EP1246952A1 - Composition and process for treating metals - Google Patents
Composition and process for treating metalsInfo
- Publication number
- EP1246952A1 EP1246952A1 EP00975346A EP00975346A EP1246952A1 EP 1246952 A1 EP1246952 A1 EP 1246952A1 EP 00975346 A EP00975346 A EP 00975346A EP 00975346 A EP00975346 A EP 00975346A EP 1246952 A1 EP1246952 A1 EP 1246952A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- moles
- ratio
- liquid composition
- aqueous liquid
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
Definitions
- This invention relates to compositions and processes for treating metal surfaces with acidic aqueous compositions for forming conversion coatings on the metals; the conversion coatings provide excellent bases for subsequent painting.
- the invention is well suited to treating iron and steel, galvanized iron and steel, zinc and those of its al- loys that contain at least 50 atomic percent zinc, and aluminum and its alloys that contain at least 50 atomic percent aluminum.
- the surface treated is predominantly ferrous; most preferably the surface treated is cold rolled steel.
- This invention is very closely related to that disclosed in U. S. Patent 5,449,415, from which it differs primarily in using a particularly advantageous type of water soluble and/or dispersible polymer.
- the object of this invention is to achieve better corrosion resistance under at least one set of corrosion promoting conditions than does the invention illustrated by examples in U. S. Patent 5,449,415, without using any more hexavalent chromium in the process than is used in preferred examples in U. S. Patent 5,449,415.
- all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word "about” in describing the broadest scope of the invention.
- At least one of the two substituents, exclusive of the single carbon atom that is bonded both to the amino nitrogen and the aromatic ring, on the amino nitrogen atom of each substituent moiety is a polyhydroxy moiety, but in the present invention both of these substituents jointly contain at least two carbon atoms and at least one hydroxy moiety but neither of these substituents on the amino nitrogen atoms individually contains more than half as many hydroxyl moieties as it has carbon atoms, unless it contains only one carbon atom.
- the composition is coated over the metal surface to be treated and then dried in place on the surface of the metal, without intermediate rinsing.
- Various embodiments of the invention include working compositions for direct use in treating metals, concentrates from which such working compositions can be prepared by dilution with water, processes for treating metals with a composition according to the invention, and extended processes including additional steps that are conventional per se, such as precleaning, rinsing, and, particularly advantageously, painting or some sim- ilar overcoating process that puts into place an organic binder containing protective coating over the conversion coating formed according to a narrower embodiment of the invention.
- Articles of manufacture including surfaces treated according to a process of the invention are also within the scope of the invention.
- An acidic aqueous composition according to the invention comprises, preferably consists essentially of, or more preferably consists of, water and: (A) a component of 'lluorometallate" anions, each of said anions consisting of (i) at least four fluorine atoms, (ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, optionally, one or both of (iii) ionizable hydrogen atoms, and (iv) one or more oxygen atoms; preferably the anions are fluorotitanate (i.e., TiF 6 "2 ) or fluorozircon- ate (i.e., ZrF 6 "2 ), most preferably fluorotitanate;
- component (B) 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; independently preferably at least, with increasing preference in the order given, 60, 70, 80, 85, 90, 95, or 99 % by weight of the total of component (B) consisting of divalent manganese, cobalt, nickel, or magnesium, more preferably of divalent manganese, cobalt, or nickel; most preferably of divalent manganese;
- fluorometallate anions each of said anions consisting of (i) at least four fluorine atoms, (ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, optionally, one or both of (iii) ionizable hydrogen atoms, and (iv) one or more oxygen atoms and one or more materials selected from the group consisting of metallic and metalloid elements and the oxides, hydroxides, and carbonates of these metallic or metalloid elements to produce a reaction product that is not part of any of components (A) through (F) as recited above; preferably this component results from reaction with silica or vanadium(V) oxide.
- component (D) can be used to provide at least part of both of components (A) and (D).
- component (B) can be provided by iron dissolved from the substrate and need not be present in the liquid composition when the liquid composition is first contacted with the substrate.
- the pH value of an acidic aqueous liquid composition according to the invention preferably is at least, with increasing preference in the order given, 0.5, 1.0, 1.4, 1.7, 2.0, or 2.3 and independently preferably is not more than, with increasing preference in the order given, 5.0, 4.0, 3.5, 3.2, 2.9, 2.6, or 2.4.
- Component (C) as defined above is to be understood as including all of the following inorganic acids and their salts that may be present in the composition: hypophos- phorous acid (H 3 PO 2 ), orthophosphorous acid (H 3 P0 3 ), pyrophosphoric acid (H 4 P 2 O 7 ), orthophosphoric acid (H 3 PO 4 ), tripolyphosphoric acid (H 5 P 3 O 10 ), and further condensed phosphoric acids having the formula H x+2 P x O 3x+1 , where x is a positive integer greater than 3.
- Component (C) also includes all phosphonic acids and their salts.
- the concentration in the total composition of phosphorus atoms contained in component (C) is preferably at least, with increasing preference in the order given, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.34, 0.38, 0.42, or 0.45 moles of phosphorus atoms per kilogram of total composition (this unit of measure being hereinafter freely applied to any other constituent as well as to phosphorus and being hereinafter usually abbreviated as "M/kg”) and independently preferably is not more than, with increasing preference in the order given, 2.0, 1 .5, 1 .0, 0.8, 0.60, 0.55, 0.50, or 0.47 M/kg.
- inorganic phosphates particularly orthophosphates, phosphites, hypo- phosphites, and/or pyrophosphates, especially orthophosphates
- component (C) are preferred for component (C) because they are more economical.
- Phosphonates are also suitable and may be advantageous for use with very hard water, because the phosphonates are more effective chelating agents for calcium ions.
- Acids and their salts in which phosphorous has a valence less than five may be less stable than the others to oxidizing agents and are therefore less preferred in compositions according to the invention that are to contain oxidizing agents; such acids and their salts are less preferred in all instances for economy.
- the polymers required for component (D) may be prepared by processes as de- scribed in one or more of the following U. S. Patents, the entire disclosures of all of which, except for any extent to which they may be inconsistent with any explicit statement herein, are hereby incorporated herein by reference: 5,891 ,952, 5,116,912, 4,517,028, 4,433,015, and 4,376,000.
- the polymers required for component (D) are made in a manner that reduces or eliminates the presence of organic solvent in the source of the polymer that is added to a mixture to make an acidic aqueous liquid composition according to the invention.
- these polymers are made by a method that does not use any organic solvent, as set forth further in the paragraphs following immediately below.
- An aqueous solution of substituted aminomethylated polyphenol polymers produced by this preferred process is a product of reaction of: (A') at least one precursor phenolic polymer or copolymer, which normally does not bear any substituted aminomethyl substituents on its aromatic rings; (B 1 ) at least one aldehyde, ketone, or mixture thereof; and (C) at least one amine.
- the preferred process comprises, preferably consists essentially of, or more pref- erably consists of, the following operations:
- contacting is most conveniently, economically, and effectively, and therefore preferably, carried out by passing the aqueous solution through a bed of ion-exchange resin beads arranged in a vertical column of sufficient length that the desired level of removal of alkali metal and quaternary ammonium cations is achieved by the time the solution has passed through the entire column, and the ion- exchange resin in the column can later be returned to its protonated form by treatment with strong acid; however, many other methods of establishing contact between the solution and the ion-exchange resin for a sufficient time to remove the unwanted cations from the aqueous solution are known to those skilled in ion-exchange, and any of these methods may be used.
- a strong acid cation exchange resin is used in operation (IV). If it is desired, as is usually preferred, to remove unreacted amine as well as inorganic cations added as part of the alkalinizing agent, a strong acid cation exchange resin is used in operation (IV). If it is desired to remove only inorganic cations, a weak acid cation exchange resin may be used instead. Suitable strong acid cation exchange resins are those of the sulfonic acid or phosphonic acid types, and suitable weak acid cation exchange resins are those of the carboxylic acid type.
- the quantities of components (A'), (B 1 ) and (C) used to prepare the substituted aminomethylated polyphenol polymer product in aqueous solution preferably are such as to have the following ratios to one another, independently for each ratio specified: the number of moles of carbonyl groups in component (B 1 ) has a ratio to the number of moles of primary and secondary amino nitrogen atoms in component (C) that is at least, with increasing preference in the order given, 0.5:1 .00, 0.7:1.00, 0.80:1.00, 0.85:1.00, 0.90:1.00, 0.95:1.00, or 0.99:1.00 and independ- ently preferably is not more than, with increasing preference in the order given,
- the number of moles of carbonyl groups in component (B 1 ) has a ratio to the number of moles of aromatic rings in component (A 1 ) that is at least, with increasing preference in the order given, 0.10:1 .00, 0.20:1 .00, 0.30:1 .00, 0.40:1.00, 0.50:1 .00, 0.60:1 .00, 0.70:1 .00, 0.80:1.00, 0.85:1.00, 0.90:1 .00, or 0.94:1 .00 and independently preferably is not more than, with increasing preference in the order given, 2.00:1.00, 1 .90:1.00, 1.80:1.00, 1.70:1.00, 1 .60:1.00, 1.50:1 .00, 1 .40:1.00,
- the quantities of components (A 1 ), (B'), and (C) preferably are such as to provide an aqueous solution at the end of operation (IV) that contains at least, with increasing preference in the order given, 1.0, 3.0, 5.0, 6.0, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0 percent of the total mass of the aqueous solution as polymer molecules that satisfy the definition for component (A) as given above.
- such polymer molecules independently preferably constitute not more than, with increasing preference in the order given, 50, 35, or 30 % of the total mass of the aqueous solution.
- the alkalinizing agent is preferably, for economy, an alkali metal hydroxide, e.g. sodium or potassium hydroxide, although tetraalkylammonium hydroxides, e.g. tetrabutylammonium hydroxide, or tetraarylammonium hydroxides can also be used with technically satisfactory results.
- a sufficient number of moles of alkalinizing agent should be present to correspond to at least, with increasing preference in the order given, 10, 15, 20, or 25 % of the number of moles of phenolic hydrogen atoms in component (A 1 ).
- Operation (I 1 ) is preferably carried out at a temperature that is at least, with increasing preference in the order given, 30, 40, 50, 55, 60, or 65 °C, in order to minimize the amount of neutralizing agent that is needed in operation (I') by increasing the solubility, or at least the speed of dissolution, in water of at least partially neutralized polymer molecules formed in this step.
- the temperature during operation (I 1 ) independently preferably is not more than, with increasing preference in the order given, 95, 90, 80, or 70 °C.
- the acid used to neutralize the alkalinizing agent can be organic or inorganic.
- Suitable acids for this purpose include carbonic acid, acetic acid, citric acid, oxalic acid, ascorbic acid, phenylphosphonic acid, chloromethylphosphonic acid; mono-, di- and tri-chloroacetic acids, trifluoroacetic acid, nitric acid, phosphoric acid, hydrofluoric acid, tetrafluoroboric acid, hexafluorotitanic acid, hexafluorosilicic acid, hexafluorozirconic acid, sulfuric acid, boric acid, hydrochloric acid, and the like.
- the most preferred acid is a mixture of at least one of the "fluorometallic" acids with phosphoric acid. This mixture is preferred at least for economy, because when these two acids are used as neutralizers in the preparation of an aqueous solution and/or dispersion of necessary component (D), this solution and/or dispersion provides at least part of both components (A) and (C), which are also needed for a composition according to this invention.
- Component (A 1 ) i.e., the precursor phenolic polymer or copolymer, is preferably selected from polymer molecules in which at least, with increasing preference in the order given, 10, 20, 30, 40, 50, 60, 70, 80, or 90 % of the mass of the polymer molecules is constituted of moieties that conform to one of the two following general formulas, or would so conform if one of the open bonds shown in the following general formulas were replaced by a bond to a hydrogen atom:
- each of R 1 through R 3 is independently selected from the group consisting of a hydrogen atom, alkyl moieties having from 1 to 5 carbon atoms, and aryl moieties having from 6 to 18 carbon atoms; each of Y- through Y 4 is independently selected from the group consisting of a hydrogen atom and alkyl and aryl moieties having from 1 to 18 carbon atoms; and
- W. or W 2 is selected from the group consisting of a hydrogen atom and hydrolyz- able moieties, preferably an acyl group, e.g. acetyl, benzoyl, and the like. Most preferably, independently for each such element of the formula, each of R 1 through
- R 3 , Y- through Y 4 , W sauce and W 2 is a hydrogen atom.
- the weight average molecular weight of component (A 1 ) preferably is at least, with increasing preference in the order given, 500, 1000, 1500, 2000, 2400, 2800, 3200,
- Component (B') is preferably an aldehyde, and most preferably is formaldehyde, especially in the form of paraformaldehyde.
- Liquid formaldehyde is generally commercially available only in a form that contains a significant quantity of methanol, e.g. 15 % methanol, as a polymerization inhibitor for the formaldehyde. Since the preferred process is carried out in the absence of organic solvents, formaldehyde free from methanol, such as uninhibited aqueous formaldehyde or paraformaldehyde, is preferably used.
- Component (C) is selected from amine molecules, preferably exclusively from secondary amines, still more preferably from secondary amines in which the total number of carbon atoms is not more than, with increasing preference in the order given, 10, 8, 6, 4, or 3.
- suitable secondary amines are methyl methanol amine, methyl ethanol amine, methyl butanol amine, ethyl methanol amine, ethyl ethanol amine, pentyl ethanol amine, pentyl pentanol amine, hexyi ethanol amine, dimethanol amine, diethanol amine, dipropanol amine, dibutanol amine, dipentanol amine, nonyl methanol amine, octyl ethanol amine, and the like.
- component (C) is selected from secondary amines in which one of the organic moieties bonded directly to the amino nitrogen atom in the amine is an unsubstituted alkyl moiety and the other is a hydroxyl substituted but otherwise unsubstituted alkyl moiety.
- the single most preferred substance for component (C) is methyl ethanol amine with the formula H 3 C-NH-(CH 2 ) 2 OH.
- component (D) of a composition according to this invention is in fact made by some other method than the preferred method described in the immediately preceding paragraphs, its chemical characteristics preferably are, with the same degree of prefer- ence, those that would result from being made according to this preferred method with preferred choices as indicated above.
- the term "stabilize(d) against settling" in the description above of component (G) and of operation (III 1 ) means that the composition containing the material does not suffer any visually detectable settling or separation into distinct liquid phases when stored, without mechanical agitation, for a period of 100, or more preferably 1000, hours at 25 °C.
- Materials for component (G) may be prepared by mixing the two types of reagents noted in the definition for component (G).
- the reaction to form this soluble species can be accelerated by use of heat and by stirring or other agitation of the composition.
- the formation of the soluble species is also aided by the presence in the composition of suitable complexing ligands, such as peroxide and fluoride.
- compositions according to the invention as defined above should be substantially free from many ingredients used in compositions for similar purposes in the prior art.
- these compositions when directly contacted with metal in a process according to this invention, contain no more than 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01 , 0.001 , or 0.0002, percent of each of the following constituents: organic materials that are liquid at 25 °C under normal atmospheric pressure and have a vapor pressure of at least 0.05 bar at 25 °C; hexavalent chromium; ferricyanide; ferrocyanide; sulfates and sulfuric acid; alkali metal and ammonium cations; pyrazole compounds; sugars; gluconic acid and its salts; glycerine; ⁇ -glucoheptanoic acid and its salts; and myoinositol phosphate esters
- none of these other operations include contacting the surfaces with any composition that contains more than, with increasing preference in the order given, 1 .0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01 , 0.003, 0.001 , or 0.0002 % of hexavalent chromium, except that a final protective coating system including an organic binder, more particularly those including a primer coat, may include hexavalent chromium as a constituent. Any such hexavalent chromium in the protective coating is generally adequately confined by the organic binder, so as to avoid adverse environmental impact.
- the acidic aqueous composition as noted above be applied to the metal surface and dried thereon within a short time interval.
- the time interval during which the liquid coating is applied to the metal being treated and dried in place thereon, when heat is used to accelerate the process is not more than 25, 15, 9, 7, 4, 3, 1.8, 1.0, or 0.7 second (hereinafter often abbreviated "sec").
- the acid aqueous composition used in the invention to a heated metal surface, such as one rinsed with hot water and subsequently dried after initial cleaning and very shortly before treating with the aqueous composition according to this invention, and/or to use infrared or microwave radiant heating and/or convection heating in order to effect very fast drying of the applied coating.
- a heated metal surface such as one rinsed with hot water and subsequently dried after initial cleaning and very shortly before treating with the aqueous composition according to this invention
- infrared or microwave radiant heating and/or convection heating in order to effect very fast drying of the applied coating.
- Preheating of the metal substrate before application of a composition according to the invention is preferred over postheating of the applied liquid composition when practical, because the latter is more likely to result in unwanted deformation of the coating film or inhomogeneous properties of the film as a result of more rapid drying in some areas than in others.
- the peak metal temperature preferably is in a range from, with increasing preference in the order given, 10 - 100, 15 - 95, 20 - 90, 20 - 80, or 20 - 70, °C.
- a composition according to this invention may be applied to the metal substrate and allowed to dry at a temperature not exceeding 40 °C. In such a case, there is no particular advantage to fast drying.
- This alternative embodiment is particularly advantageously used for "touching up" thinned or damaged coatings that are already in place over most of the surface of some article that is too large to fit into any conveniently available oven or other heating device.
- composition according to the invention is advantageously applied to the substrate to be treated with the aid of an applicator as taught in U. S. Patent 5,702,759 of Dec. 30, 1997 to White et al., the entire disclosure of which, except to any extent that may be inconsistent with any explicit statement herein, is hereby incorporated herein by reference.
- the effectiveness of a treatment according to the invention appears to depend predominantly on the total amounts of the active ingredients that are dried in place on each unit area of the treated surface, and on the nature and ratios of the active ingredi- ents to one another, rather than on the concentration of the acidic aqueous composition used.
- the surface to be coated is a continuous flat sheet or coil and precisely controllable coating techniques such as roll coaters are used, a relatively small volume per unit area of a concentrated composition may effectively be used for direct application.
- a working composition according to the invention that is intended to be dried without substantial external heating and/or to be applied without precise control of the total amount applied to have: a total concentration of 'lluorometallate" anions of component (A) that is at least, with increasing preference in the order given, 0.005, 0.010, 0.020, 0.030, 0.035,
- 0.040, 0.050, or 0.055 M/kg a total concentration of metal cations of component (B) that is at least, with increasing preference in the order given, 0.007, 0.011 , 0.020, 0.030, 0.035, 0.040, 0.045, 0.050, 0.054, 0.058, or 0.062 M/kg; - a ratio of total concentration in M/kg of metal cations of component (B) in M/kg to the total concentration in M/kg of "fluorometallate" anions of component (A) in the same composition that is at least, with increasing preference in the order given, 0.2:1 .0, 0.4:1 .0, 0.60:1.00, 0.70:1 .00, 0.80:1.00, 0.90:1.00, 0.95:1 .00, 1.00:1.00, 1 .05:1.00, 1.10:1.00, or 1.12:1.00 and independently preferably is not more than, with increasing preference in the order given, 3.0:1.00, 2.6
- a concentration of phosphorus from component (C) that is at least, with increasing preference in the order given, 0.007, 0.012, 0.017, 0.022, 0.027, 0.032, 0.037, 0.042, 0.047, 0.052, 0.057, 0.062, or 0.067 M/kg; - a ratio of moles of phosphorus from component (C) to moles of "fluorometallate" ions from component (A) in the same composition that is at least, with increasing preference in the order given, 0.2:1 .0, 0.4:1 .0, 0.60:1 .00, 0.70:1 .00, 0.80:1.00, 0.90:1 .00, 0.95:1.00, 1.00:1 .00, 1.05:1.00, 1 .10:1.00, 1.15:1 .00, or
- a ratio of moles of substituted phenol moieties from component (D) to moles of total metal cations from component (B) in the same composition that is at least, with increasing preference in the order given, 0.060:1 .00, 0.12:1 .00, 0.16:1 .00,
- Working compositions containing up to from five to ten times these amounts of active ingredients are also generally fully practical to use when coating control is precise enough to meter relatively thin uniform films of working composition onto the metal surface to be treated according to the invention. Concentrations of at least six times the values given above are also preferred for concentrated compositions from which working compositions within the more preferred ranges given above are to be made by dilution with water.
- the amount of composition applied in a process according to this invention is chosen so as to result in a total add-on mass (after drying) in the range from 5 to 500 milligrams per square meter of the substrate surface treated (this unit of add-on mass being hereinafter usually abbreviated as "mg/m 2 "), more preferably from 10 to 400 mg/m 2 , or still more preferably from 50 to 300 mg/m 2 .
- the add-on mass of the protective film formed by a process according to the invention may be conveniently monitored and controlled by measuring the add-on weight or mass of the metal atoms in the anions of component (A) as defined above. The amount of these metal atoms may be measured by any of several conventional analytical techniques known to those skilled in the art.
- the most reliable measurements generally involve dissolving the coating from a known area of coated substrate and determining the content of the metal of interest in the resulting solution.
- the total add-on mass can then be calculated from the known relationship between the amount of the metal in component (A) and the total mass of the part of the total composition that remains after drying. For the purpose of this calculation it is assumed that all water in the working composition, including any water of hydration in any solid constituent added to the composition during its preparation, is expelled by drying but that all other constituents of the liquid film of working composition coated onto the surface measured remain in the dried coating. In many instances, fully practically satisfactory quality can be achieved by experience in judging the visual appearance of the coating, without directly measuring the amount of coating added on at all.
- a working composition according to the invention may be applied to a metal work- piece and dried thereon by any convenient method, several of which will be readily apparent to those skilled in the art.
- coating the metal with a liquid film may be accomplished by immersing the surface in a container of the liquid composition, spraying the composition on the surface, coating the surface by passing it between upper and lower rollers with the lower roller immersed in a container of the liquid composition, and the like, or by a mixture of methods.
- Excessive amounts of the liquid composition that might otherwise remain on some part of the surface prior to drying may be removed before drying by any convenient method, such as drainage under the influence of gravity, squeegees, passing between rolls, wiping with a towel or other absorbent material, and the like.
- the excess may simply be dried into place on the surface, and any area of the dried substrate that exhibits a powdery appearance as a result of dried excess amounts of coating material can usually be made uniform in appearance by wiping the powdery areas with a soft cloth or similar material to remove the powdery excess of dried coating. (Insofar as it has been measured, the protective quality of the coating is also uniform after such wiping to remove any powdery excess.) Drying also may be accomplished by any convenient method, such as a hot air oven, exposure to infra-red radiation, microwave heating, and the like.
- the temperature during application of the liquid composition may be any temperature within the liquid range of the composition, although for convenience and economy in application by roller coating, normal room temperature, i.e., from 20 - 30 °C, is usually preferred. In most cases for continuous processing of coils, rapid operation is favored, and in such cases drying by infrared radiative heating, to produce a peak metal temperature in the range already given above, is generally preferred.
- a composition may be sprayed onto the surface of the substrate and allowed to dry in place. Such cycles can be repeated as often as needed until the desired thickness of coating, generally measured in mg/m 2 , is achieved.
- the temperature of the metal substrate surface during application of the working composition be in the range from 20 to 300, more preferably from 30 to 100, or still more preferably from 30 to 90 °C.
- the metal surface to be treated according to the invention is first cleaned of any contaminants, particularly organic contaminants and foreign metal fines and/or inclusions.
- cleaning may be accomplished by methods known to those skilled in the art and adapted to the particular type of metal substrate to be treated.
- the surface is most preferably cleaned with a conventional hot alkaline cleaner, then rinsed with hot water, squeegeed, and dried.
- the surface to be treated most preferably is first contacted with a conventional hot alkaline cleaner, then rinsed in hot water, then, optionally, contacted with a neutralizing acid rinse, before being contacted with an acid aqueous composition as described above.
- Abrasive cleaning particularly with high-loft type coated abrasive products, may also be used effectively before treatment according to this invention.
- the invention is particularly well adapted to treating surfaces that are to be subsequently further protected by applying conventional organic protective coatings such as paint, lacquer, and the like over the surface produced by treatment according to the invention.
- organic protective coatings such as paint, lacquer, and the like
- the practice of this invention may be further appreciated by consideration of the following, non-limiting, working and comparison examples.
- aqueous solution of a polymer for component (D) of a composition according to the invention was prepared as follows: To a 500 milliliter (hereinafter usually abbreviated as “ml”) size three-neck round bottom flask equipped with an overhead stirrer, reflux condenser, nitrogen gas inlet, heating mantle and thermocouple, about 350 grams (hereinafter usually abbreviated as "g") of deionized water, 4.2 grams of sodium hydroxide, and 29.1 g of N-methyl ethanolamine were added and mixed till dissolved. 48.4 g of solid poly(4-hydroxystyrene) with a weight average molecular weight of about 5000 Daltons was then added with mixing.
- ml 500 milliliter
- g sodium hydroxide
- N-methyl ethanolamine 29.1 g
- the mixture was then heated to 65 °C with mechanical agitation. After 1 .5 hours of mixing at 65 °C the polymer was completely dissolved.
- the resulting solution was then allowed to cool to 30 °C and 12.5 g of paraformaldehyde containing 92 % stoichiometric equivalent as formaldehyde (i.e., HCHO) was added with continued mixing. After 30 minutes, the paraformaldehyde was completely dissolved.
- the solution was then heated with mixing to 65 °C and held at that temperature for 1 .5 hours.
- the resulting pH was 5.4; the sodium concentration was less than 1 part of sodium per million parts of the solution, a concentration unit that may be freely used hereinafter for specifying the concentration of any noted material and is hereinafter usually abbreviated as "ppm", and the re- sidual formaldehyde concentration was about 90 ppm. 3.0 g of 60 % fluorotitanic acid
- a concentrate according to the invention was prepared as follows: 24.6 parts of deionized water, 3.51 parts of 75 % H 3 PO 4 in water solution, and 8.22 parts of 60 %
- a working composition according to the invention was made by mixing the concentrate described in the immediately preceding paragraph with deionized water to give a homogeneous liquid containing 15 % of the concentrate.
- this working composition was put into the reservoir of an applicator as taught in U. S. Patent 5,702,759.
- Conventional cold rolled steel test panels were prepared for use by rubbing with a water-wetted Scotch-BriteTM 96 General Purpose Scouring Pad (a high loft coated abrasive pad commercially supplied by Minnesota Mining & Manufacturing Co.) once in a lengthwise direction, next in a cross-direction, and once again in a lengthwise direction, then rinsing with hot tap water and finally wiping dry with a clean, dry, lint-free towel (Kay- dryTM EX-L 34705 Delicate Task Wiper commercially supplied by Kimberly-Clark) immed- iately before contact with whatever treatment liquid was to be used on the particular panels.
- a water-wetted Scotch-BriteTM 96 General Purpose Scouring Pad a high loft coated abrasive pad commercially supplied by Minnesota Mining & Manufacturing Co.
- Comparison Example 1 abrasive cleaning and subsequent drying as described above for the example according to the invention were used without any subsequent treatment before painting. In the remaining comparison examples, the same abrasive cleaning and subsequent drying were used prior to the following prepainting treatments as specified:
- Comparison Example 2 The cleaned substrates were treated with TOUCH-N-PREP® ALODINE® 1132, a commercial product available from the Henkel Surface Technologies Div. of Henkel Corporation, Madison Heights, Michigan, U.S.A. This product contains as its active ingredients hexavalent and trivalent chromium, fluorozirconic acid, and phosphoric acid and also contains a fluorinated surfactant.
- Comparison Example 3 This was first treated as for Comparison Example 2, dried, and then post-rinsed with a 0.25 % solution in water of the aqueous solution in water of poly(vinyl phenol) grafted with substituted aminomethyl moieties that was used to provide component (D) for the concentrate according to the invention as described above.
- Comparison Example 4 An aqueous solution of an amine oxide type substituted phenolic polymer was prepared as follows: To a 2000 ml size three-neck round bottom flask equipped with an overhead stirrer, reflux condenser, nitrogen gas inlet, heating mantle and thermocouple, about 1300 g of deionized water, 18.8 g of sodium hydroxide, 129.1 g of N-methyl ethanolamine, and 215 g of solid poly(4-hydroxy styrene) with a weight average molecular weight of about 5000 Daltons were added and mixed till dissolved. The mixture was then heated to 65 °C with mixing. After 1.5 hours of mixing at 65 °C the polymer and all other materials added were completely dissolved.
- the resulting solution was then allowed to cool to 30 °C and 55.6 g of paraformaldehyde containing 92 % stoichiometric equivalent as formaldehyde (i.e., HCHO) and 114 g of additional deionized water were added with continued mixing. After 30 minutes, the paraformaldehyde was completely dissolved. The solution was then heated with mixing to 65 °C. and held at that temperature for 1.5 hours. Heating was then discontinued, and after the solution had cooled to about 30 °C, the solution was diluted with 1784 g of additional deionized water, then mixed rapidly with 104 g of 31 % H 2 O 2 in water and 28 g of 14.6 % H 2 O 2 in water.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16245599P | 1999-10-29 | 1999-10-29 | |
US162455P | 1999-10-29 | ||
PCT/US2000/029266 WO2001032952A1 (en) | 1999-10-29 | 2000-10-24 | Composition and process for treating metals |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1246952A1 true EP1246952A1 (en) | 2002-10-09 |
EP1246952A4 EP1246952A4 (en) | 2004-12-08 |
EP1246952B1 EP1246952B1 (en) | 2009-08-26 |
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ID=22585698
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Application Number | Title | Priority Date | Filing Date |
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EP00975346A Expired - Lifetime EP1246952B1 (en) | 1999-10-29 | 2000-10-24 | Composition and process for treating metals |
Country Status (7)
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EP (1) | EP1246952B1 (en) |
AU (1) | AU1341001A (en) |
CA (1) | CA2389343A1 (en) |
DE (1) | DE60042842D1 (en) |
ES (1) | ES2334489T3 (en) |
TW (1) | TW541353B (en) |
WO (1) | WO2001032952A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6821633B2 (en) | 2002-05-17 | 2004-11-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Non-chromate conversion coating compositions, process for conversion coating metals, and articles so coated |
GB0323806D0 (en) | 2003-10-10 | 2003-11-12 | Univ Southampton | Fabrication of semiconductor metamaterials |
GB0323807D0 (en) | 2003-10-10 | 2003-11-12 | Univ Southampton | Fabrication of metamaterials |
US20060151070A1 (en) | 2005-01-12 | 2006-07-13 | General Electric Company | Rinsable metal pretreatment methods and compositions |
US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5116912A (en) * | 1987-12-04 | 1992-05-26 | Henkel Corporation | Polyphenolic compounds and uses thereof |
US5449415A (en) * | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
US5958511A (en) * | 1997-04-18 | 1999-09-28 | Henkel Corporation | Process for touching up pretreated metal surfaces |
US5885373A (en) * | 1997-06-11 | 1999-03-23 | Henkel Corporation | Chromium free, low organic content post-rinse for conversion coatings |
US5891952A (en) * | 1997-10-01 | 1999-04-06 | Henkel Corporation | Aqueous compositions containing polyphenol copolymers and processes for their preparation |
-
2000
- 2000-10-24 CA CA002389343A patent/CA2389343A1/en not_active Abandoned
- 2000-10-24 ES ES00975346T patent/ES2334489T3/en not_active Expired - Lifetime
- 2000-10-24 WO PCT/US2000/029266 patent/WO2001032952A1/en active Application Filing
- 2000-10-24 DE DE60042842T patent/DE60042842D1/en not_active Expired - Lifetime
- 2000-10-24 EP EP00975346A patent/EP1246952B1/en not_active Expired - Lifetime
- 2000-10-24 AU AU13410/01A patent/AU1341001A/en not_active Abandoned
-
2001
- 2001-01-04 TW TW89121614A patent/TW541353B/en not_active IP Right Cessation
Non-Patent Citations (2)
Title |
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No further relevant documents disclosed * |
See also references of WO0132952A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2389343A1 (en) | 2001-05-10 |
ES2334489T3 (en) | 2010-03-11 |
EP1246952A4 (en) | 2004-12-08 |
AU1341001A (en) | 2001-05-14 |
WO2001032952A1 (en) | 2001-05-10 |
EP1246952B1 (en) | 2009-08-26 |
DE60042842D1 (en) | 2009-10-08 |
TW541353B (en) | 2003-07-11 |
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