US3912548A - Method for treating metal surfaces with compositions comprising zirconium and a polymer - Google Patents

Method for treating metal surfaces with compositions comprising zirconium and a polymer Download PDF

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US3912548A
US3912548A US379138A US37913873A US3912548A US 3912548 A US3912548 A US 3912548A US 379138 A US379138 A US 379138A US 37913873 A US37913873 A US 37913873A US 3912548 A US3912548 A US 3912548A
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grams
ammonium
test
polyacrylic acid
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Harry L Faigen
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Henkel Corp
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Amchem Products Inc
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Priority to US379138A priority Critical patent/US3912548A/en
Priority to AU67569/74A priority patent/AU470781B2/en
Priority to BR4097/74A priority patent/BR7404097A/pt
Priority to JP7076174A priority patent/JPS5418664B2/ja
Priority to CA203,178A priority patent/CA1046872A/en
Priority to GB29429/74A priority patent/GB1479638A/en
Priority to FR7424138A priority patent/FR2236907B1/fr
Priority to DE2433704A priority patent/DE2433704C3/de
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Priority to CA304,595A priority patent/CA1047666A/en
Assigned to AMCHEM PRODUCTS, INC. A CORP. OF DEL. reassignment AMCHEM PRODUCTS, INC. A CORP. OF DEL. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: AMCHEM PRODUCTS, INC. (MERGED INTO), HHC, INC. (CHANGED TO)
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/68Chemical 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

Definitions

  • ABSTRACT The corrosion resistance and siccative finish bonding characteristics of a metal surface are improved by contacting the surface with an aqueous composition consisting of a soluble zirconium compound and a p01- ymeric material.
  • the aqueous composition can be applied to a surface having a conversion coating deposited thereon, to improve the qualities of the coating.
  • compositions consisting essentially of aqueous acid phosphate or acid chromate solutions have been employed to treat bare metal surfaces already possessing a conversion coating to improve the corrosion resistance and paint bonding characteristics.
  • Chromate treatments employed to deposit a coating on a metal surface or as a treatment after a conversion coating has been formed are disclosed, for example, in US. Pat. Nos. 2,825,697; 2,678,291; 2,936,254; and 2,928,763.
  • chromium containing treatments Another problem encountered with chromium containing treatments is that certain paint or lacquer systems will chip, peel, or blister when applied to a metal surface which has been treated with chromates. Workpieces having complex configurations will accumulate residues of chromium salts in areas such as crevices, pockets and joints. These areas will tend to display blis tering, peeling, and generally inferior siccative finish adhesion.
  • Resinous materials have been incorporated in a chromate treating solution, so as to provide on the metal surface a final finish or an excellent base for subsequent painting.
  • Solutions and dispersions of this kind are disclosed, for example, in US. Pat. Nos. 2,902,390; 3,053,692; 3,132,055; 3,185,596; 3,189,488 and 3,189,489.
  • these treating solutions and the protective coatings formed therefrom have not eliminated the detrimental effect of the high toxicity associated with hexavalent chromium.
  • the primary object of the present invention is to provide a method for the treatment of metal surfaces which will enhance the corrosion resistance and siccative finish bonding characteristics of the surface.
  • An added object of this invention is to provide a process and treating composition for metal surfaces which enhances the adhesion properties of a subsequently applied siccative finish while eliminating the waste effluent disposal problems encountered with compositions employed heretofore.
  • a concomitant object of this invention is to provide an improved method for treating metal surfaces on which a conversion coating has already been deposited.
  • aqueous composition employed in the present process consists essentially of a soluble zirconium compound and a polymeric material. When the composition is applied to metal substrate, a coating is obtained which enhances corrosion resistance and siccative finish bonding.
  • aqueous composition or aqueous solution utilized herein means the aqueous admixture comprising zirconium, present as a soluble zirconium compound, and a polymeric material.
  • concentration of zirconium present in the aqueous composition is expressed herein as the concentration of ZrO This means that the zirconium, present as a soluble zirconium compound in solution, is the form of tetravalent zirconium whose concentration is expressed as the concentration of its oxide.
  • the term aqueous solution when employed herein is to be understood as including an emulsion or dispersion of the polymer and zirconium compound, as well as a solution of the polymer and zirconium compound.
  • water soluble polymeric or resinous materials examples include polyacrylic acid, polyvinyl alcohol, hydroxyethyl ethers of cellulose, ethylene maleic anhydride, polyvinyl pyrollidine, and polyvinyl methyl ether.
  • An example of a polymeric material in the form of dispersed particles that can be utilized is an acrylic copolymer latice.
  • the dispersed polymer or latex should be stable, in the presence of the other ingredients comprising the aqueous composition.
  • soluble zirconium compounds can be employed.
  • the selection of the compound to be employed will depend on its commercial availability and its stability in solution with the polymeric material. It is, of course, necessary that upon its inclusion in the aqueous solution, it should not hydrolize to insoluble hydrous zirconium dioxide or an insoluble zirconium salt at the operating pH and temperature of the process, nor should it cause coagulation of the polymeric material.
  • Typical examples of zirconium compounds which can be employed in the aqueous composition are alkali metal and ammonium tluozirconate and ammonium zirconium carbonate.
  • the aqueous composition should comprise at least 0.1 grams/liter of the zirconium compound (measured as ZrO).
  • ZrO concentration of the zirconium compound
  • ammonium zirconium carbonate will be employed in the aqueous composition and its concentration, measured as ZrO will preferably be from about 0.1 grams/liter to about 3.5 grams/liter.
  • the resinous or polymeric material may include both water soluble as well as water dispersible polymers.
  • the aqueous composition comprises a water soluble polyacrylic acid.
  • Water dispersible emulsions or latexes of polyacrylic acid derivatives are also commercially available, such as the alkali metal and ammonium salts of polyacrylic acd, and the polyacrylic acid esters.
  • acrylic acid polymer or polyacrylic acid, it should be understood that this means and applies to all types of polymers to be utilized in the aqueous composition, whether they be water dispersible or water soluble salts, esters, or the acid.
  • Aqueous solutions of polyacrylic acid are available commercially, for example, those solid under the name Acrysol A-l, Acrysol A-3, and Acrysol A-5.
  • Water dispersible emulsions of polyacrylic acid esters are also available, for example those solid under the name Rhoplex Ac-35.
  • the amount of polymer utilized can vary over a wide range. It is preferred that the polymeric material in the aqueous composition be present in an amount from about 0.1 grams/liter to about 5.0 grams/liter. Naturally, the amount of polymeric material present in the solution must be sufficient to aid in the forming of a film on the metal surface.
  • a surprising aspect of the present invention is that an aqueous composition having a concentration of polymeric material within the preferred range indicated above gives satisfactory uniform coatings which adhere to the surface and improve the siccative finishing bonding characteristics of the surface.
  • the amount of polymer present should be that amount which will be particularly effective under the particular operating conditions of the treating process, so as to improve the corrosion resistant capabilities and siccative finish bonding properties of the already formed coating, or in the case where no coating has been deposited, to improve the corrosion resistance of the bare metal surface and its paint bonding characteristics. It has been found that the amount of polymeric material should preferably range from about 1.0 part to about 2.0 parts by weight for each part by weight of zirconium in the aqueous composition.
  • any polymeric material which is stable in the presence of the zirconium compound in a waterbased composition can be used in the practice of this invention.
  • the aqueous compositions to be used preferably are prepared by addition of the components to water. This negates any problems with respect to stability for prolonged periods of time should an aqueous concentrate be prepared and then be added directly to water in order to prepare the aqueous composition for use. It has been observed that, under certain conditions, should an aqueous concentrate be prepared to make up the aqueous composition, hydrolysis and salting out of both the zirconium compound and the polymer is evident.
  • each constituent is preferably added to the appropriate amount of water to prepare a working bath having constituent concentrations within the operative ranges set forth herein.
  • the zirconium compound and polymer will evidence stability by remaining uniformly distributed throughout the aqueous phase of the composition, although in certain cases stirring of the composition may be employed to maintain a uniform dispersion during operation.
  • the polymeric material should already be in solution or dispersed in the aqueous phase prior to the addition of the zirconium compound. This will further insure against any hydrolysis and precipitation of zirconium in the prepared aqueous bath.
  • the metal surface Prior to treatment with the aqueous composition, the metal surface can be treated with a solution which reacts with the surface to form a conversion coating.
  • the conversion coating will have been applied using commonly employed processes and techniques known to the art. Particularly, the conversion coatings employed are those referred to as chromate coatings or phosphate coatings.
  • chromate coatings we mean those produced from aqueous baths containing hexavalent chromium, trivalent chromium, and/or salts thereof, as well as additional constituents such as phosphoric acid, and fluoride.
  • phosphate coatings we mean those produced from aqueous solutions containing phosphoric acid and salts thereof, as well as additional constituents such as fluorides, molybdates, chlorates, nitrites, and various organic accelerators.
  • Formula 1 is an example of a suitable dry chromate coating composition which can be added to water to form a chromate coating solution which can be employed to treat metal surfaces prior to their treatment with the aqueous composition:
  • Formula 1 by weight Chromic Acid 3337 Potassium Fluozirconate l5-l6 Sodium Bifluoride 45-49 Formula 2 by weight Chromic Acid 57-60 Phosphoric Acid l5-l6 Water 24-26 Formula 3 is an example of a suitable concentrated phosphate coating solution which can be diluted to desired strength and can be employed to treat metal surfaces prior to contact with the aqueous composition.
  • compositions of the present invention can be applied to a bare metal surface having no prior coating thereon.
  • a surprising result is that the surface will maintain its original appearance and a coating will be produced which will also improve the adherence of a subsequently applied siccative finish or sanitary lacquer, such as an acrylic based coat, and the surface will portray improved corrosion resistance.
  • a coating produced in the manner described herein is extremely useful per se, since it does add corrosion resistant properties to the metal surface. Should a siccative finish be applied to the treated surface, unexpected improved adhesion of the applied siccative finish is obtained.
  • the preparation of the polymers suitable for use herein are well known to the art.
  • the acrylic acid polymer resins to be employed in the preferred compositions of the present invention are prepared by means which can be considered solution-type polymerization processes which result in a low molecular weight polymer. However, resins made by dispersion, bulk and suspension type polymerization processes can also be used. One skilled in the art will be in a position to choose the particular polymeric material to meet specific conditions and circumstances under the composition is to be employed.
  • the metal substrate is brought into contact with the aqueous composition under suitable conditions of pH, temperature, and contact time.
  • the process is employed after cleaning of the metal surface has been accomplished.
  • the cleaning step can be carried out by conventional methods which form no part of the present invention.
  • a conventional acid or alkaline cleaner can be employed followed by a water rinse. Should the surface be heavily soiled, a detergent cleaner additive may be employed in the cleaning step.
  • the time of treatment of the metal surface with the aqueous composition need only be long enough to insure complete wetting of the surface and can be as long as 30 minutes.
  • contact time between substrate and solution should be from about one second to about one minute.
  • the coating process can be effected by employing any of the contacting techniques known to the art. Contact can be effected by spray, immersion, or flow coating techniques. Preferably the aqueous composi tion will be applied to the metal by conventional spray methods.
  • the pH of the composition can vary over a wide range and is influenced by the ingredients comprising the composition, particularly the soluble zirconium compound used. It has been found that best results are obtained when the operating pH of the composition is from about 6.0 to about 8.0.
  • the process can be operated at a temperature from about 60F. to about 120F. It is preferred to operate the process at a temperature of from about F. to about F. Generally, a slight change in the temperature will not necessitate substantial alteration of the treating time, concentration parameters, or pH adjustment.
  • the surface can be subjected to a drying operation.
  • the preferred range of temperatures for the drying operation is from about 60F. to about 500F. and, of course, the length of the drying step will depend upon the temperature utilized.
  • a siccative finish such as a lacquer
  • a siccative finish can be applied to the surface with considerable adhesion improvement.
  • the workpiece is ready for use and is highly resistant to corrosive attack, such as from any liquid or foodstuff placed in a formed metallic container formed from the workpiece.
  • a particular advantage of the present invention is that after contact with the aqueous composition has been accomplished, the workpiece is resistant to corrosive attack, even when subjected to prolonged exposure to air due to processing line stoppage prior to application of the siccative finish.
  • Example 1 is set forth for the purpose of illustrating the preparation of an aqueous composition within the purview of this invention.
  • Examples 2 through 12 illustrate the improved results obtained employing the aqueous composition.
  • the impacted area is then subjected to a tape adhesion test wherein tape is applied firmly to the impacted surface and the tape is allowed to sit for a specified length of time, usually about one minute.
  • the tape is then drawn back against itself by a rapid pulling motion in a manner such that the tape is pulled from the surface at the impacted area.
  • the reverse impact test can also be effected after the surface has undergone an immersion test as described below.
  • test specimens were subjected to an Immersion Test. In this procedure, the test specimens are immersed in deionized water or in a solution consisting of deionized water and 1% by volume of a liquid detergent at 180F. for 30 minutes. The specimens are then removed from the solution and rinsed, then blotted dry. A portion of the test specimen is immediately scribed with a cross-hatch tool having eleven cutting blades spaced one millimeter apart. Using the cross-hatch tool, one hundred squares measuring one millimeter by one millimeter are scribed on the painted surface.
  • the cross-hatched area is subjected to a tape adhesion test wherein tape is applied firmly to the surface of the test panel over the entire cross-hatched area so that no air bubbles or wrinkles are present between the tape and the surface.
  • the tape is allowed to set for one minute and is then drawn back against itself with a rapid pulling motion in a manner such that the tape is pulled from the surface of the specimen.
  • a specific area on the test specimens which had not been impacted or cross-hatched was also subjected to a Tape Adhesion Test.
  • tape is applied firmly to a portion of the surface which has not been impacted or cross-hatched.
  • the tape is applied in a manner such that no air bubbles or wrinkles are present between the tape and the surface and the tape is allowed to set for one minute and then drawn back against itself with a rapid pulling motion in a manner such that the tape is pulled from the surface of the specimen.
  • This tape adhesion test is referred to herein as a Field Test.
  • test specimens were evaluated and rated, employing the rating system set forth hereinbelow.
  • the specimens were evaluated for paint loss or paint failure utilizing a rating scale of to wherein 0 represents complete paint loss and 10 represents no paint loss. This quantitative determination was performed on the impacted area, the cross-hatched area and the field test area of the test specimens.
  • EXAMPLE 2 3% inches wide aluminum coil stock was employed in this procedure.
  • the aluminum coil was put into 6 inches long test panels.
  • the panels were cleaned with an alkaline cleaner at l60F. for 15 minutes and rinsed with water.
  • the test panels were then subjected to a conventional deoxidizing process and then subjected to a chromate-phosphate processing sequence providing a chromate-phosphate conversion coating on the surface.
  • a coating solution was prepared specified in Formula 2 hereinabove was applied to the surface, depositing a chromate-phosphate coating of 5-7 mg. persquare foot.
  • One set of control panels was cleaned and deoxidized, and another set of control panels was cleaned, deoxidized, and contacted with the above chromatephosphate solution.
  • Coated test panels were immersed in an aqueous composition consisting of polyacrylic acid and ammonium zirconium carbonate having a polyacrylic acid concentration of 2.7 grams/liter and a zirconium concentration of 1.8 grams/liter, for 15 seconds at room temperature, and allowed to air dry.
  • the pH of the aqueous composition was recorded at about 7.2.
  • test panels i.e. those treated with the ammonium zirconium carbonate and polyacrylic acid composition, as well as the control panels, where then subjected to various testing procedures set forth below in order to determine the effects on the workpiece.
  • a room temperature weight loss test and high temperature pressure weight loss test were performed on the control and test panels.
  • the specimens were placed in a pressure vessel having a glass liner therein and a carbonated beverage was poured therein.
  • the vessels were sealed and kept at F. for 5 hours in one sequence and 24 hours in a second sequence.
  • the control and test specimens had been weighed prior to the test and were weighed thereafter.
  • the average weight losses in milligrams per square foot of the panels is noted in Table 1 below, based on the observed weight loss of the groups of panels in each treatment sequence.
  • EXAMPLE 3 Three inches wide aluminum can stock specimens were employed in this procedure. The specimens were cut into 6 inches long panels and cleaned in an acid cleaner at 170F. for one minute.
  • control panels Four sets of control panels were immersed in four different baths comprising zirconium acetate, the baths having zirconium concentrations of 0.5 grams/liter; 1.0 gram/liter; 1.5 grams/liter; and 2.0 grams/liter respectively (measured as ZrO).
  • ZrO Four sets of control panels were immersed in various ammonium zirconium carbonate solutions having concentrations of zirconium of 0.5 grams/liter; 1.0 gram/liter; 1.5 grams/liter and 2.0 grams/liter respectively (measured as ZrO Test panels were tested with an aqueous composition comprising ammonium zirconium carbonate and polyacrylic acid.
  • test specimens Four sets of test specimens were utilized in four aqueous compositions having zirconium concentrations of 0.5 grams/liter; 1.0 gram/liter; 1.5 grams/liter and 2.0 grams/liter and polyacrylic acid concentrations of 0.7 grams/liter/ 1.4 grams/liter; 2.1 grams/liter; and 2.8 grams/liter respectively.
  • ammonium zirconyl carbonate and polyacrylic acid composition gave outstanding results in the tests as compared to the control specimens.
  • EXAMPLE 4 Aluminum can stock was employed in this procedure. Three inch X 6 inch panels were prepared from the can stock. The specimens, namely four sets of control panels were treated in the zirconium acetate solutions as in Example 3, four sets of control panels were treated with the ammonium zirconyl carbonate solutions as in Example 3, and four sets of test panels were immersed in aqueous compositions comprising ammonium zirconyl carbonate and polyacrylic acid therein and having the respective zirconium concentrations of 0.5 grams/liter; 1.0 grams/liter and 2.0 grams/liter (measured as ZrO and polyacrylic acid concentration of 0.7 grams/liter; 1.4 grams/liter; 2.1 grams/liter and 2.8 grams/liter respectively.
  • a vinyl interior lacquer was applied to all panels and they were then subjected to a detergent immersion procedure and then reverse- Table 3 then rinsed and deoxidized and then subjected to a phosphate processing sequence providing a phosphate Reverse Cross Field Treating Baths Impact Hatch Test Zirconium Acetate Solution ZrO Concentration 0.5 g/l l 6 10 1.0 g/l 10 1 10 L5 g/l l0 1 7 2.0 g/l l0 0 0 Ammonium Zirconium Carbonate Solution ZrO Concentration 0.5 g/l 8 10 1.0 g/l 10 4 10 1.5 g/l 10 4 10 2.0 g/l l0 4 l0 Ammonium Zirconium Carbonate Polyacrylic Acid Composition ZrO Concentration Polyacrylic Acid Concentration 0.5 g/l 0.7 g/l 10 2 10 1.0 g/l 1.4 g/l 10 6 10 L5 g/l 2.] g/] 10 9.8 10 2.0 g/l 2.8
  • the phosphate coat- Groups of aluminum test specimens were employed in this procedure.
  • the cleaned test specimens comprised 3 X 6 inches panels.
  • the panels were treated with a zirconium acetate solution, an ammonium zirconium carbonate solution, and an aqueous composition comprising ammonium zirconium carbonate and polyacrylic acid having the concentration parameters indicated in Table 4 below.
  • the test panels were painted with an acrylic white paint and then were subjected to a deionized water immersion test at 180F. for one-half hour. They were then subjected to reverse-impact, cross-hatch, and field testing. The results are listed in Table 4 below.
  • the panels were then subjected to spray treatment with the following compositions: (a) polyacrylic acid; (b) ammonium zirconium carbonate; (c) ammonium fluozirconate; (d) aqueous composition comprising polyacrylic acid and ammonium zirconium carbonate; and (e) an aqueous composition comprising polyacrylic acid and ammonium fluozirconate.
  • the panels were then dried at ambient temperature.
  • the concentrations of the particular constituents in the respective treating compositions is listed in Table 8 below.
  • the panels were then treated with an acrylic exterior paint. An additional set of control panels was cleaned and then painted.
  • Control and test panels were subjected to an immersion test with detergent at 180 F. for minutes. All panels were then subjected to reverse-impact, cross-hatch, and field testing and the results are listed in Table 6 below.
  • phosphate coating solutions employed on the groups of test panels were as follows:
  • test panels from each group were con- Table 6 Adhesion Results Reverse Cross Field Compositions Impact Hatch Test 1) 0.7 g/l Polyacrylic Acid 8 9.5 9.5 2) 2.1 g/l Polyacrylic Acid 9.5 1.0 7.0
  • the panels were cleaned with an alkaline cleaner at F. for one minute. They were rinsed grams/liter. A second set from each group of coated 5 panels was treated with a deionized water rinse follow- The painted panels were then subjected to the follow- Table 8 ing tests:
  • GAF 3 l0 4.5 Polyvinyl Pyrollidone, (NP-K30, GAF) l 0 l Phosphated Starch, (ARD 1230, American Maize) 9.9 l0 l0 Hydroxy methyl cellulose, (WP-40, Union Carbide) l0 l0 l0 EXAMPLE ll 2 X 4 inches steel panels were used in this procedure. The panels were cleaned with an alkaline cleaner at 170F. for one minute and rinsed. Control panels were dried and painted with a white acrylic paint.
  • test panels were treated with an aqueous composition comprising ammonium zirconium carbonate and polyacrylic acid having a zirconium concentration of 1.0 gram/liter (measured as ZrO and a polyacrylic acid concentration of 1.0 gram/liter.
  • the panels were then dried one minute at 400F.
  • the test panels were then painted with the white acrylic paint.
  • Test and control panels were subjected to the water soak immersion test with 1.0% detergent solution and then subjected to cross hatch and field testing. The results are listed in Table l 1 below.
  • Test panels were treated with an aqueous composition comprising ammonium zirconium carbonate and polyacrylic acid having a zirconium concentration of 1.0 gram/liter and a polyacrylic acid concentration of 1.0 gram/liter. The panels were then dried one minute at 400F. and painted with the white acrylic paint.
  • Test panels and controls were subjected to the water soak immersion test with 1% detergent solution and then subjected to cross hatch and field testing. The results are listed in Table 12 below.
  • a process for treating a metallic surface to im prove the corrosion resistance and the siccative finish bonding characteristics of said surface comprising contacting the metallic surface with an aqueous composition consisting essentially of a soluble zirconium compound in an amount of from about 0.1 grams/liter to about 3.5 grams/liter, measured as ZrO and a polymeric material in an amount from about 0.1 grams/liter to about 5.0 grams/liter, wherein the said zirconium compound is selected from the group consisting of ammonium carbonate and ammonium fluozirconate and the polymeric material is selected from the group consisting of polyacrylic acid, esters, and salts thereof.
  • aqueous composition has a pH from about 6.0 to 8.0.
  • a method for treating a metal surface having thereon a conversion coating comprising applying to said conversion coating an aqueous composition consisting essentially of a soluble zirconium compound in an amount of from about 0.1 grams/liter to about 3.5 grams/liter, measured as ZrO and a polymeric material in an amount for about 0.1 grams/liter to about 5.0 grams/liter, wherein the said zirconium compound is selected from the group consisting of ammonium zirconium carbonate and ammonium fluozirconate and the polymeric material is selected from the group consisting of polyacrylic acid, esters, and salts thereof.
  • a method for improving the corrosion resistance and paint bonding characteristics of a metal surface having an initial phosphate conversion coating thereon comprising contacting the surface with an aqueous composition consisting essentially of ammonium zirconium carbonate in an amount from about 0.] grams/- liter to about 3.5 grams/liter and a polymeric material selected from the group consisting of polyacrylic acid, esters, and salts thereof in an amount from about 0. 1 grams/liter to about 5.0 grams/liter, thereafter applying an organic final finish coating.
  • An aqueous composition for treating a metal surface consisting essentially of from about 0.1 grams/liter to about 3.5 grams/liter of a soluble zirconium compound, measured as ZrO the soluble zirconium compound being selected from the group consisting of ammonium zirconium carbonate and ammonium fluozirconate, and from about 0.1 grams/liter to about 5.0 grams/liter of a polymeric material selected from the group consisting of polyacrylic acid, esters, and salts thereof, said composition having a pH from about 6.0

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US379138A 1973-07-13 1973-07-13 Method for treating metal surfaces with compositions comprising zirconium and a polymer Expired - Lifetime US3912548A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US379138A US3912548A (en) 1973-07-13 1973-07-13 Method for treating metal surfaces with compositions comprising zirconium and a polymer
AU67569/74A AU470781B2 (en) 1973-07-13 1974-04-04 Method for treating metal surfaces with compositions comprising zirconium anda polymer
BR4097/74A BR7404097A (pt) 1973-07-13 1974-05-20 Processo aperfeicoado para tratamento de uma superficie metalica
JP7076174A JPS5418664B2 (pt) 1973-07-13 1974-06-20
CA203,178A CA1046872A (en) 1973-07-13 1974-06-24 Metal surface treating aqueous polymer zirconium composition and process
GB29429/74A GB1479638A (en) 1973-07-13 1974-07-03 Processes for the treatment of metal surfaces
FR7424138A FR2236907B1 (pt) 1973-07-13 1974-07-11
DE2433704A DE2433704C3 (de) 1973-07-13 1974-07-12 Verwendung von Zirkonverbindungen und Polyacrylsäure enthaltenden wäßrigen Dispersionen zur Behandlung von Metallflächen
CA304,595A CA1047666A (en) 1973-07-13 1978-06-01 Metal surface treating aqueous polymer zirconium compositions and process

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US379138A US3912548A (en) 1973-07-13 1973-07-13 Method for treating metal surfaces with compositions comprising zirconium and a polymer

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US4091954A (en) * 1977-06-02 1978-05-30 Aluminum Company Of America Aluminum container having interior surface treated to suppress foaming and method therefor
US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
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DE3408573A1 (de) * 1982-09-30 1985-09-12 Nihon Parkerizing Co. Ltd., Tokio/Tokyo Verfahren zum behandeln von metalloberflaechen
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes
US4656097A (en) * 1985-08-19 1987-04-07 Claffey William J Post treatment of phosphated metal surfaces by organic titanates
US4670184A (en) * 1983-11-15 1987-06-02 Swedspan Ab Suspension of ammonium carbonate and/or ammonium hydrogen carbonate of improved stability and its use
US4921552A (en) * 1988-05-03 1990-05-01 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
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US4086092A (en) * 1977-04-18 1978-04-25 Polychrome Corporation Process for making photosensitive lithographic printing plates involving sequentially coating with potassium zirconium fluoride and sodium silicate
US4091954A (en) * 1977-06-02 1978-05-30 Aluminum Company Of America Aluminum container having interior surface treated to suppress foaming and method therefor
US4338140A (en) * 1978-02-21 1982-07-06 Hooker Chemicals & Plastics Corp. Coating composition and method
US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
US4273592A (en) * 1979-12-26 1981-06-16 Amchem Products, Inc. Coating solution for metal surfaces
US4422886A (en) * 1982-01-29 1983-12-27 Chemical Systems, Inc. Surface treatment for aluminum and aluminum alloys
DE3408573A1 (de) * 1982-09-30 1985-09-12 Nihon Parkerizing Co. Ltd., Tokio/Tokyo Verfahren zum behandeln von metalloberflaechen
US4670184A (en) * 1983-11-15 1987-06-02 Swedspan Ab Suspension of ammonium carbonate and/or ammonium hydrogen carbonate of improved stability and its use
US4656097A (en) * 1985-08-19 1987-04-07 Claffey William J Post treatment of phosphated metal surfaces by organic titanates
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes
US4921552A (en) * 1988-05-03 1990-05-01 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
US5129967A (en) * 1988-05-03 1992-07-14 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
US5026440A (en) * 1988-08-27 1991-06-25 Gerhard Collardin Gmbh Chromium free treatment before coating metal surfaces
US5294266A (en) * 1989-07-28 1994-03-15 Metallgesellschaft Aktiengesellschaft Process for a passivating postrinsing of conversion layers
AU634652B2 (en) * 1990-05-29 1993-02-25 Metallgesellschaft Aktiengesellschaft Process of aftertreating conversion layers
GB2246574A (en) * 1990-07-05 1992-02-05 Atochem North America Anti-corrosive coating composition for non-ferrous metals
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US5804652A (en) * 1993-08-27 1998-09-08 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5868872A (en) * 1994-04-08 1999-02-09 Henkel Kommanditgesellschaft Auf Aktien Chromium-free process for the no-rinse treatment of aluminum and its alloys and aqueous bath solutions suitable for this process
US5895532A (en) * 1994-07-26 1999-04-20 Henkel Corporation Process for treating the surface of aluminum sheet for cap manufacturing
WO1996003534A1 (en) * 1994-07-26 1996-02-08 Henkel Corporation Process for treating the surface of aluminum sheet for cap manufacturing
US6080334A (en) * 1994-10-21 2000-06-27 Elisha Technologies Co Llc Corrosion resistant buffer system for metal products
US5714093A (en) * 1994-10-21 1998-02-03 Elisha Technologies Co. L.L.C. Corrosion resistant buffer system for metal products
US6399021B1 (en) 1994-10-21 2002-06-04 Elisha Technologies Co Llc Method of treating concrete structures
US5938976A (en) * 1994-10-21 1999-08-17 Elisha Technologies Co. L.L.C. Corrosion resistant coatings containing an amorphous phase
US5928796A (en) * 1994-10-21 1999-07-27 Elisha Technologies Co Llc Corrosion resistant coatings containing an amorphous phase
US5871668A (en) * 1994-10-21 1999-02-16 Elisha Technologies Co. L.L.C. Corrosion resistant buffer system for metal products
US5634986A (en) * 1994-11-01 1997-06-03 Man-Gill Chemical Company Process for reducing metal exposures of siccative organic coatings
US5851371A (en) * 1995-02-28 1998-12-22 Henkel Corporation Reducing or avoiding surface irregularities in electrophoretic painting of phosphated metal surfaces
US5961809A (en) * 1995-03-08 1999-10-05 Henkel Kommanditgesellschaft Auf Aktien Chromium-free process for improving paint adhesion after thin-layer anodization
US5855695A (en) * 1995-10-20 1999-01-05 Ppg Industries, Inc. Non-chrome post-rinse composition for phosphated metal substrates
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
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US6033495A (en) * 1997-01-31 2000-03-07 Elisha Technologies Co Llc Aqueous gel compositions and use thereof
US6309478B1 (en) 1997-01-31 2001-10-30 Elisha Technologies Co Llc Aqueous gel compositions and use thereof
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
US5972422A (en) * 1998-05-01 1999-10-26 Basf Corporation Method for low bake repair of composite color-plus-clear coatings, and compositions for use therein
US6045872A (en) * 1998-05-01 2000-04-04 Basf Corporation Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein
US6312812B1 (en) 1998-12-01 2001-11-06 Ppg Industries Ohio, Inc. Coated metal substrates and methods for preparing and inhibiting corrosion of the same
US6217674B1 (en) 1999-05-11 2001-04-17 Ppg Industries Ohio, Inc. Compositions and process for treating metal substrates
US6168868B1 (en) 1999-05-11 2001-01-02 Ppg Industries Ohio, Inc. Process for applying a lead-free coating to untreated metal substrates via electrodeposition
US20030138567A1 (en) * 2000-02-07 2003-07-24 Bernd Schenzle Anti-corrosive agents and method for protecting metal surfaces against corrosion
US20030150524A1 (en) * 2000-03-04 2003-08-14 Winfried Wichelhaus Method for providing metal surfaces with protection against corrosion
US20040020564A1 (en) * 2000-06-21 2004-02-05 Bernd Schenzle Adhesion promoter in conversion solutions
US6527841B2 (en) * 2000-10-31 2003-03-04 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
US6511532B2 (en) * 2000-10-31 2003-01-28 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for anodized aluminum
US6521029B1 (en) * 2000-10-31 2003-02-18 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
US6669764B1 (en) * 2000-10-31 2003-12-30 The United States Of America As Represented By The Secretary Of The Navy Pretreatment for aluminum and aluminum alloys
US6663700B1 (en) * 2000-10-31 2003-12-16 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
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DE2433704B2 (de) 1979-04-19
AU6756974A (en) 1975-10-09
FR2236907A1 (pt) 1975-02-07
JPS5039232A (pt) 1975-04-11
FR2236907B1 (pt) 1979-08-03
DE2433704A1 (de) 1975-01-30
JPS5418664B2 (pt) 1979-07-09
CA1046872A (en) 1979-01-23
BR7404097A (pt) 1976-01-27
AU470781B2 (en) 1976-03-25
DE2433704C3 (de) 1981-05-21
GB1479638A (en) 1977-07-13

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