CA2819340A1 - Chromium-free conversion coating - Google Patents
Chromium-free conversion coating Download PDFInfo
- Publication number
- CA2819340A1 CA2819340A1 CA2819340A CA2819340A CA2819340A1 CA 2819340 A1 CA2819340 A1 CA 2819340A1 CA 2819340 A CA2819340 A CA 2819340A CA 2819340 A CA2819340 A CA 2819340A CA 2819340 A1 CA2819340 A1 CA 2819340A1
- Authority
- CA
- Canada
- Prior art keywords
- ppy
- coating
- silanes
- group
- pedot
- 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.)
- Granted
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
A process for treatment of a metallic surface comprising coating the surface with a conversion coating by contacting it with a conducting polymer dispersion and drying the surfaces, wherein the conducting polymer dispersion contains a conducting polymer selected from the group consisting of: Polyaniline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY) and one or more inorganic metallic salts comprising a salt of zirconium.
Description
CHROMIUM-FREE CONVERSION COATING
FIELD
This invention relates generally to the field of coatings and corrosion control on metals, and in particular to a chromium-free conversion coating for aircraft applications.
BACKGROUND
Corrosion is defined as the chemical or electrochemical reaction between a material, usually a metal, and its environment that produces a deterioration of the material and its properties.
Corrosive attack begins on the surface of the metal. The corrosion process involves two chemical changes. The metal that is attacked or oxidized undergoes an anodic change, with the corrosive agent being reduced and undergoing a cathodic change. The tendency of most metals to corrode creates one of the major problems in the maintenance of aircraft, particularly in areas where adverse environmental or weather conditions exist.
Chromium-based anti-corrosive systems containing hexavalent Chromium compounds have proven to be an extremely useful and versatile group of chemistries that are extensively used in aircraft metal treatment processes. They impart many beneficial and essential anti-corrosive characteristics to metallic substrates on which they are applied and have been used extensively for the pre-treatment of metals before coating, adhesive bonding and surface finishing.
Chemically, Chromium-based anti-corrosive systems have involved the combination(s) of hexavalent Chromium (i.e., Cr03, Cr042-, Cr2072") and Hydrofluoric Acid (HF) in the case of aluminum and its alloys. The Hydrofluoric Acid removes oxide film from the surface of the metallic substrate (i.e., Aluminum) and the hexavalent Chromium reacts with the exposed metal and a trivalent Chromium Oxide precipitates. Using Aluminum as an example:
Cr2072" + 2A1 + 2H+ Cr203 = H20 + A1203 Chromium Oxide such as that produced according to the above reaction is quite useful in anti-corrosive applications. It is quite stable in alkaline environments, it is water repellant (hydrophobic) and may act as a barrier coating towards water. Finally, it exhibits a "self-healing effect" ¨ that is, residual hexavalent Chromium present in the coating may react with damaged areas of the coating ¨ thereby producing more trivalent Chromium Oxide at damaged sites and therefore "healing" itself.
Consequently, Chromium-based, and in particular hexavalent Chromium-based systems have been extensively used in the aircraft industry because they have proven to be:
highly effective at preventing corrosion and as an adhesion promoter for organic coatings and adhesives; particularly resilient as the application/treatment process exhibits a low sensitivity towards variation in process conditions; extremely effective on most/all Aluminum alloys; and ensure considerable quality control characteristics as a skilled worker may tell the amount of Chromium on the surface of a substrate by mere inspection (color) of the coating.
Concern about Chromium ¨ and in particular hexavalent Chromium ¨ in the environment has generated a need to replace Chromium-based systems. Hexavalent Chromium salts are classified as hazardous substances (toxic, sensitizing and carcinogenic) consequently they are environmentally and toxicologically undesirable. The European Parliament has published directives requiring the elimination of hexavalent Chromium such as directive 2002/95/EC for electrical and electronic equipment and directive 2000/53/EC for automotive sector. Therefore "environmentally friendly", commercially acceptable alternative to Chromium-based systems are highly desirable.
Prior art attempts to provide Chromium-free coatings have met with limited success.
For example, R.J.Racicot and S.C.Yang describe and compare the corrosion resistance performance of a polyaniline based conductive polymer coating versus a chromate conversion coating on two aluminum alloys in a paper entitled "CORROSION PROTECTION
COMPARISON OF A CHROMATE CONVERSION COATING TO A NOVEL CONDUCTIVE
POLYMER COATING ON ALUMINUM ALLOYS", which was presented at CORROSION 97, paper 531, pp.531/1-531/7, Houston, Tx., 1997. As disclosed by the authors, the double strand polyaniline exhibited limited corrosion protection for aluminum alloys AA2024-T3 and AA7075-T6 in salt-spray and salt and acid immersion tests.
The double strand polyaniline employed is a molecular complex of two polymers, polyaniline and a second polyanion. The two linear polymers are bonded non-covalently in a side-by-side fashion to form a stable molecular complex. As noted by the authors, the
FIELD
This invention relates generally to the field of coatings and corrosion control on metals, and in particular to a chromium-free conversion coating for aircraft applications.
BACKGROUND
Corrosion is defined as the chemical or electrochemical reaction between a material, usually a metal, and its environment that produces a deterioration of the material and its properties.
Corrosive attack begins on the surface of the metal. The corrosion process involves two chemical changes. The metal that is attacked or oxidized undergoes an anodic change, with the corrosive agent being reduced and undergoing a cathodic change. The tendency of most metals to corrode creates one of the major problems in the maintenance of aircraft, particularly in areas where adverse environmental or weather conditions exist.
Chromium-based anti-corrosive systems containing hexavalent Chromium compounds have proven to be an extremely useful and versatile group of chemistries that are extensively used in aircraft metal treatment processes. They impart many beneficial and essential anti-corrosive characteristics to metallic substrates on which they are applied and have been used extensively for the pre-treatment of metals before coating, adhesive bonding and surface finishing.
Chemically, Chromium-based anti-corrosive systems have involved the combination(s) of hexavalent Chromium (i.e., Cr03, Cr042-, Cr2072") and Hydrofluoric Acid (HF) in the case of aluminum and its alloys. The Hydrofluoric Acid removes oxide film from the surface of the metallic substrate (i.e., Aluminum) and the hexavalent Chromium reacts with the exposed metal and a trivalent Chromium Oxide precipitates. Using Aluminum as an example:
Cr2072" + 2A1 + 2H+ Cr203 = H20 + A1203 Chromium Oxide such as that produced according to the above reaction is quite useful in anti-corrosive applications. It is quite stable in alkaline environments, it is water repellant (hydrophobic) and may act as a barrier coating towards water. Finally, it exhibits a "self-healing effect" ¨ that is, residual hexavalent Chromium present in the coating may react with damaged areas of the coating ¨ thereby producing more trivalent Chromium Oxide at damaged sites and therefore "healing" itself.
Consequently, Chromium-based, and in particular hexavalent Chromium-based systems have been extensively used in the aircraft industry because they have proven to be:
highly effective at preventing corrosion and as an adhesion promoter for organic coatings and adhesives; particularly resilient as the application/treatment process exhibits a low sensitivity towards variation in process conditions; extremely effective on most/all Aluminum alloys; and ensure considerable quality control characteristics as a skilled worker may tell the amount of Chromium on the surface of a substrate by mere inspection (color) of the coating.
Concern about Chromium ¨ and in particular hexavalent Chromium ¨ in the environment has generated a need to replace Chromium-based systems. Hexavalent Chromium salts are classified as hazardous substances (toxic, sensitizing and carcinogenic) consequently they are environmentally and toxicologically undesirable. The European Parliament has published directives requiring the elimination of hexavalent Chromium such as directive 2002/95/EC for electrical and electronic equipment and directive 2000/53/EC for automotive sector. Therefore "environmentally friendly", commercially acceptable alternative to Chromium-based systems are highly desirable.
Prior art attempts to provide Chromium-free coatings have met with limited success.
For example, R.J.Racicot and S.C.Yang describe and compare the corrosion resistance performance of a polyaniline based conductive polymer coating versus a chromate conversion coating on two aluminum alloys in a paper entitled "CORROSION PROTECTION
COMPARISON OF A CHROMATE CONVERSION COATING TO A NOVEL CONDUCTIVE
POLYMER COATING ON ALUMINUM ALLOYS", which was presented at CORROSION 97, paper 531, pp.531/1-531/7, Houston, Tx., 1997. As disclosed by the authors, the double strand polyaniline exhibited limited corrosion protection for aluminum alloys AA2024-T3 and AA7075-T6 in salt-spray and salt and acid immersion tests.
The double strand polyaniline employed is a molecular complex of two polymers, polyaniline and a second polyanion. The two linear polymers are bonded non-covalently in a side-by-side fashion to form a stable molecular complex. As noted by the authors, the
2 advantages to such double strand complexes is: 1) that the conductive state of the polymer is very stable; 2) with proper choice of the polymeric dopant, the conductive polymer may be dispersed in solvents and used as a coating material; and 3) the polymeric dopant provides sites for functionalization to achieve good adhesion to metal surfaces.
I.Paloumpa, A.Yfantis, P.Hoffmann, Y.Burkov, D.Yfantis and D.Schmeiber describe, in -a paper entitled MECHANISMS TO INHIBIT CORROSION OF Al ALLOYS BY POLYMERIC
CONVERSION COATINGS, which appeared in Surface and Coatings Technology,180-181, pp.308-312, 2004, describe an polypyrrole-based coating which can be formed on an aluminum surface from an aqueous polypyrrole (PPY) chemisorbed on titanium an zinc oxides and exhibits advanced corrosion resistance.
U.S. Patent No. 5,342,456 to Doaln on August 30, 1994 describes a PROCESS FOR
COATING METAL SURFACES TO PROTECT AGAINST CORROSION wherein a chromium free conversion coating can be formed on metals ¨ particularly galvanized steel, by dry-in-place aqueous acidic liquids. The liquid comprises a component of anions, particularly at least four fluorine atoms and at least one atom from a group consisting of titanium, zirconium, hafnium, silicon, and boron and optionally, one or more oxygen atoms.
Additional cations from the group consisting of cobalt, magnesium, manganese, zinc, nickel, tin, zirconium, iron, aluminum and copper, a sufficient free acid to give a pH in the range of 0.5 to 5.0 and optionally a compound that will form an organic resinous film upon drying in place.
A CORROSION RESISTANT ALUMINUM ARTICLE COATED WITH EMERALDINE
BASE POLYANILINE, was described in a United States Patent No. 5,928,795 which issued to Spellane et al on July 27, 1999. The polyaniline used as the coating was a well-known emeraldine base form and is easily formed by the oxidative polymerization of aniline in excess hydrochloric acid by ammonium persulfate followed by treatment with ammonium hydroxide.
United States Patent No. 5,980,723 which issued to Runge-Marchese et al on Nov. 9, 1999, describes an ELECTROCHEMICAL DEPOSITION OF A COMPOSITE POLYMER
METAL OXIDE, which is a process for forming polymer films through electrochemical techniques utilizing electrolytes which include conductive polymer. The resulting polymer films described are electrically conductive and corrosion and wear resistant.
Example polymer films included polyaminobenzine (polyaniline).
I.Paloumpa, A.Yfantis, P.Hoffmann, Y.Burkov, D.Yfantis and D.Schmeiber describe, in -a paper entitled MECHANISMS TO INHIBIT CORROSION OF Al ALLOYS BY POLYMERIC
CONVERSION COATINGS, which appeared in Surface and Coatings Technology,180-181, pp.308-312, 2004, describe an polypyrrole-based coating which can be formed on an aluminum surface from an aqueous polypyrrole (PPY) chemisorbed on titanium an zinc oxides and exhibits advanced corrosion resistance.
U.S. Patent No. 5,342,456 to Doaln on August 30, 1994 describes a PROCESS FOR
COATING METAL SURFACES TO PROTECT AGAINST CORROSION wherein a chromium free conversion coating can be formed on metals ¨ particularly galvanized steel, by dry-in-place aqueous acidic liquids. The liquid comprises a component of anions, particularly at least four fluorine atoms and at least one atom from a group consisting of titanium, zirconium, hafnium, silicon, and boron and optionally, one or more oxygen atoms.
Additional cations from the group consisting of cobalt, magnesium, manganese, zinc, nickel, tin, zirconium, iron, aluminum and copper, a sufficient free acid to give a pH in the range of 0.5 to 5.0 and optionally a compound that will form an organic resinous film upon drying in place.
A CORROSION RESISTANT ALUMINUM ARTICLE COATED WITH EMERALDINE
BASE POLYANILINE, was described in a United States Patent No. 5,928,795 which issued to Spellane et al on July 27, 1999. The polyaniline used as the coating was a well-known emeraldine base form and is easily formed by the oxidative polymerization of aniline in excess hydrochloric acid by ammonium persulfate followed by treatment with ammonium hydroxide.
United States Patent No. 5,980,723 which issued to Runge-Marchese et al on Nov. 9, 1999, describes an ELECTROCHEMICAL DEPOSITION OF A COMPOSITE POLYMER
METAL OXIDE, which is a process for forming polymer films through electrochemical techniques utilizing electrolytes which include conductive polymer. The resulting polymer films described are electrically conductive and corrosion and wear resistant.
Example polymer films included polyaminobenzine (polyaniline).
3 An aqueous liquid surface treatment composition having a pH value not more than 6.5 and containing phosphoric acid ions, condensed phosphoric acid ions, an oxidizing agent and a water-soluble polymer was described in United States Patent No. 6,153,022 which issued to Yoshida on Nov. 28, 2000. The patentee therein reports that such coating rapidly forms on the surface of a metal, a conversion coating that has good corrosion resistance and adhesion to subsequently applied organic coatings such as paint and is less easily damaged by mechanical stresses than prior art conversion coatings.
ELECTROACTIVE POLYMER COATINGS FOR CORROSION CONTROL were described in United States Patent No. 6,150,032, which issued to Yang et al on November 21, 2000. In that patent, the patentees describe an anti-corrosive polymeric complex which comprises a plurality of double-stranded molecular complexes including conductive polymer and a strand of a copolymer. The strands of the polymeric complex are non-covalently bonded to each other along the contour of the strands to form a side-by-side, twisted, double-stranded configuration.
United States Patent No. 6,328,874, issued to Kinlen et al on December 11, 2001 for ANODICALLY FORMED INTRINSICALLY CONDUCTIVE POLYMER-ALUMINUM OXIDE
COMPOSITE AS A COATING ON ALUMINUM, describes a method for forming a coating on aluminum by contacting the aluminum with water, at least one multifunctional polymeric organic acid, a monomer of an intrinsically conductive polymer (ICP) and polymerizing the ICP
monomer and forming aluminum oxide by imposing an electrical potential between the aluminum surface as an anode and a cathode. The intrinsically conductive polymer salt and aluminum oxide coating that is formed resists corrosion and is resistant to de-doping during immersion in hot water.
A NONCHROMATE RUST PREVENTIVE AGENT FOR ALUMINUM, METHOD OF
RUST PREVENTION AND RUST-PREVENTIVE ALUMINUM PRODUCTS was described in United States Patent No. 6,419,731 which issued to lnbe et al on July 16,2002.
The patentees therein describe a nonchromate rust preventive agent for aluminum that comprises a zirconium compound, a fluoride ion, a water soluble resin and an aluminum salt.
Sako et al, in United States Patent No. 6,736,908 entitled "COMPOSITION AN
PROCESS FOR TREATING METAL SURFACES AND RESULTING ARTICLE", which issued on May 18, 2004, describes a metal treating composition comprising at least a specific type of
ELECTROACTIVE POLYMER COATINGS FOR CORROSION CONTROL were described in United States Patent No. 6,150,032, which issued to Yang et al on November 21, 2000. In that patent, the patentees describe an anti-corrosive polymeric complex which comprises a plurality of double-stranded molecular complexes including conductive polymer and a strand of a copolymer. The strands of the polymeric complex are non-covalently bonded to each other along the contour of the strands to form a side-by-side, twisted, double-stranded configuration.
United States Patent No. 6,328,874, issued to Kinlen et al on December 11, 2001 for ANODICALLY FORMED INTRINSICALLY CONDUCTIVE POLYMER-ALUMINUM OXIDE
COMPOSITE AS A COATING ON ALUMINUM, describes a method for forming a coating on aluminum by contacting the aluminum with water, at least one multifunctional polymeric organic acid, a monomer of an intrinsically conductive polymer (ICP) and polymerizing the ICP
monomer and forming aluminum oxide by imposing an electrical potential between the aluminum surface as an anode and a cathode. The intrinsically conductive polymer salt and aluminum oxide coating that is formed resists corrosion and is resistant to de-doping during immersion in hot water.
A NONCHROMATE RUST PREVENTIVE AGENT FOR ALUMINUM, METHOD OF
RUST PREVENTION AND RUST-PREVENTIVE ALUMINUM PRODUCTS was described in United States Patent No. 6,419,731 which issued to lnbe et al on July 16,2002.
The patentees therein describe a nonchromate rust preventive agent for aluminum that comprises a zirconium compound, a fluoride ion, a water soluble resin and an aluminum salt.
Sako et al, in United States Patent No. 6,736,908 entitled "COMPOSITION AN
PROCESS FOR TREATING METAL SURFACES AND RESULTING ARTICLE", which issued on May 18, 2004, describes a metal treating composition comprising at least a specific type of
4 dissolved and/or dispersed organic resin, a dissolved vanadium compound in which the valence of the vanadium is from 3 to 5, and a dissolved compound that contains at least one of the metals Zr, Ti, Mo, W, Mn, and Ce. According to the patentees, the treatment provides metal surfaces with superior corrosion resistance, alkali resistance, and fingerprint resistance.
=
Advantageously, their composition contains no Chromium.
United States Patent No. 6,758,916 for COMPOSITION AND PROCESS FOR
TREATING METALS issued to David McCormick on July 6, 2004 describes a chromium-free conversion coating at least equivalent in corrosion protective quality to conventional chromate conversions that can be formed on metals, particularly cold rolled steel, by dry-in-place aqueous acidic liquid. The liquid has a pH value between 0.5 and 5.0 and comprises "fluorometallate" anions consisting of at least four fluorine atoms; at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and optionally, one or more of ionizable hydrogen atoms and oxygen atoms; a component of divalent or tetravalent cations of elements selected from the group consisting of cobalt, magnesium, manganese, zinc, nickel, tin, copper, zirconium, iron, and strontium - in very precise relative proportions.
Despite the developments of the prior art, the corrosion resistance imparted by non-chromate type treatments is invariably less than that provided by chromate type methods and agents and has not satisfied practical needs ¨ particularly those in the aircraft industries. One object of present invention therefore is to provide a chromium-free coating which, despite being chromium-free, is capable of providing corrosion protection equivalent to or superior than a chromium-type coating, or at least to provide a commercially viable alternative to known coatings.
Wim J. Van Ooij et al. described, in a paper entitled "Modified silane coatings as an alternative to chromates for corrosion protection of aluminum alloys", which was published in Silanes and other coupling agents Vol. 3, pp 135-159, Ed. K.L.Mittal, 2004, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(trimethoxysilylpropyl)amine and vinyltriacetoxysilane based treatments applied onto AA2024-T3 alloys which also incorporated cerium nitrate, tolytriazole and benzotriazole corrosion inhibitors and silica nanoparticles.
Self-healing effects were reported for some of the treatments as well as good paint adhesion performance.
=
Advantageously, their composition contains no Chromium.
United States Patent No. 6,758,916 for COMPOSITION AND PROCESS FOR
TREATING METALS issued to David McCormick on July 6, 2004 describes a chromium-free conversion coating at least equivalent in corrosion protective quality to conventional chromate conversions that can be formed on metals, particularly cold rolled steel, by dry-in-place aqueous acidic liquid. The liquid has a pH value between 0.5 and 5.0 and comprises "fluorometallate" anions consisting of at least four fluorine atoms; at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and optionally, one or more of ionizable hydrogen atoms and oxygen atoms; a component of divalent or tetravalent cations of elements selected from the group consisting of cobalt, magnesium, manganese, zinc, nickel, tin, copper, zirconium, iron, and strontium - in very precise relative proportions.
Despite the developments of the prior art, the corrosion resistance imparted by non-chromate type treatments is invariably less than that provided by chromate type methods and agents and has not satisfied practical needs ¨ particularly those in the aircraft industries. One object of present invention therefore is to provide a chromium-free coating which, despite being chromium-free, is capable of providing corrosion protection equivalent to or superior than a chromium-type coating, or at least to provide a commercially viable alternative to known coatings.
Wim J. Van Ooij et al. described, in a paper entitled "Modified silane coatings as an alternative to chromates for corrosion protection of aluminum alloys", which was published in Silanes and other coupling agents Vol. 3, pp 135-159, Ed. K.L.Mittal, 2004, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(trimethoxysilylpropyl)amine and vinyltriacetoxysilane based treatments applied onto AA2024-T3 alloys which also incorporated cerium nitrate, tolytriazole and benzotriazole corrosion inhibitors and silica nanoparticles.
Self-healing effects were reported for some of the treatments as well as good paint adhesion performance.
5 Wim J. Van Ooij et al. described, in a paper entitled "Overview: The Potential of silanes for chromate replacement in metal finishing industries" which was published in Silicon Chemistry Volume 3, Numbers 1-2 (2006), that bis-(3-triethoxysilylpropyl) tetrasulfide treated 7075-T6 panels did not exhibit any sign of corrosion after 336 hours of salt spray exposure.
It is known that alcohol-based silanes offer a higher corrosion resistance to the water-based silane systems as the higher alcohol content removes more water from the film upon drying and the silanol groups can react more easily to form a cross-linked and denser film.
Also, the water-soluble silanes remain more hydrophilic even after drying, so they allow higher ingress of water than the solvent-based silanes. It is therefore important that these low-VOC
water-based silanes systems are further modified to increase their corrosion inhibition efficiency. In the publication "Effects of addition of corrosion inhibitors to silane films on the performance of AA2024-T3 in a 0.5M NaCI solution" by Wim J. Van Ooij et al., which was published in Progress in Organic Coatings 53 (2005) 153-168, corrosion inhibitors (tolytriazole, benzotriazole and inorganic cerium salts) were added to silane films and their corrosion properties studied in 0.5 M NaCI solution. The water-based silane solutions were prepared by mixing Bis[3-(trimethoxysilyppropyl]amine and Vinyltriacetoxysilane in 2:1 and 4:1 parts by volume and about 5% of this mixture was hydrolyzed with 95% of DI water.
Silane films when loaded with organic or inorganic inhibitors provided improved corrosion resistance. A scratch cell test confirmed that the cerium salts were also potential inhibitors for adding self-healing capabilities for silane films.
The publication "A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different slime solutions" by A.M. Cabral et al.
that was published in Progress in organic coatings 54 (2005) 322-331, reported a comparative study of AA-2024-T3 pre-treated with three different slime solutions (1, 2-Bis(Triethoxysily1) Ethane, bis-(3-triethoxysilylpropyl)tetrasulfide and y-mercaptopropyltrimethoxysilane). The silane treated samples were further treated with y-aminopropyltrimethoxy silane prior to paint them with a polyurethane enamel. The AC impedance results showed that silane films provided protection to the substrate. For a short time, the performance was even better than that conferred by the chromate reference treatment.
J.B. Bajat et al. described, in a paper entitled "Corrosion stability of epoxy coatings on aluminum pretreated by vinyltriethoxysilane", which was published in Corrosion Science 50 (2008) 2078-2084, the electrochemical and transport properties and adhesion of epoxy
It is known that alcohol-based silanes offer a higher corrosion resistance to the water-based silane systems as the higher alcohol content removes more water from the film upon drying and the silanol groups can react more easily to form a cross-linked and denser film.
Also, the water-soluble silanes remain more hydrophilic even after drying, so they allow higher ingress of water than the solvent-based silanes. It is therefore important that these low-VOC
water-based silanes systems are further modified to increase their corrosion inhibition efficiency. In the publication "Effects of addition of corrosion inhibitors to silane films on the performance of AA2024-T3 in a 0.5M NaCI solution" by Wim J. Van Ooij et al., which was published in Progress in Organic Coatings 53 (2005) 153-168, corrosion inhibitors (tolytriazole, benzotriazole and inorganic cerium salts) were added to silane films and their corrosion properties studied in 0.5 M NaCI solution. The water-based silane solutions were prepared by mixing Bis[3-(trimethoxysilyppropyl]amine and Vinyltriacetoxysilane in 2:1 and 4:1 parts by volume and about 5% of this mixture was hydrolyzed with 95% of DI water.
Silane films when loaded with organic or inorganic inhibitors provided improved corrosion resistance. A scratch cell test confirmed that the cerium salts were also potential inhibitors for adding self-healing capabilities for silane films.
The publication "A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different slime solutions" by A.M. Cabral et al.
that was published in Progress in organic coatings 54 (2005) 322-331, reported a comparative study of AA-2024-T3 pre-treated with three different slime solutions (1, 2-Bis(Triethoxysily1) Ethane, bis-(3-triethoxysilylpropyl)tetrasulfide and y-mercaptopropyltrimethoxysilane). The silane treated samples were further treated with y-aminopropyltrimethoxy silane prior to paint them with a polyurethane enamel. The AC impedance results showed that silane films provided protection to the substrate. For a short time, the performance was even better than that conferred by the chromate reference treatment.
J.B. Bajat et al. described, in a paper entitled "Corrosion stability of epoxy coatings on aluminum pretreated by vinyltriethoxysilane", which was published in Corrosion Science 50 (2008) 2078-2084, the electrochemical and transport properties and adhesion of epoxy
6 coatings electrodeposited on aluminum 99.7 pretreated by vinyltriethoxyslane (VTES). It was concluded that 5% solution for 10 minutes provided enhanced adhesion and also improved the corrosion stability of a protective system VTES/epoxy coating. The same authors reported, in a publication entitled "Corrosion protection of aluminium pretreated by vinyltriethoxysilane in sodium chloride solution", which was published in Corrosion Science 52 (2010) 1060-1069, EIS and potential-time measurements of VTES films deposited on A199.5%
substrates in 3%
NaCI medium exposure. It was shown that the concentration of VTES had a great influence on the corrosion behavior and morphology of the VTES films while curing time exhibited smaller influence of the VTES film properties.
B. Naderi Zand et al. described, in a paper entitled "Corrosion and adhesion study of polyurethane coating on silane pretreated aluminium", which was published in Surface &
Coatings Technology 203 (2009) 1677-1681, the effect of the silane pretreatment's pH on the adhesion strength and on the corrosion protection of subsequent polyurethane (PU) coating on aluminum alloy substrate. The practical adhesion of the coating on the substrate was measured in dry, wet and recovered states via pull-off method for desmutted, chromated and vinyltrimethoxysilane (VTMS) pretreated AA1050 aluminum alloy. VTMS resulted in good adhesion performance in dry, wet and recovered states at pH < isoelectric point (IEP).
Corrosion protection of PU coating was studied with EIS and salt spray in the presence of silane layer. At pH < IEP protective performance was considerably higher and comparable with that of chromated specimens.
F. Brusciotti et al. described, in a paper entitled "Characterization of thin water-based silane pre-treatments on aluminium with the incorporation of nano-dispersed Ce02 particles", which was published in Surface and Coatings Technology 205 (2010) 603-613, novel thin films of water-based 1, 2-bis(Triethoxysilyl)ethane (BTSE) with the incorporation of nano-dispersed Ce02 particles for improved barrier properties. EIS investigations pointed out a better performance for the coatings where the Ce02particles were nano-dispersed and uniformly distributed in the layer.
U.S. Pat. No. 6,071,566 which was issued to Kevon Brown et al., relates to a method that comprises applying a solution containing one or more vinyl silanes with or more multi-silyl-functional silanes for treating a metal substrate providing corrosion resistance. The method is particularly suitable for use in zinc coated surfaces. The particular preferred vinyl silane is
substrates in 3%
NaCI medium exposure. It was shown that the concentration of VTES had a great influence on the corrosion behavior and morphology of the VTES films while curing time exhibited smaller influence of the VTES film properties.
B. Naderi Zand et al. described, in a paper entitled "Corrosion and adhesion study of polyurethane coating on silane pretreated aluminium", which was published in Surface &
Coatings Technology 203 (2009) 1677-1681, the effect of the silane pretreatment's pH on the adhesion strength and on the corrosion protection of subsequent polyurethane (PU) coating on aluminum alloy substrate. The practical adhesion of the coating on the substrate was measured in dry, wet and recovered states via pull-off method for desmutted, chromated and vinyltrimethoxysilane (VTMS) pretreated AA1050 aluminum alloy. VTMS resulted in good adhesion performance in dry, wet and recovered states at pH < isoelectric point (IEP).
Corrosion protection of PU coating was studied with EIS and salt spray in the presence of silane layer. At pH < IEP protective performance was considerably higher and comparable with that of chromated specimens.
F. Brusciotti et al. described, in a paper entitled "Characterization of thin water-based silane pre-treatments on aluminium with the incorporation of nano-dispersed Ce02 particles", which was published in Surface and Coatings Technology 205 (2010) 603-613, novel thin films of water-based 1, 2-bis(Triethoxysilyl)ethane (BTSE) with the incorporation of nano-dispersed Ce02 particles for improved barrier properties. EIS investigations pointed out a better performance for the coatings where the Ce02particles were nano-dispersed and uniformly distributed in the layer.
U.S. Pat. No. 6,071,566 which was issued to Kevon Brown et al., relates to a method that comprises applying a solution containing one or more vinyl silanes with or more multi-silyl-functional silanes for treating a metal substrate providing corrosion resistance. The method is particularly suitable for use in zinc coated surfaces. The particular preferred vinyl silane is
7 vinyltriethoxysilane (VS) and the preferred multi-functional silane is 1, 2-bis(triethoxysilyl)ethane (BTSE).
Accordingly, one object of present invention is to tackle the disadvantages associated with the prior art, to provide a chromium-free coating with an improved adhesion properties, or at least to provide a commercially viable alternative to known coatings.
SUMMARY
In a first aspect, the present invention relates to a process for treatment of metallic surfaces, said process comprising the steps of:
pre-treating the surfaces;
coating the surfaces with a conversion coating by contacting them with a conducting polymer dispersion containing:
one or more silanes, and inorganic metallic salts selected from at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc in concentrations of the metal salt between 2.0 and 20 g/L and a pH value of between 1 and 6.0; and drying the surfaces.
In the following passages different aspects/embodiments are defined in more detail.
Each aspect/embodiment so defined may be combined with any other aspect/embodiment or aspects/embodiments unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Chemical conversion coatings must perform a dual function: to improve the corrosion resistance of the substrate alloy and to promote a good adhesion of the subsequent organic coatings. Additionally, these coatings can be used in parts where surface contact electrical resistance is also a requirement (the maximum electrical resistance values allowed by the MIL-DTL-81706-B standard are 5000pD/square inch before the salt spray exposure test and 1 00001AI/square inch after 168h of salt spray exposure test under an applied electrode pressure of 200 pound per square inch (psi). Individual readings not greater than 20% in
Accordingly, one object of present invention is to tackle the disadvantages associated with the prior art, to provide a chromium-free coating with an improved adhesion properties, or at least to provide a commercially viable alternative to known coatings.
SUMMARY
In a first aspect, the present invention relates to a process for treatment of metallic surfaces, said process comprising the steps of:
pre-treating the surfaces;
coating the surfaces with a conversion coating by contacting them with a conducting polymer dispersion containing:
one or more silanes, and inorganic metallic salts selected from at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc in concentrations of the metal salt between 2.0 and 20 g/L and a pH value of between 1 and 6.0; and drying the surfaces.
In the following passages different aspects/embodiments are defined in more detail.
Each aspect/embodiment so defined may be combined with any other aspect/embodiment or aspects/embodiments unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Chemical conversion coatings must perform a dual function: to improve the corrosion resistance of the substrate alloy and to promote a good adhesion of the subsequent organic coatings. Additionally, these coatings can be used in parts where surface contact electrical resistance is also a requirement (the maximum electrical resistance values allowed by the MIL-DTL-81706-B standard are 5000pD/square inch before the salt spray exposure test and 1 00001AI/square inch after 168h of salt spray exposure test under an applied electrode pressure of 200 pound per square inch (psi). Individual readings not greater than 20% in
8 excess of the specified maximums shall be acceptable, provided that the average of all readings does not exceed the specified maximum resistance).
New processes and compositions for Cr-free conversion coatings with good corrosion resistance were invented by the authors and the patent application US
2010/0009083 was submitted. The conversion coatings described in the abovementioned patent application showed very good corrosion performance. However, the present inventors have now discovered that they can improve the adhesion of these coatings to subsequent organic coatings without jeopardizing the corrosion protection.
Indeed, the inclusion of a silane in the coating of US2010/0009083 has been found to provide a significant improvement. The conducting polymer dispersion described in the patent comprises at least one silane compound apart from the other bath components (conducting polymer and inorganic salts). The silane compounds enhance the adhesion performance so the coatings comply with the requirements of aeronautical applications while the corrosion protection as described in the examples is maintained.
Moreover, the new conversion coatings obtained with the conducting polymer dispersions comprising at least one silane compound offer low surface contact electrical resistance, compliant with the requirements for aeronautical applications.
The process and composition has now been optimized in order to enhance the adhesion of the subsequent organic coatings, while maintaining the corrosion protection of the substrate. Additionally, the coatings obtained with these processes based on compositions comprising at least one silane compound have proven to have low contact electrical surface resistance, compliant with the requirements for aeronautical applications.
The challenge has been to optimize the chemical conversion process and the coating composition to enhance the adhesion and reduce the electrical resistance without jeopardizing the corrosion protection.
In the process of silane treatment of metals, two main reactions occur on the basis of the number of silanols (SiOH) after the silane molecules are adsorbed onto the metal surface.
On the one hand, the condensation between silanols (SiOH) from the silane solution and the metal hydroxyls (Me0H) from the metal surface hydroxides forms metallo-siloxane bonds
New processes and compositions for Cr-free conversion coatings with good corrosion resistance were invented by the authors and the patent application US
2010/0009083 was submitted. The conversion coatings described in the abovementioned patent application showed very good corrosion performance. However, the present inventors have now discovered that they can improve the adhesion of these coatings to subsequent organic coatings without jeopardizing the corrosion protection.
Indeed, the inclusion of a silane in the coating of US2010/0009083 has been found to provide a significant improvement. The conducting polymer dispersion described in the patent comprises at least one silane compound apart from the other bath components (conducting polymer and inorganic salts). The silane compounds enhance the adhesion performance so the coatings comply with the requirements of aeronautical applications while the corrosion protection as described in the examples is maintained.
Moreover, the new conversion coatings obtained with the conducting polymer dispersions comprising at least one silane compound offer low surface contact electrical resistance, compliant with the requirements for aeronautical applications.
The process and composition has now been optimized in order to enhance the adhesion of the subsequent organic coatings, while maintaining the corrosion protection of the substrate. Additionally, the coatings obtained with these processes based on compositions comprising at least one silane compound have proven to have low contact electrical surface resistance, compliant with the requirements for aeronautical applications.
The challenge has been to optimize the chemical conversion process and the coating composition to enhance the adhesion and reduce the electrical resistance without jeopardizing the corrosion protection.
In the process of silane treatment of metals, two main reactions occur on the basis of the number of silanols (SiOH) after the silane molecules are adsorbed onto the metal surface.
On the one hand, the condensation between silanols (SiOH) from the silane solution and the metal hydroxyls (Me0H) from the metal surface hydroxides forms metallo-siloxane bonds
9 (Me0Si). On the other hand, the condensation among the excess SiOH groups adsorbed on the metals forms a siloxane (SiOSi) film on the top of the coating.
Preferably a medium is used for silane solution preparation; silanes may be classified in water-based or solvent-based silanes. It is desirable to use water-based silane systems with nil or very little alcohol content, due to VOC restrictions. Preferably the one or more silanes are water soluble.
Preferably the one or more silanes are present in an amount of from 0.01 v%. ¨
1.0 v%
(v/v) of the polymer dispersion, more preferably from 0.1 v% to 0.5v%. With this range of silane content the beneficial effects of the silane are observed, without compromising the corrosion resistance.
Preferably, the one or more silanes are of the formula YSiX(3_a)Za wherein, X are independently selected hydrolysable groups, Y is non-hydrolysable and includes a functional group, Z is independently selected from H or alkyl, and a is 0, 1 or 2.
By hydrolysable group it is meant that the group is susceptible to nucleophilic attack to cleave the group from the silicon atom. X are independently selected hydrolysable groups. It is preferred that the hydrolysable groups are selected from methoxy (OCH3) or ethoxy (0C2H5).
These groups allow for good adhesion of the compound to nucleophilic sites on the metal and/or further coatings.
By non-hydrolysable it is meant that the group is not susceptible to nucleophilic attack to cleave the group from the silicon atom. Preferably the Y moiety is joined to the silicon atom by a silicon-carbon bond.
Y includes a functional group. That is, Y includes a group capable of reacting to link the silicon atom to a further coating, a further silane or to the metal substrate.
The functional group is preferably selected from vinyl (-CH=CH2), amino (-NH2), epoxy or mercapto (-SH)). The functional group may consist of this functional group, but preferably the functional group is linked to the silicon atom by an alkyl chain, preferably a lower alkyl (C1-C6) chain, an alkylether or an alkylamine. Thus, for example, Y may preferably be: -(CH2)õ-NH2; -(CH2),-SH, or -(CH2)n- HC=CH2, and n is preferably 0-6, preferably 1-6, more preferably 0-3.
In one embodiment the functional group may be a further silicon-containing moiety.
Thus, Y may be ¨RSIX3_aZa, where X, Z and a are as defined above. R may be an alkyl, an ether or an alkylamine. For example, R is an ether, such as CH2OCH2 or R is an amine, such as (CH2)3NH(CH2)3. According to their chemical structures, silane molecules are divided into two major categories, mono-silanes and bis-silanes. Bis-type silanes have two silicon atoms in their molecule whereas mono-silanes have only one, with a general formula of X3Si-R-SiX3.
Preferably the silane is symmetrical in this way for ease of synthesis and to minimize production costs. The main difference between mono and bis-silanes is that the number of hydrolysable X groups is double in a bis-silane molecule than in a mono-silane molecule.
Thus, it is reported that bis-silanes offer stronger interfacial adhesion (with the substrate) and denser films leading to better corrosion performance compared to mono-silanes, especially in unpainted state.
By "alkyl" is meant a straight or branched chain saturated cyclic (i.e., cycloalkyl) or acyclic hydrocarbon group of from 1 to 12 carbons, unless otherwise specified.
Exemplary alkyl groups include C1-C8, C1-C6, C1-C4, C2-C7, C3-C12, and C3-C6 alkyl.
Specific examples include methyl, ethyl, 1-propyl, 2-propyl, 2-methyl-1-propyl, 1-butyl, 2-butyl, and the like. Unless otherwise noted, alkyl groups, used in any context herein, may optionally be substituted with halogen, amino or sulfyl groups, or may include one or more heteroatoms in the alkyl chain, such as oxygen (an ether) or nitrogen (an amine).
Z is independently selected from H or alkyl. That is, Z is a non-hydrolysable group that does not include a functional group for linking the silane to a further coating, a further silane or to the metal substrate. In particular, it is preferred that a is 0.
Preferably, the one or more silanes are selected from (3-Glycidoxypropyl) trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyl]amine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
Preferably, said conducting polymer is one selected from the group consisting of:
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY).
Preferably the coating step is applied to the surfaces by spraying, or immersion. If the coating step is immersion, preferably it is for a period of substantially 2 minutes in the treatment bath. Preferably said drying step is performed at substantially room temperature.
The pretreatment step serves to prepare the surface of the metal for the coating.
.5 Accordingly, the pretreatment step at least involves the cleaning of the surface. Preferably said pretreatment step further comprises the steps of:
degreasing the surfaces;
cleaning the surfaces; and deoxidizing the surfaces.
Preferably the method further comprising the steps of: rinsing the surfaces after cleaning; and rinsing the surfaces after deoxidizing; and not-rinsing the surfaces after coating.
Preferably the inorganic metal salt is or comprises a salt of Zirconium, the concentration of inorganic metallic salts of Zirconium are produced/adjusted with K2ZrF6 and the pH is adjusted with H2ZrF6 and/or NI-140H.
Preferably said metallic sheets are ones selected from the group consisting of aluminum, copper, iron, or alloys thereof, and preferably is selected from the group consisting of 2024-T3 and 7075-T6.
Preferably the inorganic salts are present in a concentration of 2.0 to 8.0 g/L and/or wherein the contacting step is carried out at a pH of 2 to 5.
According to a second aspect, there is provided a conversion coating for the treatment of metallic surfaces, said coating comprising one or more silanes, and a conducting polymer dispersion containing an inorganic metallic salt of at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc, wherein the concentration of the inorganic metallic salt is between 2.0 and 20 g/L and the pH
of the coating is between 1 and 6Ø
Preferably the one or more silanes are as described above and as discussed herein.
Preferably the conducting polymer is one selected from the group consisting of:
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY), and/or wherein the one or more silanes are selected from (3-Glycidoxypropyl)trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyppropyl]amine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
These and other features and advantages of the present invention will become .5 apparent with reference to the attached drawing and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete understanding of the present invention may be realized by reference to the accompanying drawing and tables in which:
FIG. 1 is a process flow chart depicting the steps associated with our chromium-free conversion coating of the present invention.
TABLE 1 shows the properties of several conducting polymers used in the present invention according to data provided by suppliers of the polymers;
TABLE 2 shows the experimental conditions for PEDOT/Zr for both tested alloys according to the present invention;
TABLE 3 shows the experimental conditions for PPY/Zr for both tested alloys according to the present invention;
TABLE 4 shows the measured corrosion of alloys treated with PEDOT/Zr according to the present invention; and TABLE 5 shows the measured corrosion of selected alloys treated with PPY/Zr according to the present invention.
TABLE 6 is a table that shows the molecular and structural formula of several silanes used in the present disclosure.
TABLE 7 is a table that shows the experimental conditions for PEDOT/Zr/silane for both tested alloys according to the disclosure.
TABLE 8 is a table that shows the experimental conditions for PPY/Zr/silane for both tested alloys according to the disclosure.
TABLE 9 is a table that shows the measured corrosion, adhesion and surface contact electrical resistance of alloys treated with PEDOT/Zr according to the disclosure.
TABLE 10 is a table that shows the measured corrosion, adhesion and surface contact electrical resistance of alloys treated with PPY/Zr according to the disclosure.
DETAILED DESCRIPTION
As can be appreciated by those skilled in the art, chemical conversion surface treatments/coatings generally involve the process of immersion or other contact of a metal = 5 (i.e., Aluminum and/or Alloys of Aluminum) with an active bath or spray that ¨ through a redox reaction at the metallic surface or chemical deposition at the metallic surface due to physicochemical changes in the treatment bath ¨ form a superficial adhered protective coating. Such conversion coatings typically exhibit quite low solubility and ¨
in the case of Aluminum ¨ a thickness of approximately 20nm to lmm, depending upon the process parameters and the alloy treated, while the substrate thickness lost is quite small or minimal.
The color of the resulting conversion coating obtained depends upon the base material and the bath/spray parameters.
Advantageously, our inventive conversion coating may be prepared in a single-step immersion process. Accordingly, parts, i.e., panels, to be coated are bathed in a conducting polymer dispersion in which different inorganic salts and silanes along with other additives that affect the bath and/or resulting coating, i.e., bath dispersion agents, wetting agents, or polymeric film formation agents.
FIG 1 depicts an overview of the steps involved in our inventive process. More particularly, our inventive process includes three general phases namely, pretreatment, conversion, and drying. And while our discussion herein is concerned primarily with Aluminum and certain specific alloys of Aluminum, our invention is not so limited. In particular, different metal compositions and alloys as well as additional applications, i.e., automotive, industrial, etc., would benefit from our inventive method and resulting coating as well.
Returning now to FIG 1, it may be observed that Pretreatment begins by degreasing the panels to be coated (Block 110). Degreasing may be performed using any of a variety of known detergent solutions and/or organic solvents. Additionally, such degreasing ¨ like all of the process steps ¨ may be performed by spray application or bath/immersion or a mixture of the two techniques.
Once the panel(s) to be coated is degreased, it is then cleaned/washed with an alkali solution (Block 120). Such solutions are commercially available under various trade names i.e., TURCO (4215NCLT), and this alkali cleaning/washing is advantageously performed for approximately 10 minutes at a modest elevated temperature, i.e., 50 C. After cleaning/washing, the panel is rinsed with water and then deoxidized (Block 130), with, for example TURCO Smut Go NC for approximately 5 minutes at ambient temperature(s) and then rinsed. Advantageously, other pickling or desmutting steps can be used depending on the treated substrate material and surface material or thickness to be removed.
As can be now appreciated, our inventive process employs commercially available pretreatment steps which are well known and understood. Advantageously, such pretreatment is compatible with a variety of alloys and their application is widely understood.
In an exemplary embodiment, conversion treatment (Block 140) includes immersion of aluminum alloy panels, in a bath for a period of time followed by direct (no rinse) drying (Block 150) of the treated panels. Generally, the conversion treatment bath is prepared by an initial stirring of a conducting, polymeric dispersion. Advantageously, the polymer dispersion(s) used may be commercially available water-based ones and exhibit satisfactory formulation(s) including solid content, pH, and dispersive additives. Consequently, only a minimal amount of stirring is required for these commercial dispersions. Of further advantage, the conversion treatment in the bath is only a 2 minutes process.
Such conducting polymeric dispersions include Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY) among others. The particular conducting polymeric dispersions used in our examples and their physical properties are shown in Table 1. While we have limited our discussion herein to those conducting polymeric dispersions exhibiting superior performance in our experiments, it should be noted that a number of dispersions may be suitable ¨ depending upon the particular application requirements. More specifically, dispersions of polyphenylene, polyphenylene vinylene, polyethylenesulfide and derivatives of all the mentioned conducting polymers should produce satisfactory results.
In addition, other polymeric components such as acrylics, polyurethanes, epoxies, amino resins, phenolics, vinylics, polyesters, etc., may be added to enhance particular characteristics of the coating.
Returning now to the description of our inventive method, after stirring the conducting polymeric dispersion (and any polymeric components), a quantity of inorganic salt(s) or mixtures thereof are added to the conducting polymeric dispersion and subsequently mixed until the added salts are suitably dissolved. Example salts include the inorganic salts of Molybdenum, Manganese, Zirconium and Titanium. More particularly, Sodium Molybdate, Potassium Permanganate, Potassium Hexafluorozirconate and Potassium Hexaflorotitanate have been used with success. Final concentrations of the added salts in the bath solution(s) may vary over a wide range, i.e., 2-20 g/L.
After the inorganic salt(s) or mixtures thereof are added to the conducting polymeric dispersion and subsequently mixed until the added salts are suitably dissolved, a quantity of silane(s) or mixtures thereof are added to the conducting polymeric/salt(s) dispersion and subsequently mixed until the added silanes are suitably dissolved. The particular silanes used in the examples and their molecular and structural formula are shown in table 6. (3-Glycidoxypropyl)trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyl]amine (BAS) and Vinyltriacetoxysilane (VTAS) have been used with success. The final concentrations of the added salts in the bath solution(s) may vary over a range, e.g., % 0.01 vol.
(% v/v) ¨ % 1.0 vol.
(% v/v).
Finally, the polymeric dispersion/inorganic salt /silane solution is subsequently pH
adjusted using alkaline compounds such as ammonia or phosphate or acidic compounds, including hexaflorozirconic acid and fluorhydric acid.
EXPERIMENTAL / RESULTS
A number of samples of two particular aluminum alloys, namely 2024T3 and alloys were subjected to our inventive Chromium-free conversion process and evaluated.
Those showing superior characteristics in salt spray fog corrosion tests (SSFCT) were obtained using PPY and PEDOT in combination with Hexaflorozirconate. The particular experimental conditions are shown in Table 2, Table 3 for PEDOT/Zr, PPY/Zr, based compositions and Table 4, and Table 5 show the obtained results respectively.
For all of the samples shown in these Tables, the drying conditions were substantially room temperature and pressure, for a period of time of at least 24 hours.
More specifically, Table 2 shows the experimental conditions for PEDOT/Zr. In this set, the [Zr] concentration was effected by varying the amounts of K2ZrF6 and the pH was adjusted with H2ZrF6 and/or NH4OH.
Table 3 shows the experimental conditions used for a PPY/Zr set of samples. In this particular set, the [Zr] concentration was effected by varying the amounts of K2ZrF6 and the pH
was adjusted with H2ZrF6 and/or NH4OH.
Turning now to Table 4, there it shows the corrosion resistance for our inventive PEDOT/Zr conversion coating on both 2024-T3 and 7075-T6 aluminum alloys. The results obtained were after 168 hours of salt spray fog corrosion testing (SSFCT) and the hexavalent chromium based commercial ALODINE 1200S exhibits the best corrosion performance, with a corrosion score of 10Ø The corrosion score values go from 0 for the worst corrosion performance to 10 for best corrosion performance.
Similarly, Table 5 shows the corrosion resistance for our inventive PPY/Zr coating on the 2024-T3 and 7075-T6 alloys as well as the ALODINE 1200S treated alloys.
A number of samples of two particular aluminum alloys, namely 2024T3 and alloys, were subjected to the polymeric dispersion/inorganic salt /silane chromium-free conversion process and evaluated. Those showing superior characteristics in salt spray fog corrosion tests (SSFCT) were obtained using PPY and PEDOT in combination with hexaflorozirconate and GPMS, TMSE and BTSE silanes ¨ added either alone or in combination. Those showing superior characteristics in the scribed wet tape paint adhesion tests of a subsequently applied organic coating were obtained using PPY and PEDOT in combination with hexaflorozirconate and GPMS, TMSE, BTSE, BAS and VTAS silanes ¨
added either alone or in combination ¨. Some of the proposed treatments provided combined superior characteristics in salt spray fog corrosion tests and in the scribed wet tape paint adhesion tests of a subsequently applied organic coating. Additionally, some of those treatments providing combined superior characteristics in salt spray fog corrosion tests and in wet tape paint adhesion tests of a subsequently applied organic coating also provided superior characteristics in surface contact electrical resistance measurements. The particular experimental conditions are shown in the tables of TABLES 8 and 9 for PEDOT/Zr/silane, PPY/Zr/silane, based compositions and the tables of TABLES 10 and 11 show the obtained results, respectively. For all of the samples shown in these tables of TABLES
8-11, the drying conditions were substantially room temperature and pressure, for a period of time of at least 24 hours.
More specifically, the table of TABLE 8 shows the experimental conditions for PEDOT/Zr/silane. In this set, the [Zr] (zirconium) concentration was effected by varying the amounts of K2ZrF6 (potassium hexafluorozircoante) and the pH was adjusted with H2ZrF6 (fluorozirconic acid) and/or NH4OH (ammonium hydroxide).
The table of TABLE 9 shows the experimental conditions for a PPY/Zr/silane set of samples. In this particular set, the [Zr] (zirconium) concentration was effected by varying the amounts of K2ZrF6 (potassium hexafluorozirconate) and the pH was adjusted with H2ZrF6 (fluorozirconic acid) and/or NH4OH (ammonium hydroxide).
Turning now to the table of TABLE 10, there it shows the corrosion resistance for the PEDOT/Zr/silane conversion coating on both 2024-T3 and 7075-T6 aluminum alloys. The results obtained were after 168 hours of salt spray fog corrosion testing (SSFCT) and the hexavalent chromium based commercial ALODINE 1200S exhibited the best corrosion performance, with a corrosion score of 10Ø The corrosion score values go from 0 (zero) for the worst corrosion performance to 10 (ten) for best corrosion performance.
The table in TABLE 8 also shows the adhesion performance of a subsequently applied organic coating on both 2024-T3 and 7075-T6 aluminum alloys. The paint adhesion performance was measured according to a wet tape paint adhesion test. Once dried (after 14 days air curing), the corresponding conversion coated panels were painted with an epoxy primer according to the MIL-PRF-85582 standard. The epoxy primer used was a water-reducible epoxy primer system made of 10PW20-4 base and ECW-104 hardener according to MIL-PRF-85582 Type 1 Class 2, provided by Ala Nobel Aerospace Coatings, By. Two parallel, 2 inch long scratches, 3/4 to 1 inch apart through the coating and to the substrate were made on the panels.
The parallel scratches were joined with two intersecting lines, or an "X" pattern. The primed and scribed panels were immersed in deionised water during 24 hours, prior to carrying out the wet paint adhesion tests. Within 2 minutes after removing test panels from water adhesive tape was applied and pressed against the test surface with firm hand pressure and then removed. The hexavalent chromium based commercial ALOD1NE 1200S exhibited the best pant adhesion performance, with an adhesion score of 1 0ØThe adhesion test score values go from 0 (zero) for the worst adhesion performance (total detachment of the primer) to 10 (ten) for best adhesion performance (no detachment of the primer). The table in TABLE 8 also shows the surface contact electrical resistance for the PEDOT/Zr/silane conversion coating on 2024-T3, 7075-T6 and 6061-T6 aluminum alloys. The surface contact electrical resistance of the coatings was measured as described in the MIL-DTL-81706-B standard. The applied load shall be within one percent of the calculated 200psi applied pressure. The contacting electrodes were copper or silver-plated copper with a finish not rougher than that obtained by the use of 000 metallographic abrasive paper. The electrodes were flat enough so that when the load was applied without a specimen between them, light is not visible through the contacting surface. The area of the upper electrode was one square inch (25 square mm) and the area of the lower electrodes was larger. The maximum electrical resistance values allowed by aeronautical standards for 6061 T6 alloy are of 5000J/square inch (5 ma/square inch) before salt spray exposure test. The hexavalent chromium based commercial ALODINE
1200S exhibited the lowest surface contact electrical resistance for the 2024-T3 and 7075-T6 alloys. The values for the PEDOT/Zr/silane treatments were also well below the 5 ma/square inch.
Similarly, the table of TABLE11 shows the corrosion resistance, the paint adhesion performance and the surface contact electrical resistance measurements for the PPY/Zr/silane coatings on the 2024-T3, 7075-T6 and 6061-T6 alloys as well as the ALODINE
1200S treated alloys.
At this point, it should be noted that in addition to the Zr salts used in these exemplary tests, other salts ¨ either alone or in combination ¨ may produce satisfactory results as well.
In particular, salts of Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt, Magnesium, and Zinc may be employed. Additionally, other bath components such as pH
adjusting compounds, solvents, non-aqueous dispersion media, other silanes, dispersing agents, surfactants and coalescing solvents may be used to provide various degrees of coating effectiveness. Further, while our inventive method and resulting coating(s) have been described in the context of immersion bath(s), it is understood that alternative coating, i.e., spray coating may be used as well. Lastly, other metallic substrates, such as steel, aluminum, copper, and/or iron and/or their alloys, will benefit from our method and coating(s).
Material i PANI PEDOT PPY
Property Polymer Po!yenning Polyethylenedioxythlophsrie Polypyrrole Solid Content 6.0% 1.2 ¨ 1.4% 6.0%
Dilution with Water Water Water pH 2.3 1.5 ¨ 2.5 3 or kiss .., Conductivity p 1 ¨ 2 Up To 10 0.01 ¨ 0.001 (SIC")) Pellets Cast Film Cast Film Surface Resistivity 10E4 10E0 10E4-10E6 (Ohm) , Viscosity is Pas 60 - 100 niPas N.A.
Supplier Pardpol Bayer Essays Trade Name Panipol W Baytron P Eeonoiner 7000 PEDOT / Zr Experiment [PEDOT] (%) Rd (Wt.)* pH "
, , v PEDOT 1 0.43 8 2 PEDOT 2 0.86 s 3.5 PEDOT 3 0.43 2 2 PEDOT 4 1.30 2 2 PEDOT 5 , 0.43 8 s -PEDOT 6 1.30 2 5 PEDOT 7 1.30 s 2 PEDOT 8 0.86 , 5 3.5 PEDOT 9 0.43 2 s PEDOT 10 0.86 s 3.5 PEDOT 11 1.30 8 s .
PEDOT 12 0.43 s 3.5 PED07' 13 0.86 2 3.5 PEDOT 14 0.86 5 2 ..- _ Experimental Conditions for PEDOT / Zr *PI iiii.* PcIrFol git.; " pH Milusted with VC. andior NN4OH
, PPY / Zr Experiment IPEDOT] (%) [Zr] (g/L)* pH **
PPY 4 2 2 2 , PPY 5 4 5 3.5 PPY 8 4 5 3.5 PPY 8 4 6 3.5 PPY 9 6 s 2 . .
PPY 11 e 2 5 .
PPY 12 2 5 3.5 PPY 13 4 23.5 . .
Experimental Conditions for PPY / Zr .rzil all. 0 PC,2Zry sk; " pH Adjusted with Hpfs and/or NH4OH
Corrosion Score EXPERIMENT
PEDOT 1 3.0 3.0 PEDOT 2 3.6 8.5 PEDOT 3 1.0 3.6 , PEDOT 4 1.5 3.7 PEDOT 5 4.0 9.0 PEDOT 8 2.0 8.5 PEDOT 7 2.0 3.5 PEDOT 8 3.5 82 , PEDOT 9 3.6 9.0 PEDOT 10 4,0 4.5 PEDOT 11 8.0 2.7 .
PEDOT 12 9.5 95 PEDOT 13 2.5 6.6 PEDOT 14 2.6 2.0 Experimental Results for PEDOT / Zr Corrosion Score EXPERIMENT
PPY 1 1.0 1.50 PPY 2 1.0 1.75 PPY 3 4.0 5.0 PPY 4 1.0 1.75 PPY 5 5.0 5.5 PPY 6 , 4.0 5.5 PPY7 4.0 4.5 PPY 8 4.0 5.25 PPY 9 0.75 1.75 PPY 10 4.75 8.0 PPY 11 2.6 6.0 PPY 12 4.0 5.0 PPY 13 3.0 4.0 PPY 14 0.5 1.5 Experimental Results for PPY I Zr SHORT
= COMPOUND MOLECULAR FORMULA ESTRUCTURAL FORMULA
NAME
(3- 9CH3 Glycidoxypropyl) GPMS C9H2005S1 trimethoxysilane OCH3 0 1,2-Bis OCH3 OCH3 (thmethoxysily1) TMSE C8H2206Si2 H3CO-Si , ethane ocH3 OCH3 H
1,2- H3c,,..õ0-T¨\ 3 H
Bis(Triethoxysily1) BTSE [-CH2Si(0C2H5)3]2 c3 Ethane cH3 cH3 Bis[3-(trimethoxysily1) BAS [(CH30)3Si(CH2)312NH
propygamine Vinyltriacetoxy VTAS (C,H3C0.,2)3sir.õ..1-4=cH2 silane TABLE 7- Experimental conditions for PEDOT/Zr/Silane PEDOT / Zr / Silane Experiment [PEDOT] (%) [Zr] (g/L)* [Silane] (% vol.) pH**
PEDOT 15 0.43 5 0.10 GPMS 3.5 PEDOT 16 0.43 5 0.25 GPMS 3.5 PEDOT 17 0.15 5 0.10 GPMS 3.5 PEDOT 18 0.15 5 0.06 TMSE 3.5 * [Zr] g/L = [K2ZrF6] g/L
** pH adjusted with H2ZrF6 and/or NH4OH
TABLE 8 - Experimental conditions for PPY/Zr/Silane PPY / Zr / Silane Experiment [PPY] (%) [Zr] (g/L)* [Silane] (% vol.) pH**
PPY 15 0.25 5 0.10 GPMS 3.5 PPY 16 0.25 5 0.10 GPMS 3.0 PPY 17 0.25 5 0.05 GPMS 3.0 PPY 18 0.10 5 0.10 GPMS 3.5 PPY 19 0.50 5 0.10 GPMS 3.5 PPY 20 0.15 5 0.10 GPMS 3.5 PPY 21 0.25 5 0.25 GPMS 3.5 PPY 22 0.50 5 0.25 GPMS 3.5 PPY 23 0.25 5 0.06 TMSE 3.5 PPY 24 0.25 5 0.06 TMSE 5.0 PPY 25 0.25 5 0.15 TMSE 3.5 PPY 26 0.25 5 0.15 TMSE 5.0 PPY 27 2.0 8 0.06 TMSE 5.0 PPY 28 0.25 5 0.10 GPMS + 0.09 TMSE 3.5 PPY 29 0.25 8 0.06 TMSE 3.5 PPY 30 0.25 8 0.15 TMSE 3.5 PPY 31 0.25 8 0.10 GPMS + 0.09 TMSE 3.5 PPY 32 0.25 5 0.08 BTSE 3.5 PPY 33 0.25 5 0.08 BTSE 5.0 PPY 34 0.25 5 0.21 BTSE 3.5 PPY 35 0.25 5 0.21 BTSE 5.0 PPY 36 0.25 5 0.10 GPMS + 0.13 BTSE 3.5 PPY 37 0.25 8 0.08 BTSE 3.5 PPY 38 0.25 5 0.10 GPMS + 0.25 3.0 (BAS:VTAS 4:1 vol.) PPY 39 0.25 5 0.25 BAS:VTAS 4:1 vol. 3.0 PPY 40 0.25 5 0.10 GPMS + 0.05 TMSE 3.0 PPY 41 0.25 5 0.10 GPMS + 0.10 TMSE 3.0 PPY 42 0.25 5 0.10 GPMS + 0.15 TMSE 3.0 PPY 43 0.25 5 0.10 BTSE 3.0 PPY 44 0.25 5 0.25 BTSE 3.0 PPY 45 0.25 5 0.25 BTSE 2.5 PPY 46 0.25 5 0.05 GPMS + 0.15 TMSE 3.0 PPY 47 0.25 5 0.10 GPMS + 0.20 TMSE 3.0 * [Zr] g/L = [K2ZrF6] g/L
** pH adjusted with H2ZrF6 and/or NH4OH
, , - TABLE 9 - Experimental results for PEDOT/Zr/Silane EXPERIMENT CORROSION ADHESION SCORE SURFACE CONTACT ELECTRICAL
SCORE RESISTANCE (mohm/sq inch) 2024 T: 7075 16 2024 T3 7075 T6 2024 T3 7075 T6 6061 PEDOT 12 9.5 9.5 0 0 2.21 1.29 0.23 PEDOT 15 4.0 7.8 1.60 2.15 - - -PEDOT 16 4.0 7.5 8.65 7.80 - - -PEDOT 17 6.4 9.4 9.70 9.70 - - -PEDOT 18 - 8.0 - 9.65 - - -Alodine 1200S 10.0 10.0 10.0 10.0 0,71 0,86 X
, , TABLE 10 - Experimental results for PPY/Zr/Silane EXPERIMENT CORROSION SCORE ADHESION SCORE SURFACE CONTACT ELECTRICAL
RESISTANCE (mohm/sq inch) . PPY 10 4.75 8.0 0 0 1.21 2.06 0.42 PPY 15 - 9.0 - 9.8 - - 0.69 PPY 16 7.2 8.7 9.75 9.8 - - -PPY 17 - 9.3 - 9.8 - - -PPY 18 5.0 8.2 9.8 9.8 - - -PPY 19 6.2 8.5 4.05 8.05 - - -PPY 20 7.0 8.0 9.8 9.8 - - -PPY 21 4.6 7.6 9.75 9.8 - - -PPY 22 5.3 7.3 5.1 8.5 - - -PPY 23 _ 9.0 - 9.7 - - -PPY 24 _ 9.5 - 9.45 - - -PPY 25 _ 9.3 - 9.6 - - -PPY 26 _ 8.5 _ 9.5 _ _ -PPY 27 _ 8.5 - 7.05 - - -PPY 28 _ 9.2 - 9.8 - - -PPY 29 _ 8.8 - 9.75 - - -PPY 30 - 8.5 - 9.75 - - -PPY 31 _ 8.7 _ 9.75 _ _ -PPY 32 _ 8.4 - 9.75 - - -PPY 33 - 9.0 - 9.7 - - -PPY 34 _ 8.5 - 9.7 - - -PPY 35 _ 8.6 - 9.55 - - -PPY 36 _ 8.0 - 9.7 - - -PPY 37 _ 9.0 - 9.75 - - -PPY 38 _ <9.3 - 9.8 - - -PPY 39 _ <9.3 _ 9.8 _ - -PPY 40 _ <9.3 _ 9.8 _ . _ PPY 41 _ <9.3 _ 9.8 - - _ PPY 42 _ 9.3 _ 9.75 _ _ _ PPY 43 _ <9.3 - 9.8 - - -PPY 44 _ <9.3 _ 9.8 _ - -PPY 45 _ <9.3 - 8.65 - - -PPY 46 _ <9.3 - 9.8 - - -PPY 47 _ <9.3 - 9.8 - - -Alodine 1200 10.0 10.0 10.0 10.0 0,71 0,86 X
, While we have discussed and described our invention using some specific examples, those skilled in the art will recognize that our teachings are not so limited.
More specifically, it is understood that our inventive method and coating may be used in virtually any application requiring corrosion protection, and/or adhesion of subsequently applied organic coating(s) and/or low electrical surface contact resistance and in particular those applications concerned with the problems associated with hexavalent Chromium. Accordingly, it is understood that our inventive method and coating may be applicable to any automotive, marine, construction, industrial, or household use in addition to aeronautical applications and therefore should be only limited by the scope of the claims attached hereto.
Preferably a medium is used for silane solution preparation; silanes may be classified in water-based or solvent-based silanes. It is desirable to use water-based silane systems with nil or very little alcohol content, due to VOC restrictions. Preferably the one or more silanes are water soluble.
Preferably the one or more silanes are present in an amount of from 0.01 v%. ¨
1.0 v%
(v/v) of the polymer dispersion, more preferably from 0.1 v% to 0.5v%. With this range of silane content the beneficial effects of the silane are observed, without compromising the corrosion resistance.
Preferably, the one or more silanes are of the formula YSiX(3_a)Za wherein, X are independently selected hydrolysable groups, Y is non-hydrolysable and includes a functional group, Z is independently selected from H or alkyl, and a is 0, 1 or 2.
By hydrolysable group it is meant that the group is susceptible to nucleophilic attack to cleave the group from the silicon atom. X are independently selected hydrolysable groups. It is preferred that the hydrolysable groups are selected from methoxy (OCH3) or ethoxy (0C2H5).
These groups allow for good adhesion of the compound to nucleophilic sites on the metal and/or further coatings.
By non-hydrolysable it is meant that the group is not susceptible to nucleophilic attack to cleave the group from the silicon atom. Preferably the Y moiety is joined to the silicon atom by a silicon-carbon bond.
Y includes a functional group. That is, Y includes a group capable of reacting to link the silicon atom to a further coating, a further silane or to the metal substrate.
The functional group is preferably selected from vinyl (-CH=CH2), amino (-NH2), epoxy or mercapto (-SH)). The functional group may consist of this functional group, but preferably the functional group is linked to the silicon atom by an alkyl chain, preferably a lower alkyl (C1-C6) chain, an alkylether or an alkylamine. Thus, for example, Y may preferably be: -(CH2)õ-NH2; -(CH2),-SH, or -(CH2)n- HC=CH2, and n is preferably 0-6, preferably 1-6, more preferably 0-3.
In one embodiment the functional group may be a further silicon-containing moiety.
Thus, Y may be ¨RSIX3_aZa, where X, Z and a are as defined above. R may be an alkyl, an ether or an alkylamine. For example, R is an ether, such as CH2OCH2 or R is an amine, such as (CH2)3NH(CH2)3. According to their chemical structures, silane molecules are divided into two major categories, mono-silanes and bis-silanes. Bis-type silanes have two silicon atoms in their molecule whereas mono-silanes have only one, with a general formula of X3Si-R-SiX3.
Preferably the silane is symmetrical in this way for ease of synthesis and to minimize production costs. The main difference between mono and bis-silanes is that the number of hydrolysable X groups is double in a bis-silane molecule than in a mono-silane molecule.
Thus, it is reported that bis-silanes offer stronger interfacial adhesion (with the substrate) and denser films leading to better corrosion performance compared to mono-silanes, especially in unpainted state.
By "alkyl" is meant a straight or branched chain saturated cyclic (i.e., cycloalkyl) or acyclic hydrocarbon group of from 1 to 12 carbons, unless otherwise specified.
Exemplary alkyl groups include C1-C8, C1-C6, C1-C4, C2-C7, C3-C12, and C3-C6 alkyl.
Specific examples include methyl, ethyl, 1-propyl, 2-propyl, 2-methyl-1-propyl, 1-butyl, 2-butyl, and the like. Unless otherwise noted, alkyl groups, used in any context herein, may optionally be substituted with halogen, amino or sulfyl groups, or may include one or more heteroatoms in the alkyl chain, such as oxygen (an ether) or nitrogen (an amine).
Z is independently selected from H or alkyl. That is, Z is a non-hydrolysable group that does not include a functional group for linking the silane to a further coating, a further silane or to the metal substrate. In particular, it is preferred that a is 0.
Preferably, the one or more silanes are selected from (3-Glycidoxypropyl) trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyl]amine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
Preferably, said conducting polymer is one selected from the group consisting of:
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY).
Preferably the coating step is applied to the surfaces by spraying, or immersion. If the coating step is immersion, preferably it is for a period of substantially 2 minutes in the treatment bath. Preferably said drying step is performed at substantially room temperature.
The pretreatment step serves to prepare the surface of the metal for the coating.
.5 Accordingly, the pretreatment step at least involves the cleaning of the surface. Preferably said pretreatment step further comprises the steps of:
degreasing the surfaces;
cleaning the surfaces; and deoxidizing the surfaces.
Preferably the method further comprising the steps of: rinsing the surfaces after cleaning; and rinsing the surfaces after deoxidizing; and not-rinsing the surfaces after coating.
Preferably the inorganic metal salt is or comprises a salt of Zirconium, the concentration of inorganic metallic salts of Zirconium are produced/adjusted with K2ZrF6 and the pH is adjusted with H2ZrF6 and/or NI-140H.
Preferably said metallic sheets are ones selected from the group consisting of aluminum, copper, iron, or alloys thereof, and preferably is selected from the group consisting of 2024-T3 and 7075-T6.
Preferably the inorganic salts are present in a concentration of 2.0 to 8.0 g/L and/or wherein the contacting step is carried out at a pH of 2 to 5.
According to a second aspect, there is provided a conversion coating for the treatment of metallic surfaces, said coating comprising one or more silanes, and a conducting polymer dispersion containing an inorganic metallic salt of at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc, wherein the concentration of the inorganic metallic salt is between 2.0 and 20 g/L and the pH
of the coating is between 1 and 6Ø
Preferably the one or more silanes are as described above and as discussed herein.
Preferably the conducting polymer is one selected from the group consisting of:
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY), and/or wherein the one or more silanes are selected from (3-Glycidoxypropyl)trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyppropyl]amine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
These and other features and advantages of the present invention will become .5 apparent with reference to the attached drawing and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete understanding of the present invention may be realized by reference to the accompanying drawing and tables in which:
FIG. 1 is a process flow chart depicting the steps associated with our chromium-free conversion coating of the present invention.
TABLE 1 shows the properties of several conducting polymers used in the present invention according to data provided by suppliers of the polymers;
TABLE 2 shows the experimental conditions for PEDOT/Zr for both tested alloys according to the present invention;
TABLE 3 shows the experimental conditions for PPY/Zr for both tested alloys according to the present invention;
TABLE 4 shows the measured corrosion of alloys treated with PEDOT/Zr according to the present invention; and TABLE 5 shows the measured corrosion of selected alloys treated with PPY/Zr according to the present invention.
TABLE 6 is a table that shows the molecular and structural formula of several silanes used in the present disclosure.
TABLE 7 is a table that shows the experimental conditions for PEDOT/Zr/silane for both tested alloys according to the disclosure.
TABLE 8 is a table that shows the experimental conditions for PPY/Zr/silane for both tested alloys according to the disclosure.
TABLE 9 is a table that shows the measured corrosion, adhesion and surface contact electrical resistance of alloys treated with PEDOT/Zr according to the disclosure.
TABLE 10 is a table that shows the measured corrosion, adhesion and surface contact electrical resistance of alloys treated with PPY/Zr according to the disclosure.
DETAILED DESCRIPTION
As can be appreciated by those skilled in the art, chemical conversion surface treatments/coatings generally involve the process of immersion or other contact of a metal = 5 (i.e., Aluminum and/or Alloys of Aluminum) with an active bath or spray that ¨ through a redox reaction at the metallic surface or chemical deposition at the metallic surface due to physicochemical changes in the treatment bath ¨ form a superficial adhered protective coating. Such conversion coatings typically exhibit quite low solubility and ¨
in the case of Aluminum ¨ a thickness of approximately 20nm to lmm, depending upon the process parameters and the alloy treated, while the substrate thickness lost is quite small or minimal.
The color of the resulting conversion coating obtained depends upon the base material and the bath/spray parameters.
Advantageously, our inventive conversion coating may be prepared in a single-step immersion process. Accordingly, parts, i.e., panels, to be coated are bathed in a conducting polymer dispersion in which different inorganic salts and silanes along with other additives that affect the bath and/or resulting coating, i.e., bath dispersion agents, wetting agents, or polymeric film formation agents.
FIG 1 depicts an overview of the steps involved in our inventive process. More particularly, our inventive process includes three general phases namely, pretreatment, conversion, and drying. And while our discussion herein is concerned primarily with Aluminum and certain specific alloys of Aluminum, our invention is not so limited. In particular, different metal compositions and alloys as well as additional applications, i.e., automotive, industrial, etc., would benefit from our inventive method and resulting coating as well.
Returning now to FIG 1, it may be observed that Pretreatment begins by degreasing the panels to be coated (Block 110). Degreasing may be performed using any of a variety of known detergent solutions and/or organic solvents. Additionally, such degreasing ¨ like all of the process steps ¨ may be performed by spray application or bath/immersion or a mixture of the two techniques.
Once the panel(s) to be coated is degreased, it is then cleaned/washed with an alkali solution (Block 120). Such solutions are commercially available under various trade names i.e., TURCO (4215NCLT), and this alkali cleaning/washing is advantageously performed for approximately 10 minutes at a modest elevated temperature, i.e., 50 C. After cleaning/washing, the panel is rinsed with water and then deoxidized (Block 130), with, for example TURCO Smut Go NC for approximately 5 minutes at ambient temperature(s) and then rinsed. Advantageously, other pickling or desmutting steps can be used depending on the treated substrate material and surface material or thickness to be removed.
As can be now appreciated, our inventive process employs commercially available pretreatment steps which are well known and understood. Advantageously, such pretreatment is compatible with a variety of alloys and their application is widely understood.
In an exemplary embodiment, conversion treatment (Block 140) includes immersion of aluminum alloy panels, in a bath for a period of time followed by direct (no rinse) drying (Block 150) of the treated panels. Generally, the conversion treatment bath is prepared by an initial stirring of a conducting, polymeric dispersion. Advantageously, the polymer dispersion(s) used may be commercially available water-based ones and exhibit satisfactory formulation(s) including solid content, pH, and dispersive additives. Consequently, only a minimal amount of stirring is required for these commercial dispersions. Of further advantage, the conversion treatment in the bath is only a 2 minutes process.
Such conducting polymeric dispersions include Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY) among others. The particular conducting polymeric dispersions used in our examples and their physical properties are shown in Table 1. While we have limited our discussion herein to those conducting polymeric dispersions exhibiting superior performance in our experiments, it should be noted that a number of dispersions may be suitable ¨ depending upon the particular application requirements. More specifically, dispersions of polyphenylene, polyphenylene vinylene, polyethylenesulfide and derivatives of all the mentioned conducting polymers should produce satisfactory results.
In addition, other polymeric components such as acrylics, polyurethanes, epoxies, amino resins, phenolics, vinylics, polyesters, etc., may be added to enhance particular characteristics of the coating.
Returning now to the description of our inventive method, after stirring the conducting polymeric dispersion (and any polymeric components), a quantity of inorganic salt(s) or mixtures thereof are added to the conducting polymeric dispersion and subsequently mixed until the added salts are suitably dissolved. Example salts include the inorganic salts of Molybdenum, Manganese, Zirconium and Titanium. More particularly, Sodium Molybdate, Potassium Permanganate, Potassium Hexafluorozirconate and Potassium Hexaflorotitanate have been used with success. Final concentrations of the added salts in the bath solution(s) may vary over a wide range, i.e., 2-20 g/L.
After the inorganic salt(s) or mixtures thereof are added to the conducting polymeric dispersion and subsequently mixed until the added salts are suitably dissolved, a quantity of silane(s) or mixtures thereof are added to the conducting polymeric/salt(s) dispersion and subsequently mixed until the added silanes are suitably dissolved. The particular silanes used in the examples and their molecular and structural formula are shown in table 6. (3-Glycidoxypropyl)trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyl]amine (BAS) and Vinyltriacetoxysilane (VTAS) have been used with success. The final concentrations of the added salts in the bath solution(s) may vary over a range, e.g., % 0.01 vol.
(% v/v) ¨ % 1.0 vol.
(% v/v).
Finally, the polymeric dispersion/inorganic salt /silane solution is subsequently pH
adjusted using alkaline compounds such as ammonia or phosphate or acidic compounds, including hexaflorozirconic acid and fluorhydric acid.
EXPERIMENTAL / RESULTS
A number of samples of two particular aluminum alloys, namely 2024T3 and alloys were subjected to our inventive Chromium-free conversion process and evaluated.
Those showing superior characteristics in salt spray fog corrosion tests (SSFCT) were obtained using PPY and PEDOT in combination with Hexaflorozirconate. The particular experimental conditions are shown in Table 2, Table 3 for PEDOT/Zr, PPY/Zr, based compositions and Table 4, and Table 5 show the obtained results respectively.
For all of the samples shown in these Tables, the drying conditions were substantially room temperature and pressure, for a period of time of at least 24 hours.
More specifically, Table 2 shows the experimental conditions for PEDOT/Zr. In this set, the [Zr] concentration was effected by varying the amounts of K2ZrF6 and the pH was adjusted with H2ZrF6 and/or NH4OH.
Table 3 shows the experimental conditions used for a PPY/Zr set of samples. In this particular set, the [Zr] concentration was effected by varying the amounts of K2ZrF6 and the pH
was adjusted with H2ZrF6 and/or NH4OH.
Turning now to Table 4, there it shows the corrosion resistance for our inventive PEDOT/Zr conversion coating on both 2024-T3 and 7075-T6 aluminum alloys. The results obtained were after 168 hours of salt spray fog corrosion testing (SSFCT) and the hexavalent chromium based commercial ALODINE 1200S exhibits the best corrosion performance, with a corrosion score of 10Ø The corrosion score values go from 0 for the worst corrosion performance to 10 for best corrosion performance.
Similarly, Table 5 shows the corrosion resistance for our inventive PPY/Zr coating on the 2024-T3 and 7075-T6 alloys as well as the ALODINE 1200S treated alloys.
A number of samples of two particular aluminum alloys, namely 2024T3 and alloys, were subjected to the polymeric dispersion/inorganic salt /silane chromium-free conversion process and evaluated. Those showing superior characteristics in salt spray fog corrosion tests (SSFCT) were obtained using PPY and PEDOT in combination with hexaflorozirconate and GPMS, TMSE and BTSE silanes ¨ added either alone or in combination. Those showing superior characteristics in the scribed wet tape paint adhesion tests of a subsequently applied organic coating were obtained using PPY and PEDOT in combination with hexaflorozirconate and GPMS, TMSE, BTSE, BAS and VTAS silanes ¨
added either alone or in combination ¨. Some of the proposed treatments provided combined superior characteristics in salt spray fog corrosion tests and in the scribed wet tape paint adhesion tests of a subsequently applied organic coating. Additionally, some of those treatments providing combined superior characteristics in salt spray fog corrosion tests and in wet tape paint adhesion tests of a subsequently applied organic coating also provided superior characteristics in surface contact electrical resistance measurements. The particular experimental conditions are shown in the tables of TABLES 8 and 9 for PEDOT/Zr/silane, PPY/Zr/silane, based compositions and the tables of TABLES 10 and 11 show the obtained results, respectively. For all of the samples shown in these tables of TABLES
8-11, the drying conditions were substantially room temperature and pressure, for a period of time of at least 24 hours.
More specifically, the table of TABLE 8 shows the experimental conditions for PEDOT/Zr/silane. In this set, the [Zr] (zirconium) concentration was effected by varying the amounts of K2ZrF6 (potassium hexafluorozircoante) and the pH was adjusted with H2ZrF6 (fluorozirconic acid) and/or NH4OH (ammonium hydroxide).
The table of TABLE 9 shows the experimental conditions for a PPY/Zr/silane set of samples. In this particular set, the [Zr] (zirconium) concentration was effected by varying the amounts of K2ZrF6 (potassium hexafluorozirconate) and the pH was adjusted with H2ZrF6 (fluorozirconic acid) and/or NH4OH (ammonium hydroxide).
Turning now to the table of TABLE 10, there it shows the corrosion resistance for the PEDOT/Zr/silane conversion coating on both 2024-T3 and 7075-T6 aluminum alloys. The results obtained were after 168 hours of salt spray fog corrosion testing (SSFCT) and the hexavalent chromium based commercial ALODINE 1200S exhibited the best corrosion performance, with a corrosion score of 10Ø The corrosion score values go from 0 (zero) for the worst corrosion performance to 10 (ten) for best corrosion performance.
The table in TABLE 8 also shows the adhesion performance of a subsequently applied organic coating on both 2024-T3 and 7075-T6 aluminum alloys. The paint adhesion performance was measured according to a wet tape paint adhesion test. Once dried (after 14 days air curing), the corresponding conversion coated panels were painted with an epoxy primer according to the MIL-PRF-85582 standard. The epoxy primer used was a water-reducible epoxy primer system made of 10PW20-4 base and ECW-104 hardener according to MIL-PRF-85582 Type 1 Class 2, provided by Ala Nobel Aerospace Coatings, By. Two parallel, 2 inch long scratches, 3/4 to 1 inch apart through the coating and to the substrate were made on the panels.
The parallel scratches were joined with two intersecting lines, or an "X" pattern. The primed and scribed panels were immersed in deionised water during 24 hours, prior to carrying out the wet paint adhesion tests. Within 2 minutes after removing test panels from water adhesive tape was applied and pressed against the test surface with firm hand pressure and then removed. The hexavalent chromium based commercial ALOD1NE 1200S exhibited the best pant adhesion performance, with an adhesion score of 1 0ØThe adhesion test score values go from 0 (zero) for the worst adhesion performance (total detachment of the primer) to 10 (ten) for best adhesion performance (no detachment of the primer). The table in TABLE 8 also shows the surface contact electrical resistance for the PEDOT/Zr/silane conversion coating on 2024-T3, 7075-T6 and 6061-T6 aluminum alloys. The surface contact electrical resistance of the coatings was measured as described in the MIL-DTL-81706-B standard. The applied load shall be within one percent of the calculated 200psi applied pressure. The contacting electrodes were copper or silver-plated copper with a finish not rougher than that obtained by the use of 000 metallographic abrasive paper. The electrodes were flat enough so that when the load was applied without a specimen between them, light is not visible through the contacting surface. The area of the upper electrode was one square inch (25 square mm) and the area of the lower electrodes was larger. The maximum electrical resistance values allowed by aeronautical standards for 6061 T6 alloy are of 5000J/square inch (5 ma/square inch) before salt spray exposure test. The hexavalent chromium based commercial ALODINE
1200S exhibited the lowest surface contact electrical resistance for the 2024-T3 and 7075-T6 alloys. The values for the PEDOT/Zr/silane treatments were also well below the 5 ma/square inch.
Similarly, the table of TABLE11 shows the corrosion resistance, the paint adhesion performance and the surface contact electrical resistance measurements for the PPY/Zr/silane coatings on the 2024-T3, 7075-T6 and 6061-T6 alloys as well as the ALODINE
1200S treated alloys.
At this point, it should be noted that in addition to the Zr salts used in these exemplary tests, other salts ¨ either alone or in combination ¨ may produce satisfactory results as well.
In particular, salts of Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt, Magnesium, and Zinc may be employed. Additionally, other bath components such as pH
adjusting compounds, solvents, non-aqueous dispersion media, other silanes, dispersing agents, surfactants and coalescing solvents may be used to provide various degrees of coating effectiveness. Further, while our inventive method and resulting coating(s) have been described in the context of immersion bath(s), it is understood that alternative coating, i.e., spray coating may be used as well. Lastly, other metallic substrates, such as steel, aluminum, copper, and/or iron and/or their alloys, will benefit from our method and coating(s).
Material i PANI PEDOT PPY
Property Polymer Po!yenning Polyethylenedioxythlophsrie Polypyrrole Solid Content 6.0% 1.2 ¨ 1.4% 6.0%
Dilution with Water Water Water pH 2.3 1.5 ¨ 2.5 3 or kiss .., Conductivity p 1 ¨ 2 Up To 10 0.01 ¨ 0.001 (SIC")) Pellets Cast Film Cast Film Surface Resistivity 10E4 10E0 10E4-10E6 (Ohm) , Viscosity is Pas 60 - 100 niPas N.A.
Supplier Pardpol Bayer Essays Trade Name Panipol W Baytron P Eeonoiner 7000 PEDOT / Zr Experiment [PEDOT] (%) Rd (Wt.)* pH "
, , v PEDOT 1 0.43 8 2 PEDOT 2 0.86 s 3.5 PEDOT 3 0.43 2 2 PEDOT 4 1.30 2 2 PEDOT 5 , 0.43 8 s -PEDOT 6 1.30 2 5 PEDOT 7 1.30 s 2 PEDOT 8 0.86 , 5 3.5 PEDOT 9 0.43 2 s PEDOT 10 0.86 s 3.5 PEDOT 11 1.30 8 s .
PEDOT 12 0.43 s 3.5 PED07' 13 0.86 2 3.5 PEDOT 14 0.86 5 2 ..- _ Experimental Conditions for PEDOT / Zr *PI iiii.* PcIrFol git.; " pH Milusted with VC. andior NN4OH
, PPY / Zr Experiment IPEDOT] (%) [Zr] (g/L)* pH **
PPY 4 2 2 2 , PPY 5 4 5 3.5 PPY 8 4 5 3.5 PPY 8 4 6 3.5 PPY 9 6 s 2 . .
PPY 11 e 2 5 .
PPY 12 2 5 3.5 PPY 13 4 23.5 . .
Experimental Conditions for PPY / Zr .rzil all. 0 PC,2Zry sk; " pH Adjusted with Hpfs and/or NH4OH
Corrosion Score EXPERIMENT
PEDOT 1 3.0 3.0 PEDOT 2 3.6 8.5 PEDOT 3 1.0 3.6 , PEDOT 4 1.5 3.7 PEDOT 5 4.0 9.0 PEDOT 8 2.0 8.5 PEDOT 7 2.0 3.5 PEDOT 8 3.5 82 , PEDOT 9 3.6 9.0 PEDOT 10 4,0 4.5 PEDOT 11 8.0 2.7 .
PEDOT 12 9.5 95 PEDOT 13 2.5 6.6 PEDOT 14 2.6 2.0 Experimental Results for PEDOT / Zr Corrosion Score EXPERIMENT
PPY 1 1.0 1.50 PPY 2 1.0 1.75 PPY 3 4.0 5.0 PPY 4 1.0 1.75 PPY 5 5.0 5.5 PPY 6 , 4.0 5.5 PPY7 4.0 4.5 PPY 8 4.0 5.25 PPY 9 0.75 1.75 PPY 10 4.75 8.0 PPY 11 2.6 6.0 PPY 12 4.0 5.0 PPY 13 3.0 4.0 PPY 14 0.5 1.5 Experimental Results for PPY I Zr SHORT
= COMPOUND MOLECULAR FORMULA ESTRUCTURAL FORMULA
NAME
(3- 9CH3 Glycidoxypropyl) GPMS C9H2005S1 trimethoxysilane OCH3 0 1,2-Bis OCH3 OCH3 (thmethoxysily1) TMSE C8H2206Si2 H3CO-Si , ethane ocH3 OCH3 H
1,2- H3c,,..õ0-T¨\ 3 H
Bis(Triethoxysily1) BTSE [-CH2Si(0C2H5)3]2 c3 Ethane cH3 cH3 Bis[3-(trimethoxysily1) BAS [(CH30)3Si(CH2)312NH
propygamine Vinyltriacetoxy VTAS (C,H3C0.,2)3sir.õ..1-4=cH2 silane TABLE 7- Experimental conditions for PEDOT/Zr/Silane PEDOT / Zr / Silane Experiment [PEDOT] (%) [Zr] (g/L)* [Silane] (% vol.) pH**
PEDOT 15 0.43 5 0.10 GPMS 3.5 PEDOT 16 0.43 5 0.25 GPMS 3.5 PEDOT 17 0.15 5 0.10 GPMS 3.5 PEDOT 18 0.15 5 0.06 TMSE 3.5 * [Zr] g/L = [K2ZrF6] g/L
** pH adjusted with H2ZrF6 and/or NH4OH
TABLE 8 - Experimental conditions for PPY/Zr/Silane PPY / Zr / Silane Experiment [PPY] (%) [Zr] (g/L)* [Silane] (% vol.) pH**
PPY 15 0.25 5 0.10 GPMS 3.5 PPY 16 0.25 5 0.10 GPMS 3.0 PPY 17 0.25 5 0.05 GPMS 3.0 PPY 18 0.10 5 0.10 GPMS 3.5 PPY 19 0.50 5 0.10 GPMS 3.5 PPY 20 0.15 5 0.10 GPMS 3.5 PPY 21 0.25 5 0.25 GPMS 3.5 PPY 22 0.50 5 0.25 GPMS 3.5 PPY 23 0.25 5 0.06 TMSE 3.5 PPY 24 0.25 5 0.06 TMSE 5.0 PPY 25 0.25 5 0.15 TMSE 3.5 PPY 26 0.25 5 0.15 TMSE 5.0 PPY 27 2.0 8 0.06 TMSE 5.0 PPY 28 0.25 5 0.10 GPMS + 0.09 TMSE 3.5 PPY 29 0.25 8 0.06 TMSE 3.5 PPY 30 0.25 8 0.15 TMSE 3.5 PPY 31 0.25 8 0.10 GPMS + 0.09 TMSE 3.5 PPY 32 0.25 5 0.08 BTSE 3.5 PPY 33 0.25 5 0.08 BTSE 5.0 PPY 34 0.25 5 0.21 BTSE 3.5 PPY 35 0.25 5 0.21 BTSE 5.0 PPY 36 0.25 5 0.10 GPMS + 0.13 BTSE 3.5 PPY 37 0.25 8 0.08 BTSE 3.5 PPY 38 0.25 5 0.10 GPMS + 0.25 3.0 (BAS:VTAS 4:1 vol.) PPY 39 0.25 5 0.25 BAS:VTAS 4:1 vol. 3.0 PPY 40 0.25 5 0.10 GPMS + 0.05 TMSE 3.0 PPY 41 0.25 5 0.10 GPMS + 0.10 TMSE 3.0 PPY 42 0.25 5 0.10 GPMS + 0.15 TMSE 3.0 PPY 43 0.25 5 0.10 BTSE 3.0 PPY 44 0.25 5 0.25 BTSE 3.0 PPY 45 0.25 5 0.25 BTSE 2.5 PPY 46 0.25 5 0.05 GPMS + 0.15 TMSE 3.0 PPY 47 0.25 5 0.10 GPMS + 0.20 TMSE 3.0 * [Zr] g/L = [K2ZrF6] g/L
** pH adjusted with H2ZrF6 and/or NH4OH
, , - TABLE 9 - Experimental results for PEDOT/Zr/Silane EXPERIMENT CORROSION ADHESION SCORE SURFACE CONTACT ELECTRICAL
SCORE RESISTANCE (mohm/sq inch) 2024 T: 7075 16 2024 T3 7075 T6 2024 T3 7075 T6 6061 PEDOT 12 9.5 9.5 0 0 2.21 1.29 0.23 PEDOT 15 4.0 7.8 1.60 2.15 - - -PEDOT 16 4.0 7.5 8.65 7.80 - - -PEDOT 17 6.4 9.4 9.70 9.70 - - -PEDOT 18 - 8.0 - 9.65 - - -Alodine 1200S 10.0 10.0 10.0 10.0 0,71 0,86 X
, , TABLE 10 - Experimental results for PPY/Zr/Silane EXPERIMENT CORROSION SCORE ADHESION SCORE SURFACE CONTACT ELECTRICAL
RESISTANCE (mohm/sq inch) . PPY 10 4.75 8.0 0 0 1.21 2.06 0.42 PPY 15 - 9.0 - 9.8 - - 0.69 PPY 16 7.2 8.7 9.75 9.8 - - -PPY 17 - 9.3 - 9.8 - - -PPY 18 5.0 8.2 9.8 9.8 - - -PPY 19 6.2 8.5 4.05 8.05 - - -PPY 20 7.0 8.0 9.8 9.8 - - -PPY 21 4.6 7.6 9.75 9.8 - - -PPY 22 5.3 7.3 5.1 8.5 - - -PPY 23 _ 9.0 - 9.7 - - -PPY 24 _ 9.5 - 9.45 - - -PPY 25 _ 9.3 - 9.6 - - -PPY 26 _ 8.5 _ 9.5 _ _ -PPY 27 _ 8.5 - 7.05 - - -PPY 28 _ 9.2 - 9.8 - - -PPY 29 _ 8.8 - 9.75 - - -PPY 30 - 8.5 - 9.75 - - -PPY 31 _ 8.7 _ 9.75 _ _ -PPY 32 _ 8.4 - 9.75 - - -PPY 33 - 9.0 - 9.7 - - -PPY 34 _ 8.5 - 9.7 - - -PPY 35 _ 8.6 - 9.55 - - -PPY 36 _ 8.0 - 9.7 - - -PPY 37 _ 9.0 - 9.75 - - -PPY 38 _ <9.3 - 9.8 - - -PPY 39 _ <9.3 _ 9.8 _ - -PPY 40 _ <9.3 _ 9.8 _ . _ PPY 41 _ <9.3 _ 9.8 - - _ PPY 42 _ 9.3 _ 9.75 _ _ _ PPY 43 _ <9.3 - 9.8 - - -PPY 44 _ <9.3 _ 9.8 _ - -PPY 45 _ <9.3 - 8.65 - - -PPY 46 _ <9.3 - 9.8 - - -PPY 47 _ <9.3 - 9.8 - - -Alodine 1200 10.0 10.0 10.0 10.0 0,71 0,86 X
, While we have discussed and described our invention using some specific examples, those skilled in the art will recognize that our teachings are not so limited.
More specifically, it is understood that our inventive method and coating may be used in virtually any application requiring corrosion protection, and/or adhesion of subsequently applied organic coating(s) and/or low electrical surface contact resistance and in particular those applications concerned with the problems associated with hexavalent Chromium. Accordingly, it is understood that our inventive method and coating may be applicable to any automotive, marine, construction, industrial, or household use in addition to aeronautical applications and therefore should be only limited by the scope of the claims attached hereto.
Claims (16)
1. A process for treatment of metallic surfaces, said process comprising the steps of:
pre-treating the surfaces;
coating the surfaces with a conversion coating by contacting them with a conducting polymer dispersion containing:
one or more silanes, and inorganic metallic salts selected from at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc in concentrations of the metal salt between 2.0 and 20 g/L and a pH value of between 1 and 6.0; and drying the surfaces.
pre-treating the surfaces;
coating the surfaces with a conversion coating by contacting them with a conducting polymer dispersion containing:
one or more silanes, and inorganic metallic salts selected from at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc in concentrations of the metal salt between 2.0 and 20 g/L and a pH value of between 1 and 6.0; and drying the surfaces.
2. The process according to claim 1, wherein the one or more silanes are water soluble.
3. The process according to claim 1 or claim 2, wherein the one or more silanes are present in an amount of from 0.01 v%. ¨ 1.0 v% (v/v) of the polymer dispersion.
4. The process according to any of the proceeding claims, wherein the one or more silanes are of formula (1), YSiX(3-a)Za (formula (1)) wherein, X are independently selected hydrolysable groups, Y is non-hydrolysable and includes a functional group, Z is independently selected from H or alkyl, and a is 0, 1 or 2, preferably 0.
5. The process according to claim 4, wherein the hydrolysable groups are selected from methoxy or ethoxy.
6. The process according to claim 4 or claim 5, wherein:
the functional group is selected from vinyl, amino, epoxy or mercapto; and/or the functional group is linked to the silicon atom by an alkyl group, an alkylether group or an alkylamine group.
the functional group is selected from vinyl, amino, epoxy or mercapto; and/or the functional group is linked to the silicon atom by an alkyl group, an alkylether group or an alkylamine group.
7. The process according to claim 4 or claim 5, wherein Y is ¨RSiX3-a Z a, and wherein R is an alkyl group, an alkylether group or an alkylamine group.
8. The process according to any of the proceeding claims, wherein the one or more silanes are selected from (3-Glycidoxypropyl)trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyppropyllamine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
9. The process according to any of the proceeding claims, wherein said conducting polymer is one selected from the group consisting of: Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY).
10. The process according to any one of the preceding claims wherein said pretreatment step further comprises the steps of:
degreasing the surfaces;
cleaning the surfaces; and deoxidizing the surfaces.
degreasing the surfaces;
cleaning the surfaces; and deoxidizing the surfaces.
11. The process according to any of the preceding claims, wherein the inorganic metal salt is or comprises a salt of Zirconium, the concentration of inorganic metallic salts of Zirconium are produced/adjusted with K2ZrF6 and the pH is adjusted with H2ZrF6 and/or NH4OH.
12. The process of any one of the preceding claims, wherein said metallic sheets are ones selected from the group consisting of aluminum, copper, iron, or alloys thereof, and preferably is selected from the group consisting of 2024-T3 and 7075-T6.
13. The process of any one of the preceding claims, wherein the inorganic salts are present in a concentration of 2.0 to 8.0 g/L and/or wherein the contacting step is carried out at a pH of 2 to 5.
14. A conversion coating for the treatment of metallic surfaces, said coating comprising a conducting polymer dispersion containing one or more silanes, and an inorganic metallic salt of at least one of Molybdenum, Magnesium, Zirconium, Titanium, Vanadium, Cerium, Hafnium, Silicon, Aluminum, Boron, Cobalt and Zinc, wherein the concentration of the inorganic metallic salt is between 2.0 and 20 g/L and the pH of the coating is between 1 and 6Ø
15. The coating according to claim 14, wherein the one or more silanes are water soluble and/or wherein the one or more silanes are present in an amount of from 0.01 v%. ¨ 1.0 v%
(v/v) of the polymer dispersion.
(v/v) of the polymer dispersion.
16. The coating of claim 15 or claim 16, wherein the conducting polymer is one selected from the group consisting of:
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY), and/or wherein the one or more silanes are selected from (3-Glycidoxypropyl) trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyljamine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
Polyanaline (PANI), Polyethylenedioxythiophene (PEDOT) and Polypyrrole (PPY), and/or wherein the one or more silanes are selected from (3-Glycidoxypropyl) trimethoxysilane (GPMS), 1,2-Bis(trimethoxysilyl)ethane (TMSE), 1, 2-Bis(Triethoxysily1) Ethane (BTSE), Bis[3-(trimethoxysilyl)propyljamine (BAS) and Vinyltriacetoxysilane (VTAS), or combinations of two or more thereof.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12382337.9A EP2703522B1 (en) | 2012-08-31 | 2012-08-31 | Chromium-free conversion coating |
| EP12382337.9 | 2012-08-31 | ||
| US13/662,412 US9476125B2 (en) | 2006-08-08 | 2012-10-26 | Chromium-free conversion coating |
| US13/662,412 | 2012-10-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2819340A1 true CA2819340A1 (en) | 2014-02-28 |
| CA2819340C CA2819340C (en) | 2019-04-30 |
Family
ID=50180660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2819340A Active CA2819340C (en) | 2012-08-31 | 2013-06-17 | Chromium-free conversion coating |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6275975B2 (en) |
| CA (1) | CA2819340C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2955248A1 (en) * | 2012-08-31 | 2015-12-16 | The Boeing Company | Chromium-free conversion coating |
| EP2915903B1 (en) * | 2014-03-05 | 2018-02-21 | The Boeing Company | Chromium-free conversion coating |
| US12084546B2 (en) | 2018-11-29 | 2024-09-10 | Teijin Limited | Thermosetting resin composition, film adhesive, prepreg, and production method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0623159T3 (en) * | 1992-01-21 | 1999-11-22 | Zipperling Kessler & Co | Conjugated polymer paint preparations which provide corrosion resistance to metal surfaces |
| JPH1161429A (en) * | 1997-08-28 | 1999-03-05 | Nippon Steel Corp | Surface treated metal material |
| US6736908B2 (en) * | 1999-12-27 | 2004-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Composition and process for treating metal surfaces and resulting article |
| JP4220111B2 (en) * | 2000-07-24 | 2009-02-04 | 大日本塗料株式会社 | Corrosion protection method for weathering steel |
| US20040009300A1 (en) * | 2000-10-11 | 2004-01-15 | Toshiaki Shimakura | Method for pretreating and subsequently coating metallic surfaces with paint-type coating prior to forming and use og sybstrates coated in this way |
| JP2002348488A (en) * | 2001-05-28 | 2002-12-04 | Mitsubishi Rayon Co Ltd | Conductive coloring composition, conductor and its forming method |
| AU2002340053A1 (en) * | 2001-09-27 | 2003-04-07 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Conducting polymer for pretreatment of metallic and non-metallic surfaces |
| US20060134339A1 (en) * | 2004-12-21 | 2006-06-22 | Shengxian Wang | Coating compositions and methods of making and using them |
| JP4603435B2 (en) * | 2005-07-12 | 2010-12-22 | 日新製鋼株式会社 | Organic resin coated steel sheet |
| EP1887105B1 (en) * | 2006-08-08 | 2014-04-30 | The Boeing Company | Chromium-free conversion coating |
| WO2009019855A1 (en) * | 2007-08-06 | 2009-02-12 | Nisshin Steel Co., Ltd. | Aqueous emulsion coating material and coated steel sheet using the same |
-
2013
- 2013-06-17 CA CA2819340A patent/CA2819340C/en active Active
- 2013-08-29 JP JP2013178052A patent/JP6275975B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CA2819340C (en) | 2019-04-30 |
| JP6275975B2 (en) | 2018-02-07 |
| JP2014047353A (en) | 2014-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10550478B2 (en) | Chromium-free conversion coating | |
| CA2659641C (en) | Chromium-free conversion coating | |
| US9290846B2 (en) | Chromium-free conversion coating | |
| EP1629136B1 (en) | Composition for coating metals to protect against corrosion | |
| EP1163297B1 (en) | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture | |
| Van Ooij et al. | Corrosion protection properties of organofunctional silanes—an overview | |
| US20100129674A1 (en) | Aminobenzoic acid polymer compositions and films; methods of forming and using the same | |
| CA2819340C (en) | Chromium-free conversion coating | |
| JP6936742B2 (en) | Chrome-free chemical coating | |
| JP7117292B2 (en) | Improved method for corrosion protective pretreatment of metal surfaces including steel, galvanized steel, aluminum, aluminum alloys, magnesium and/or zinc-magnesium alloys | |
| Palanivel | Modified silane thin films as an alternative to chromates for corrosion protection of AA2024-T3 alloy | |
| CN110809641A (en) | Inorganic non-chromium aqueous treatment composition and method for coating metal surfaces | |
| Suryanarayanan | Integral Epoxy Resin-silane Primer System for Hot-dip Galvanized Steel | |
| Iroh | I, Karthik Suryanarayanan |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |
Effective date: 20161109 |