similar to the percent solids of the components listed in the table preceding the above three tables.
  • a process according to the invention in its simplest form consists of bringing a metal surface to be passivated into physical contact with a working composition according to the invention as described above for a period of time, then discontinuing such contact and drying the surface previously contacted.
  • Suitable metal surfaces include galvanized and/or aluminized steel, and solid alloys of aluminum and/or zinc.
  • Physical contact and subsequent separation can be accomplished by any of the methods well known in the metal treatment art, such as immersion for a certain time, then discontinuing immersion and removing adherent liquid by drainage under the influence of natural gravity or with a squeegee or similar device; spraying to establish the contact, then discontinuing the spraying and removing excess liquid as when contact is by immersion; roll coating of the amount of liquid followed by drying into place, and the like.
  • the temperature of the working passivating aqueous liquid composition during a passivation process according to the invention is at least, with increasing preference in the order given, 15°C, 20°C, 25°C, 30°C, 34°C or 37°C. and independently preferably, primarily for reasons of economy, is not more than 66 °C, 60 °C, 55 °C, or 50 °C.
  • the quality of the passivation layer formed is not known to be substantially affected by the temperature during passivating if the temperature is within any of these preferred limits; the primary reason for the preference for a minimum temperature during passivating that is greater than the normal ambient temperature is that with such a passivating temperature and squeegeeing off of any adherent liquid promptly after discontinuing contact of the surface to be passivated with a working passivating aqueous liquid composition according to the invention, the surface will dry spontaneously in ambient air within a few seconds to form a passivated surface according to the invention. This method of operation is particularly well adapted to most existing coil processing plants.
  • the time during which physical contact is maintained between the metal surface to be passivated and a working passivating aqueous liquid composition according to the invention preferably, for reasons of economy of operation, is as short as possible, consistent with formation of a passivating layer as effective as desired. More specifically, the time of contact preferably is not more than, with increasing preference in the order given, 200, 150, 100, 75, 50, 40, 30, 25, 20, 15, 13, 11, 10, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.5, 1.0, 0.5 or 0.1 seconds. Spraying a heated working passivating aqueous liquid composition onto the surface to be passivated followed by removing excess liquid with a squeegee has been found effective in forming a passivated surface according to this invention within a few seconds at most.
  • the surface to be passivated preferably is not rinsed with water or other diluent between contact with a working passivating aqueous liquid composition according to the invention and drying. Drying can be accomplished by simple exposure to ambient air for a sufficient time, and indeed is preferably accomplished in this way if the passivated surface has been formed at a sufficiently high temperature that drying occurs within a few seconds of separation from contact with the working passivating aqueous liquid composition according to the invention as described above. Alternatively, one may hasten the drying by exposure of the wet surface after passivation to a higher temperature than the normal ambient temperature, in an oven or by any of the other means such as infrared radiant heating, microwave drying, and the like well known per se in the art.
  • the coating is thick enough that aqueous liquid composition according to the invention corresponds to at least, with increasing preference in the order given, 5, 10, 15, 20, 21.5, 30, 38, 43, 50, 60, or 64.6 milligrams per square meter of the metal surface passivated (hereinafter usually abbreviated as "mg/m 2 "), measured as total weight of the coating, and independently, preferably is not more than, with increasing preference in the order given, 600, 575, 540, 450, 300, 200, 172, 150, 129, 115, 100, or 90 mg/m 2 measured as total weight of the coating.
  • the amount of total coating weight added- on may conveniently be measured with commercially available instruments, or by other means known to those skilled in the art.
  • the coating is thick enough that aqueous liquid composition according to the invention corresponds to at least, with increasing preference in the order given, 0.24, 0.5, 1.0, 2.0, 4.0, 6.0, or 8.0 milligrams per square meter of the metal surface passivated (hereinafter usually abbreviated as "mg/m 2 "), measured as titanium atoms, and independently preferably corresponds to not more than 133, 125, 100, 75, 50, 40, 24, or 17 mg/m 2 measured as Titanium atoms.
  • the amount of titanium added-on may conveniently be measured with a commercially available instrument, a PORTASPECTM Model 2501 X-ray spectrograph from Cianflone Scientific, or by other means known to those skilled in the art.
  • a protective layer containing at least an organic binder preferably a thickness after drying that is at least, with increasing preference in the order given, 0.2, 0.4, 0.6, 0.8, or 1.0 micrometers (hereinafter usually abbreviated as " ⁇ m") and independently preferably, primarily for reasons of economy, is not more than 10, 7, 5, 3, 2.5, 2.0, 1.5, or 1.3 ⁇ m.
  • this relatively thin clear overcoating can serve adequately as the final coating layer in many instances.
  • additional thicker coatings of paint and like materials adapted to a specific purpose as known per se in the art may be applied directly over this initial thin acrylic overcoating, or directly over the passivated metal surface itself.
  • the passivated surface may remain uncovered, i.e., not painted.
  • the passivating coating can act as a temporary coating.
  • the passivating coating is intended to provide temporary corrosion protection for preventing corrosion and staining during the time period after galvanizing and prior to final finishing, i.e. , during storage and shipping.
  • the passivating coating could then be removed and the substrate coated with a more permanent corrosion resistant coating, as is known in the art.
  • the more permanent corrosion resistant coatings can be provided by a suitable conversion coating process. Suitable conversion coating composition and processes are disclosed in U.S. Patent Nos. 4,961,794; 4,838,957; 5,073,196;
  • the passivating coating is to be removed, it is presently contemplated that this can be readily done by exposing the passivating coating to a suitable alkaline cleaner solution.
  • the substrate to be passivated may, but is not necessarily, thoroughly cleaned by any of various methods well known to those skilled in the art to be suitable for the particular substrate to be coated.
  • galvanized metal surfaces are mentioned in connection with the present invention, they are understood to be material surfaces of electrolytically galvanized or hot-dip-galvanized or even alloy-galvanized steel, preferably electrolytically galvanized or hot-dip-galvanized steel strip.
  • steel is meant unalloyed to low-alloyed steel of the type used, for example, in the form of sheets for automotive bodywork.
  • galvanized steel, particularly electrolytically galvanized steel in strip form has grown considerably in significance in recent years.
  • galvanized steel in the context of the present invention is understood to encompass electrolytically galvanized steel and also hot-dip- galvanized steel and also applies generally to alloy-galvanized steel, zinc/nickel alloys, zinc/iron alloys (Galvanealed) an zinc/aluminum alloys (GALFAN ® , from Eastern Alloys, Inc., of Maybrook, New York, GALVALUMETM, from BIEC International, Inc. of Vancouver, Washington) playing a particularly crucial role as zinc alloys.
  • GALVALUMETM zinc/aluminum alloys
  • Example 1 Working compositions 1 and 2 were prepared as set forth below in
  • Test panels of HDG (hot dipped galvanized) steel and Galvalume ® steel were prepared in the following manner.
  • the HDG steel panels were cleaned with a 3 wt. % solution of Parco ® Cleaner 1200, available from Henkel Corporation, at a temperature of about 140°F for about 20 seconds. The panels were then hot water rinsed at a temperature of about 120°F for about 10 seconds. The panels were then squeegeed dry. Compositions 1 and 2 were then diluted to about 66 wt. % and were then applied to the panels using a No. 3 draw bar. The panels were then dried in an IR oven. The total coating weight on the panels were about 4-8 mg/ft 2 .
  • Galvalume ® steel panels were cleaned and treated in the same manner except they were only cleaned for about 7 seconds.
  • HDG and Galvalume ® steel test panels were prepared and subjected to NSS testing for 336 hours in the manner set forth above in Example 1. The results are shown below in Table 5.
  • HDG and Galvalume ® steel test panels were cleaned with a 4 wt. % solution of Ridoline ® 321 at a temperature of about 140 °F for about 30 seconds. The panels were then hot water rinsed at a temperature of about 120°F for about 10 seconds. The panels were then squeegeed dry. Composition 1 was applied to the panels using various drawbars. The test panels were then subjected to (i) Stack testing, (ii) Butler Water Immersion testing, and (iii) NSS testing for 72 hours in the manner set forth above in Example 1. The results are shown below in Tables 6, 7, and 8.
  • BR black rust
  • WR WR
  • RR red rust
  • the panels were cut to 4" x 4" size.
  • Any duplicate test panels were stacked face-to-face with an amount of deionized water (as indicated in drops or as a spray) being applied between the two test panels to wet the surfaces.
  • test panels were clamped together in a test jig and tightened to about 50 in. «lb. torque.
  • the stack of panels were placed in a humidity test cabinet at 100 °F and 100% humidity.
  • the test panels were evaluated at the time intervals shown in table 6 for black rust (BR) and white rust (WR).
  • Samples were cut into 3-1/2" x 7-1/2" panels such that the samples support themselves on the sides of the glass tray approximately Vi " from the bottom of the tray.
  • the samples were placed in the glass tray.
  • Enough distilled water was added to the tray to cover the sample with 3/4" of water.
  • the uncovered trays were placed in a humidity cabinet at 100% humidity and 100°F.
  • test panels were evaluated at the time intervals shown in table 7 for black rust and white rust.
  • HDG steel test panels were cleaned with a 4 wt. % solution of Ridoline ® 321 at a temperature of about 140°F for about 30 seconds. The panels were then hot water rinsed at a temperature of about 120°F for about 10 seconds. The panels were then squeegeed dry. Compositions 1 and 4 were applied to the panels using various drawbars. The panels were then cleaned with a 4.5 wt. % solution of Parco ® cleaner 1200 for about 30 seconds at about 150°F. The test panels were observed to be fully cleaned in accordance with the following procedure.
  • the cleaned test panels were rinsed with D.I. water and dried. A drop of about a 3 wt. % copper sulfate pentahydrate solution was dropped on the panels. A 100% reaction, evidenced by the area of the panel that contacts the drop turning black, witl ⁇ i a second of contact, was observed on all the panels, indicating that the panels were fully cleaned.
  • HDG steel test panels prepared in the same manner as set forth in Example 4 were then subjected to the following procedure and subjected to T-bend testing. The results are shown below in Table 9.
  • A pretreat 3 panels with Bonderite ® 1402W, prime coat with UY9R 24235, and top coat with CLS 9872 from Akzo.
  • B pretreat 3 panels with Bonderite ® 1303 and Parcolene ® 62, prime coat with UY9R 24235, and top coat with CL 9872 from Akzo.
  • the T-bend test was carried out in accordance with ASTM D4145.
  • 0T is the best, 0T-2T are acceptable. From the above results, it confirms that panels treated with the chrome free passivate of the present invetnion are treatable and paintable.
  • HDG steel test panels were coated with composition 1. Samples C and D were cleaned with a 4.5 wt. % solution of Parco ® cleaner 1200 for about 25 seconds at about 160°F. Samples C and D were subjected to the same test as set forth in Example 4 and were observed to be fully cleaned. The sample designations are shown below.
  • A Composition 1 treatment on HDG at high coating weights (8-16 mg/ft 2 ).
  • B Composition 1 treatment on HDG at low coating weights (4-8 mg/ft 2 ).
  • C Sample A cleaned with Parco ® Cleaner 1200.
  • D Sample B cleaned with Parco ® Cleaner 1200.
  • test panels were submitted to Evans Analytical GroupTM for surface analysis using X-Ray Photoelectron Spectroscopy.
  • the surfaces were analyzed as three depths- (i) as received, (ii) about 75 A (angstroms) below the as received surface, and (iii) about 150 A (angstroms) below the as received surface.
  • the spectroscopy analysis confirmed that samples C and D were fully cleaned.

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  • Chemical Treatment Of Metals (AREA)

Abstract

Dans au moins un mode de réalisation, l'invention concerne un procédé de traitement temporaire anticorrosif d'une surface métallique constituée en majeur partie d'aluminium et/ou de zinc, ledit procédé consistant a) à placer la surface du métal en contact avec une composition anticorrosive contenant 2-400 g/L ions phosphate, 0,5-400 g/L ions fluorométallate et possédant un pH entre 1,0 et 4,0, pendant une durée entre 0,1 et 200 secondes, b) à sécher la composition de traitement anticorrosif sur la surface métallique afin d'obtenir une première couche de passivation sur ladite surface, c) à supprimer ce premier revêtement de passivation de ladite surface métallique et d) à effectuer le revêtement par conversion de cette surface. Dans certains modes de réalisation, la solution de phosphate contient de l'acide phosphorique et la solution de fluorométallate contient de l'acide hexafluorotitanique.
PCT/US2003/035882 2002-11-15 2003-11-12 Composition et procede de passivation pour surfaces zinciferes et aluniferes WO2004046421A1 (fr)

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US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions

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US20050072495A1 (en) 2005-04-07

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