US20060042726A1 - Non-chrome passivation of steel - Google Patents
Non-chrome passivation of steel Download PDFInfo
- Publication number
- US20060042726A1 US20060042726A1 US10/933,014 US93301404A US2006042726A1 US 20060042726 A1 US20060042726 A1 US 20060042726A1 US 93301404 A US93301404 A US 93301404A US 2006042726 A1 US2006042726 A1 US 2006042726A1
- Authority
- US
- United States
- Prior art keywords
- recited
- composition
- metal
- fluoacid
- polyoxyethylene
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 238000002161 passivation Methods 0.000 title claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 title description 3
- 239000010959 steel Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000004816 latex Substances 0.000 claims abstract description 20
- 229920000126 latex Polymers 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 10
- -1 polyoxyethylene Polymers 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 8
- 239000008397 galvanized steel Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims 4
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000007739 conversion coating Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001983 poloxamer Polymers 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FSFVPNRYRFVFEI-UHFFFAOYSA-N 1-(2,4,4-trimethylpentan-2-yl)-2-[2-(2,4,4-trimethylpentan-2-yl)phenoxy]benzene Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1OC1=CC=CC=C1C(C)(C)CC(C)(C)C FSFVPNRYRFVFEI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003708 H2TiF6 Inorganic materials 0.000 description 1
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical compound C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
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
- C23C22/361—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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D119/00—Coating compositions based on rubbers, not provided for in groups C09D107/00 - C09D117/00
- C09D119/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D121/00—Coating compositions based on unspecified rubbers
- C09D121/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the present invention relates to non-chromate coatings for metals. More particularly, the present invention relates to non-chromate coatings for steel surfaces to improve corrosion resistance and adhesion of paints to the surface.
- the invention provides a dried in place coating which is particularly effective at treating galvanized steel coil strip.
- a chromate conversion coating on the surface of galvanized steel are to provide corrosion resistance, improve adhesion of coatings and for aesthetic reasons. Chromate passivation of a galvanized steel surface is done to provide corrosion resistance and for aesthetic reasons on materials which are not to be painted.
- the conversion coating improves adhesion of coating layers such as paints, inks, lacquers and plastic coatings.
- Galvanized steel is typically treated with an aqueous composition containing hexavalent or trivalent chromium ions with other additives to create a chromium conversion coating.
- the present invention provides a method of treating the surface of metals, such as steel or galvanized steel, to provide for the formation of a coating which increases the corrosion resistance and adhesion properties of the metal surface.
- the passivation or conversion coating formed by the present invention may be dried in place or rinsed.
- the methods of the invention comprise contacting the requisite metal surface with a chromate free aqueous treatment composition comprising: (a) a film forming latex polymer; (b) a fluoacid; (c) phosphoric acid; and (d) a polyoxyethylene/oxypropylene block copolymer.
- an improved, non-chromate conversion or passivation coating can be provided on metal surfaces, particularly galvanized steel surfaces, by contacting the surface with an aqueous coating solution or dispersion of:
- compositions of the invention have been found to provide an aqueous pretreatment agent for the treatment of galvanized metal surfaces which provides improved corrosion resistance and adhesion of latex applied coating when the treatment is dried in place.
- the film forming latex polymer component this can be chosen from a wide variety of materials such as styrene-butadiene copolymers, acrylate resins, polyvinylacetate, urethanes, amido-amine polymers, and similar materials.
- Some commercially available latex materials include: Description Type “Neocar” (Union Carbide) Vinyl Ester/Acrylic “Res 3077” (Rohm & Haas) Vinyl Acetate/Acrylic “Airflex” 500 (Air Products) Vinyl Acetate/Ethylene “Airflex 4514 (Air Products) Vinyl Chloride/Amide Terpolymer Airflex 4500 (Air Products) Vinyl Chloride/Amide Terpolymer Flexhane 620 (Air Products) Urethane Vinac 884 (Air Products) Vinyl Acetate Dow 620 (Dow) SBR Airflex 4530 (Air Products) ethylene vinyl chloride Kymene 736 polyamido amine U Car Latex 651 acrylate
- U Car Latex 651 As the film forming latex polymer component. This is commercially available form Union Carbide and is reportedly an acrylic copolymer resin emulsion having as major latex components butyl acrylate, methyl methacrylate, and methacrylic acid polymers.
- this is preferably a fluoacid of a Group IVB metal or mixtures thereof.
- Fluotitanic acid H 2 TiF 6 is presently preferred with fluozirconic acid, H 2 ZrF 6 , also mentioned as exemplary. Combinations of these acids are also used.
- phosphoric acid As stated above, phosphoric acid, H 3 PO 4 , and salts thereof are also present in the treatment formulation.
- phosphoric acid refers to both the acid and salt form.
- a polyoxyethylene/oxypropylene block copolymer is exemplary.
- the ethylene oxide (EO):propylene oxide (PO) repeat units of the copolymers may be present in a molar ratio of about 1:1-9; preferably 1:5-9; most preferably 1:9. Molecular weights of these block copolymers will range from about 2,000-4,000.
- These copolymers are commercially available from BASF under the “Pluronic” trademark. Presently, “Pluronic 101” is preferred for use.
- This specific copolymer has a ratio of EO:PO blocks of about 1:9 and a molecular weight of about 3,300.
- compositions in accordance with the invention are chromate free and include 0.01-50 wt % film forming latex 0.01-40 wt % H 3 PO 4 0.01-30 wt % fluoacid 0.01-20 wt % non-ionic polymer surfactant wherein the weight of the composition is, in total, 100 wt %.
- compositions having the following range (in wt %) of the components 1-20 wt % film forming latex 1-50 wt % H 3 PO 4 1-40 wt % fluoacid 0.01-15 wt % non-ionic polymer surfactant remainder water.
- the sum of all composition components equals 100 wt %.
- the pH of the compositions may vary from about 1.0 to 2.0.
- the requisite metal surface may be contacted by the treatment in spray, immersion or roller applications.
- the treatment is then dried and the metal surface is ready for painting or other coating applications.
- the conversion or passivation treatment of the present invention is applied to result in a conversion coating weight of greater than about 1 milligram per square foot to treated surface with a weight of 2-150 milligrams per square foot being more preferred.
- working solutions comprising about 3-100, preferably 10-100 wt % concentrations of the above “More preferred” formulation are used to contact the desired metal surfaces.
- One tested treatment candidate formulation “A” was a latex emulsion including the following components: 1) U Car Latex 651 5.8 wt % (65% actives) 2) H 3 PO 4 22.0 wt % 3) Fluotitanic acid 10 wt % 4) Pluronic 101 0.5 wt % 5) Water remainder
- U Car Latex 651 is an acrylic copolymer resin emulsion having a viscosity 20° C., cP (Brookfield, LVT #3, 50 rpm) of 400 and a particle size in microns of 0.45. It is available from the Union Carbide Corporation of Danbury, Conn. Its major constituents are 1) butyl acrylate, methyl methacrylate, methacrylic acid polymers in an amount of ⁇ 65 wt %; 2) water ⁇ 35%; 3) glycols, polyethylene, mono [(1,1,3,3-tetramethylbutyl)phenyl] ether in an amount of less than 2%; and 4) ammonia in 0.2 wt %. It is a white liquid.
- cP Brookfield, LVT #3, 50 rpm
- Pluronic 101 is a difunctional block copolymer surfactant terminating in primary hydroxy groups and is available from BASF Corporation in Mount Olive, N.J. It is a block copolymer having hydrophobic propylene oxide (PO) repeat units and hydrophilic ethylene oxide (EtO) repeat units in a molar ratio of about 9:1. The overall molecular weight of the copolymer is about 3300.
- PO propylene oxide
- EtO hydrophilic ethylene oxide
- Test panels for the examples were prepared as follows: G70/70 hot dipped galvanized steel test panels purchased from ACT Laboratories were spray cleaned with a 3% aqueous solution of an alkaline surfactant product and then rinsed with DI water and subsequently coated with the test treatment formulations by spin coat application, followed by forced air drying.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
- The present invention relates to non-chromate coatings for metals. More particularly, the present invention relates to non-chromate coatings for steel surfaces to improve corrosion resistance and adhesion of paints to the surface. The invention provides a dried in place coating which is particularly effective at treating galvanized steel coil strip.
- The purposes of the formation of a chromate conversion coating on the surface of galvanized steel are to provide corrosion resistance, improve adhesion of coatings and for aesthetic reasons. Chromate passivation of a galvanized steel surface is done to provide corrosion resistance and for aesthetic reasons on materials which are not to be painted. The conversion coating improves adhesion of coating layers such as paints, inks, lacquers and plastic coatings. Galvanized steel is typically treated with an aqueous composition containing hexavalent or trivalent chromium ions with other additives to create a chromium conversion coating.
- Growing concerns exist regarding the pollution effects of chromates discharged into rivers and waterways by such processes. Because of the high solubility and the strongly oxidizing character of hexavalent chromium ions, conventional chromate conversion processes require extensive waste treatment procedures to control their discharge. In addition, the disposal of the solid sludge from such waste treatment procedures is a significant problem.
- Accordingly, there is a need in the art to provide an effective non-chromate treatment to provide a dried in place conversion or passivation coating to inhibit metal surface corrosion and enhance adhesion of paint or other coatings that may be applied to the metal surface.
- The present invention provides a method of treating the surface of metals, such as steel or galvanized steel, to provide for the formation of a coating which increases the corrosion resistance and adhesion properties of the metal surface. The passivation or conversion coating formed by the present invention may be dried in place or rinsed. The methods of the invention comprise contacting the requisite metal surface with a chromate free aqueous treatment composition comprising: (a) a film forming latex polymer; (b) a fluoacid; (c) phosphoric acid; and (d) a polyoxyethylene/oxypropylene block copolymer. Other objects and advantages of the invention will be apparent from the following description and the appended claims.
- The inventors have found that an improved, non-chromate conversion or passivation coating can be provided on metal surfaces, particularly galvanized steel surfaces, by contacting the surface with an aqueous coating solution or dispersion of:
-
- (a) a film forming latex polymer;
- (b) a fluoacid;
- (c) phosphoric acid; and
- (d) a nonionic polymer surfactant.
- Compositions of the invention have been found to provide an aqueous pretreatment agent for the treatment of galvanized metal surfaces which provides improved corrosion resistance and adhesion of latex applied coating when the treatment is dried in place.
- As to the film forming latex polymer component, this can be chosen from a wide variety of materials such as styrene-butadiene copolymers, acrylate resins, polyvinylacetate, urethanes, amido-amine polymers, and similar materials. Some commercially available latex materials include:
Description Type “Neocar” (Union Carbide) Vinyl Ester/Acrylic “Res 3077” (Rohm & Haas) Vinyl Acetate/Acrylic “Airflex” 500 (Air Products) Vinyl Acetate/Ethylene “Airflex 4514 (Air Products) Vinyl Chloride/Amide Terpolymer Airflex 4500 (Air Products) Vinyl Chloride/Amide Terpolymer Flexhane 620 (Air Products) Urethane Vinac 884 (Air Products) Vinyl Acetate Dow 620 (Dow) SBR Airflex 4530 (Air Products) ethylene vinyl chloride Kymene 736 polyamido amine U Car Latex 651 acrylate - At present, it is preferred to utilize “U Car Latex 651” as the film forming latex polymer component. This is commercially available form Union Carbide and is reportedly an acrylic copolymer resin emulsion having as major latex components butyl acrylate, methyl methacrylate, and methacrylic acid polymers.
- As to the fluoacid that is present in the treatment formulation, this is preferably a fluoacid of a Group IVB metal or mixtures thereof. Fluotitanic acid H2TiF6, is presently preferred with fluozirconic acid, H2ZrF6, also mentioned as exemplary. Combinations of these acids are also used.
- As stated above, phosphoric acid, H3PO4, and salts thereof are also present in the treatment formulation. The phrase “phosphoric acid” used herein, refers to both the acid and salt form.
- With regard to the non-ionic polymer surfactant, a polyoxyethylene/oxypropylene block copolymer is exemplary. The ethylene oxide (EO):propylene oxide (PO) repeat units of the copolymers may be present in a molar ratio of about 1:1-9; preferably 1:5-9; most preferably 1:9. Molecular weights of these block copolymers will range from about 2,000-4,000. These copolymers are commercially available from BASF under the “Pluronic” trademark. Presently, “Pluronic 101” is preferred for use. This specific copolymer has a ratio of EO:PO blocks of about 1:9 and a molecular weight of about 3,300.
- Compositions in accordance with the invention are chromate free and include
0.01-50 wt % film forming latex 0.01-40 wt % H3PO4 0.01-30 wt % fluoacid 0.01-20 wt % non-ionic polymer surfactant wherein the weight of the composition is, in total, 100 wt %. - More preferred are compositions having the following range (in wt %) of the components
1-20 wt % film forming latex 1-50 wt % H3PO4 1-40 wt % fluoacid 0.01-15 wt % non-ionic polymer surfactant remainder water. - The sum of all composition components equals 100 wt %. The pH of the compositions may vary from about 1.0 to 2.0.
- The requisite metal surface may be contacted by the treatment in spray, immersion or roller applications. The treatment is then dried and the metal surface is ready for painting or other coating applications.
- The conversion or passivation treatment of the present invention is applied to result in a conversion coating weight of greater than about 1 milligram per square foot to treated surface with a weight of 2-150 milligrams per square foot being more preferred. For use in commercial applications, working solutions comprising about 3-100, preferably 10-100 wt % concentrations of the above “More preferred” formulation are used to contact the desired metal surfaces.
- The invention will now be described in conjunction with the following examples which are to be regarded as being illustrative of certain embodiments of the invention but should not be viewed to restrict the scope of the same.
- One tested treatment candidate formulation “A”, was a latex emulsion including the following components:
1) U Car Latex 651 5.8 wt % (65% actives) 2) H3PO4 22.0 wt % 3) Fluotitanic acid 10 wt % 4) Pluronic 101 0.5 wt % 5) Water remainder - U Car Latex 651 is an acrylic copolymer resin emulsion having a viscosity 20° C., cP (Brookfield, LVT #3, 50 rpm) of 400 and a particle size in microns of 0.45. It is available from the Union Carbide Corporation of Danbury, Conn. Its major constituents are 1) butyl acrylate, methyl methacrylate, methacrylic acid polymers in an amount of <65 wt %; 2) water −35%; 3) glycols, polyethylene, mono [(1,1,3,3-tetramethylbutyl)phenyl] ether in an amount of less than 2%; and 4) ammonia in 0.2 wt %. It is a white liquid.
- Pluronic 101 is a difunctional block copolymer surfactant terminating in primary hydroxy groups and is available from BASF Corporation in Mount Olive, N.J. It is a block copolymer having hydrophobic propylene oxide (PO) repeat units and hydrophilic ethylene oxide (EtO) repeat units in a molar ratio of about 9:1. The overall molecular weight of the copolymer is about 3300.
- Test panels for the examples were prepared as follows: G70/70 hot dipped galvanized steel test panels purchased from ACT Laboratories were spray cleaned with a 3% aqueous solution of an alkaline surfactant product and then rinsed with DI water and subsequently coated with the test treatment formulations by spin coat application, followed by forced air drying.
-
- A. NSS—Neutral Salt Spray Test per ASTM B 117 and rated according to ASTM D-1654 (% white rust).
- B. Water Resistance—ASTM D 4585—Water Resistance of Coatings Using Controlled Condensation wherein condensation is produced by exploring one surface of a coated specimen to a heated, saturated mixture of air and water vapor while the reverse side of the specimen is exposed to the cooling effect of room temperature. (% white rust).
- C. Water Resistance of Coatings in 100% Relative Humidity according to ASTM 2247-97 (% white rust).
- Test Results
Test & Result ASTM D2247-97; ASTM B117/D1654 ASTM D4585 100% Rel Humidity Treatment 48 Hrs. NSS 240 Hrs QCT 408 hours A 1 0 0 C-1 1 0 0 C-2 100 1 10
C-1 is a state of the art, chrome containing hexavalent chromium passivation.
C-2 is commercially available non-chrome passivation.
- While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (21)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/933,014 US20060042726A1 (en) | 2004-09-02 | 2004-09-02 | Non-chrome passivation of steel |
| CA2578965A CA2578965C (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface |
| EP05793978.7A EP1838898B1 (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface |
| CN2005800294625A CN101018888B (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface |
| MX2007002619A MX2007002619A (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface. |
| PCT/US2005/031091 WO2006028894A2 (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface |
| RU2007111918/02A RU2396370C2 (en) | 2004-09-02 | 2005-08-30 | Chromium-free passivation of steel |
| ES05793978.7T ES2573537T3 (en) | 2004-09-02 | 2005-08-30 | Method and composition to form a conversion coating without chromium on a steel surface |
| BRPI0515626A BRPI0515626B1 (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a chrome-free conversion coating on steel surface |
| AU2005282751A AU2005282751B2 (en) | 2004-09-02 | 2005-08-30 | Method and composition for forming a non-chrome conversion coating on steel surface |
| US12/154,502 US8980015B2 (en) | 2004-09-02 | 2008-05-23 | Non-chrome passivation of steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/933,014 US20060042726A1 (en) | 2004-09-02 | 2004-09-02 | Non-chrome passivation of steel |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/154,502 Continuation US8980015B2 (en) | 2004-09-02 | 2008-05-23 | Non-chrome passivation of steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20060042726A1 true US20060042726A1 (en) | 2006-03-02 |
Family
ID=35453711
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/933,014 Abandoned US20060042726A1 (en) | 2004-09-02 | 2004-09-02 | Non-chrome passivation of steel |
| US12/154,502 Expired - Fee Related US8980015B2 (en) | 2004-09-02 | 2008-05-23 | Non-chrome passivation of steel |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/154,502 Expired - Fee Related US8980015B2 (en) | 2004-09-02 | 2008-05-23 | Non-chrome passivation of steel |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US20060042726A1 (en) |
| EP (1) | EP1838898B1 (en) |
| CN (1) | CN101018888B (en) |
| AU (1) | AU2005282751B2 (en) |
| BR (1) | BRPI0515626B1 (en) |
| CA (1) | CA2578965C (en) |
| ES (1) | ES2573537T3 (en) |
| MX (1) | MX2007002619A (en) |
| RU (1) | RU2396370C2 (en) |
| WO (1) | WO2006028894A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060169363A1 (en) * | 2005-01-14 | 2006-08-03 | Jasdeep Sohi | Stable, non-chrome, thin-film organic passivates |
| WO2012045713A1 (en) * | 2010-10-05 | 2012-04-12 | Basf Se | Method for passivating metallic surfaces with aqueous compositions comprising surfactants |
| US8986467B2 (en) | 2010-10-05 | 2015-03-24 | Basf Se | Method for passivating metallic surfaces with aqueous compositions comprising surfactants |
| CN110054956A (en) * | 2019-04-02 | 2019-07-26 | 广州市宏彩金属饰品有限公司 | A kind of preparation method of the film coating agent for Treatment of Metal Surface |
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| CN101619452A (en) * | 2008-07-01 | 2010-01-06 | 上海品新冶金设备有限公司 | Non-chrome passivating agent for steel, zinc plates, aluminum and aluminum alloy pieces, zinc and zinc alloy |
| CN101619451A (en) * | 2008-07-01 | 2010-01-06 | 上海品新冶金设备有限公司 | Non-chrome passivating agent for steel, zinc plates, aluminum and aluminum alloy pieces, zinc and zinc alloy |
| DE102013107506A1 (en) * | 2013-07-16 | 2015-01-22 | Thyssenkrupp Rasselstein Gmbh | Method for passivation of band-shaped black plate |
| CN103695888B (en) * | 2013-12-24 | 2015-12-02 | 山东建筑大学 | Bundy tube galvanized chromium-free olive passivation agent I |
| CN105154861A (en) * | 2015-07-06 | 2015-12-16 | 安徽景昌铝业有限公司 | Chromate-free passivation treatment process for aluminum profile material |
| DE102015113878B4 (en) * | 2015-08-21 | 2023-03-16 | Thyssenkrupp Ag | Process for the thermal treatment of a black plate coated with a conversion layer |
| CN109312469A (en) * | 2016-06-22 | 2019-02-05 | 凯密特尔有限责任公司 | Improved method for anti-corrosion pretreatment of metal surfaces comprising steel, galvanized steel, aluminum, magnesium and/or zinc-magnesium alloys |
| CN111218689A (en) * | 2019-12-11 | 2020-06-02 | 陈克华 | Steel surface corrosion conversion coating liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060169363A1 (en) * | 2005-01-14 | 2006-08-03 | Jasdeep Sohi | Stable, non-chrome, thin-film organic passivates |
| WO2012045713A1 (en) * | 2010-10-05 | 2012-04-12 | Basf Se | Method for passivating metallic surfaces with aqueous compositions comprising surfactants |
| CN103154318A (en) * | 2010-10-05 | 2013-06-12 | 巴斯夫欧洲公司 | Method for passivating metallic surfaces with aqueous compositions comprising surfactants |
| US8986467B2 (en) | 2010-10-05 | 2015-03-24 | Basf Se | Method for passivating metallic surfaces with aqueous compositions comprising surfactants |
| CN110054956A (en) * | 2019-04-02 | 2019-07-26 | 广州市宏彩金属饰品有限公司 | A kind of preparation method of the film coating agent for Treatment of Metal Surface |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2007002619A (en) | 2007-05-15 |
| AU2005282751B2 (en) | 2011-07-21 |
| RU2396370C2 (en) | 2010-08-10 |
| CN101018888A (en) | 2007-08-15 |
| US8980015B2 (en) | 2015-03-17 |
| CA2578965A1 (en) | 2006-03-16 |
| CA2578965C (en) | 2016-08-23 |
| WO2006028894A2 (en) | 2006-03-16 |
| AU2005282751A1 (en) | 2006-03-16 |
| BRPI0515626B1 (en) | 2016-11-08 |
| US20080223490A1 (en) | 2008-09-18 |
| EP1838898B1 (en) | 2016-03-16 |
| BRPI0515626A (en) | 2008-07-29 |
| ES2573537T3 (en) | 2016-06-08 |
| EP1838898A2 (en) | 2007-10-03 |
| WO2006028894A3 (en) | 2006-06-01 |
| CN101018888B (en) | 2012-03-28 |
| RU2007111918A (en) | 2008-10-10 |
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