US3907608A - Coated metal and method - Google Patents
Coated metal and method Download PDFInfo
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- US3907608A US3907608A US370437A US37043773A US3907608A US 3907608 A US3907608 A US 3907608A US 370437 A US370437 A US 370437A US 37043773 A US37043773 A US 37043773A US 3907608 A US3907608 A US 3907608A
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- metal
- coating
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- chromium
- coating composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/226—Non-corrosive coatings; Primers applied before welding
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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
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12049—Nonmetal component
- Y10T428/12056—Entirely inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
Definitions
- ABSTRACT A coating on a metal substrate of CrO and pulverulent metal in aqueous medium and containing particular organic liquid provides a corrosion and alkali resistant coatingto the metal.
- the resulting coated substrates have eleetroconductivity, e.g., for application of electrocoating primer, after the ap' plieation and baking of the coating composition on a substrate.
- compositions of typically aluminum flake, a polymeric glycol plus a wetting agent have been taught in U.S. Pat. No. 3,318,716 as useful anti-foaming compositions in paste or liquid form. They may be used to supply very minor amounts of pigmentation to coating compositions but do not ostensibly lend particular advantages to resulting coatings except as attributed to the metal flake component.
- compositions containing aluminum flake provide a barrier coating or film on the underlying substrate.
- This barrier coating provides an essentially inert metal-.
- compositions are of particular interest herein,.
- reaction products of chromium compound e.g. chromic acid
- high boiling organic solvents for example, in U.S. Pat. No. 2,355,889 the reaction product of chromic acid and ethylene glycol monoethyl ether is shown to have utility whenincorporated into a paint.
- reaction products of typically glycol-ethers and chromic acid have been shown to be useful in their own right and when simply used as such reaction product in water, for obtaining corrosion resistant coatings on metallic surfaces.
- the low molecular weight ethers of glycols are employed for the reaction product.
- compositions containing a hexavalent chromium-providing substance along with a pulverulent metal may further contain up to ten volume percent of a surface active agent.
- agent may be an alkyl ether of an alkylene glycol or a polyalkylene glycol.
- a coating composition for metals has now been found that offers excellent coating uniformity on the coated substrate. Resulting coatings exhibit augmented adhesion and desirablecolor and non-staining characteristics. The coating uniformity extends to nontearing, a particular problem of prior aqueous medium compositions that is exhibited by variations in coating uniformity resulting when parts removed from a coating bath drained unevenly leaving excessive coating composition build-up where the drainage was greatest.
- Such coating characteristics have been obtained without sacrifice to coating bath stability, including retention of pulverulent metal flake inertness in the bath as well as excellent dispersion in the coating bath.
- coatings of excellent protective value and including augmented resistance to mild alkali
- such coatings exhibit electroconductivity. e.g., for subsequent weldability or application of clectroeoat paint.
- the present invention is directed to an aqueous coating composition for application to, and curing on, a metal substrate, thereby preparing an adherent, water insoluble, alkali and corrosion resistant as well as substantially resinfree coating on said substrate, which composition before curing comprises an intimate mixture in aqueous liquid medium of: (a) a hexavalent-chromium-providing substance, supplied by about to weight percent chromic acid and providing below about 100 grams per liter of @hfomium.
- CrO t (19) below about 500 grains per liter of liquid medium of pulverulent metal selected from the group consisting of zinc, aluminum, mixtures thereof and alloys of same, said composition having a weight ratio of chromium, expressed as CrO to pulverulent metal of between about 1:1 and l:l5; (e) below about 50 volume percent but substantially above volume percent, based on the volume of the total liquid of the aqueous composition, of water soluble organic liquid substance maintains liquidity above 100C.
- the present invention relates to a coated metal substrate, and the preparation of such a substrate, exhibiting the above described adherent, alkali and corrosion resistant coating. It is further directed to the preparation of weldable substrates and to welded articles, and additionally to precursor constituents for preparing aqueous coating compositions.
- the metal substrates contemplated by the present invention are exemplified by the metal substrates to which a chromic acid plus pulverulent metal in a liquid coating may or can be applied for enhancing corrosion resistance of such substrate metals.
- such metal substrates may be aluminum and its alloys, zinc and its alloys, copper and cupriferous, e.g., brass and bronze.
- exemplary metal substrates include cadmium, titanium, nickel, and its alloys, tin, lead, chromium, magnesium and alloys thereof, and for weldability, preferably a ferrous metal substrate such as iron, stainless steel, or steel such as cold rolled steel or hot rolled and pickled steel. All of these for convenience are usually referred to herein simply as the substrate.”
- the hexavalent-chromiumcontaining aqueous coating composition is often referred to herein as "treating compositions" and the "residue” on a metal surface is such resulting surface condition obtained after application of such composition to, and heating resulting applied composition on, a metal substrate.
- the high boiling organic compound is often termed herein as the high boiling hydrocarbon" orjust the hydrocarbon.”
- the corrosion-resistant, hexavalent-chromiumcontaining aqueous composition contains chromic acid as the hexavalent-chromium-providing substance or its equivalent in aqueous medium, for example, chromium trioxidc or chromic acid anhydride. But a minor amount, e.g., percent or less, of such chromium can be supplied by a salt such as ammonium dichromate. or by sodium or potassium salts, or by substances such as calcium, barium, magnesium, zinc, cadmium, and strontium dichromate.
- a minor amount such as 20 percent or less of the hexavalentchromium-providing substance might be a mixed chromium compound, i.e., include trivalent chromium compounds.
- the aqueous composition might contain only a small amount, e.g., 5 grams per liter of hexavalent chromium, expressed as CrO and may contain as much as about 100 grams per liter of composition of hexavalent chromium, expressed as CrO it will typically contain between about 20-60 grams.
- liquid medium For supplying the liquid medium, without considering the contribution by the hydrocarbon, water virtually always supplies the whole amount.
- Other liquids may possibly be used, but preferably only a very minor amount of the aqueous medium, basis the high boiling organic compound free medium, is such other liquid material.
- Such other liquids that might be contemplated include alcohols, most notably t-butanol, and halogenated hydrocarbon liquid, some of which have been discussed in US. Pat. Nos. 2,762,732 and 3,437,531.
- a substantial amount of liquid in the aqueous liquid medium i.e., up to 50 volume percent based on the total volume of liquid in the aqueous medium, can be supplied by the high boiling hydrocarbon.
- Such organic liquid compound also must supply substantially above 15 volume percent, on a similar basis, of such total liquid and advantageously for enhanced coating characteristics, supplies above about 20 volume percent. Lesser amounts of such, total liquid will not contribute sufficient hydrocarbon to assure consistently augmented properties of the coating, although such amounts might achieve enhanced dispersion and compositional flow characteristics. It is most important that this high boiling organic compound be liquid at l 00C., and by such herein it is meant to be liquid at C. at atmospheric pressure.
- hydrocarbon should also be easily soluble in water to at least contribute to twenty volume percent of the liquid medium at ambient temperature. It is meant herein to include such hydrocarbons as may be termed miscible" in water at such proportion under such temperature condition.
- hydrocarbons as are more specifically detailed hereinbelow are serviceable as being soluble in water so long as they mix or blend uniformly with water and preferably at the 20-50 volume percent range. Yet, such hydrocarbons must not be highly toxic to avoid uneconomical expense in handling and use.
- Such hydrocarbons as are serviceable in the present invention are also those that are retained during baking on the metal substrate in sufficient amount and duration to permit participation of the hydrocarbon in the formation of a coating.
- This participation is best exemplified by such characteristics as reduction of chromium in the coating from hexavalent to the trivalent state, most desirable leafing into a layered, substantially uniform coating of the metallic flake as well as characteristics of the resultant coating, for example as exhibited from mild alkali resistance testing.
- the organic compounds contain carbon, oxygen and hydrogen and have at least one oxygen-containing constitutcnt that may be hydroxyl, or 0x0, or a low molecular weight ether group, i.e., a C C ether group.
- polymeric hydrocarbons are not particularly suitable and advantageously serviceable hydrocarbons contain less than about 15 carbon atoms.
- Particular hydrocarbons which can or have been used include tri'. and tetraethylene glycol, di-and tripropylene glycol, the monomethyl, dimethy, and
- the pulverulent metal flake e.g., zine flake or aluminum flake, or mixtures of such flakes, but preferably zinc flake for galvanic protection and coatability, is most typically such a pulverulent metal flake having a thickness on the order of 0. l0.3 micron and most typi cally a size in the longest dimension of not substantially above about 50 microns.
- Aluminum flake also sometimes termed leafing aluminum pigment has been discussed, for example, in US. Pat. No. 2,312,088.
- Flake may be blended with pulverulent metal powder, but typically in only minor amounts of the powder, and such powder should have particle size so that all parti cles pass 100 mesh and a major amount pass 325 mesh (mesh is used herein as US. Standard Sieve Series).
- the powders are generally spherical as opposed to the leaflng characteristic of the flake.
- the coating composition should be made up with an amount of pulverulent'metal sufflcient to supply not substantially above about 500 grams of metal per liter of coating composition liquid medium.
- the presence of greater than about 500 grams per liter of pulverulent metal flake is undesirable, for example, can add expense without a significant increase in protection for the coated substrate.
- the composition contains at a minimum about 50 grams of metal per liter and preferably contains between about 150-400 grams of metal per liter.
- a very minor amount of dispersing agent is also added in this pre-blend.
- Such a pre-blend, or admix is desirably stable and may there fore have advantages in mixing prior to storage or shipment. It can thereafter-be readily admixed with other ingredients, e.g., water and chromic acid, for the formation of the coating composition.
- the dispersing agent when it is present it will form less than about 3 weight percent, and typically from about 0.2 to about 0.9 weight percent, of such blend basis of the total weight of the blend. Further, because the pre-blend has been found to be suitable with the preferred zinc flake, such flake preferably contributes from about 80 to 100 weight percent of the pulverulent metal present therein.
- the admix which may also be termed a coating composition precursor constituent, is prepared to contain a weight ratio of the hydrocarbon to the pulverulent metal flake of between about 1:25 1:0.3. Within this ratio, and preferably within a weight ratio of hydrocarbon to pulverulent meta] flake of between about 1:2 to 1:08, the admix will exhibit desirable stability while providing ready mixing with further compositional constituents to yield the aqueous coating composition.
- the chromium, expressed as CrO should not exceed more than about 100 grams per liter of composition medium. Greater than about 100 grams per liter of chromium is uneconomical and can deleteriously detract from the characteristics of the coated metal surface, for example, the most desirable corrosion resistance for the coated metal substrate. Further such composition should have a weight ratio of chromium, expressed as CrO to metal flake of between about 1:1 to 1:15.
- a ratio of beyond about l:l5 may not provide sufficient chromium in the coating to achieve augmented bonding of the pulverulent metal to the metal substrate.
- a ratio of about 1:] may be achieved, but should preferably be at metal concentrations of less than about grams per liter.
- the metal content approaches about 500 grams per liter and thus the chromium content can approach about 100 grams per liter the upper weight ratio of chromium, expressed as CrO to pulverulent metal approaches 1:5.
- These coating compositons are virtually always made as very concentrated coating compositions at a ratio of between about 1:4 and 1:9 and have particular utility in the coating of small parts as opposed to application to large substrate areas such as metal coils.
- the coating ingredients may be combined into separate packages, c.g., a two package system with one containing the hexavalentchromium-providing substance in an aqueous medium, and the other package being a water-free dispersion in high boiling hydrocarbon of pulverulent metal; each package may additionally contain some surface active agent, or it may all be in the package with the metal.
- separate packages are then mixed before application to the metal substrate.
- Such coating compositions may be applied to the metal substrate by any conventional method for coating a substrate with a liquid, for example, dip coating, roller coating or reverse roller coating, or combinations of techniquesas, for example, spray and brush techniques.
- a liquid for example, dip coating, roller coating or reverse roller coating, or combinations of techniquesas, for example, spray and brush techniques.
- the composition is applied by simply dipping the article into the composition.
- the metal surface can be a preheated metal surface to assist in the curing of the composition, or the coating composition may be applied from a heated bath, for example, one heated up to 200F.
- the coating composition should contain some, and generally contains up to, for example, about 0.05 volume percent, basis total composition liquid, and typically not above about 1-2 volume percent, ofa dispersing agent. Such agent may be present in as little as 0.0005 volume percent, also on a total liquid basis. It is generally contemplated to employ a dispersing agent that is a nonionic surfactant which may be an ethoxylated alkylphenol such as a nonyl or octyl phenol. It is also contemplated to employ the nonionic ethoxylated aliphatic alcohols, representatives of which include the oleyl, lauryl, and stearyl alcohols.
- a dispersing agent that is a nonionic surfactant which may be an ethoxylated alkylphenol such as a nonyl or octyl phenol. It is also contemplated to employ the nonionic ethoxylated aliphatic alcohols, representatives of which include the oleyl, la
- nonionic surfactants that are also readily commercially available and are contemplated for use in the present invention include, for example, carboxylic esters that encompass the glycerol esters and the anhydrosorbitol esters, as well as the polyoxyethylene esters of fatty, rosin, and tall oil acids. It is also further contemplated to use carboxylic amide nonionic surfactants for dispersing the pulverulent metal and these are meant herein to include the polyoxyethylene fatty acid amides.
- the preferred agents for effecting pulverulent metal dispersibility are polyethoxy adducts, exemplified by the alkylphenoxypolyethoxyalkanols, and derivatives thereof, some of which are described in US. Pat.
- Such agents are nonionic and have between about 7 and 50 oxyethylene units in the molecule.
- the agent 7 is present in the coating composition in an amount between about 0.001-002 volume percent, on a total liquid basis.
- the resulting coating weights on the metal substrate may vary to a considerable degree but, exclusive of the metal flake the residue will most typically always be present in an amount supplying above about milligrams per square foot of chromium, expressed as chromium and not CrO Furthermore, residues containing below about 15 milligrams per square foot of chromium, expressed as chromium and not CrO should be topcoated to impart significant enhancement in corrosion resistance of the coated substrate. Also if the coated metal substrate is to be subsequently formed,
- the residue should contain not substantially above about 150 milligrams per square foot of chromium as the coating may be subjected to cracking or crazing during forming operation, although for typically finished products when subsequent forming is not contemplated, and extended corrosion resistance without topcoating may be desirable, such residue may contain up to about 500 milligrams per square foot of chromium.
- a subsequent paint topcoating is also a consideration for the amount of pulverulent metal that should be present on the surface of the substrate in the coating residue.
- Such residues containing about 10-200 milligrams per square foot of pulverulent metal are virtually always topcoated.
- subsequently topcoated I residues can contain substantially more pulverulent metal, e.g., 600-700 milligrams per square foot of such metal, and the substrate may contain up to about 5,000
- the present invention is directed to coatings wherein there is an excess of pulver for example, 5,000 milligrams persquare foot of pulverulent metal, the weight ratio of chromium to pulverulent metal will be less than about 0.2:1. It has also been found that for coating small parts, e.g., parts adapted for individual dipping in a coating bath, which can be'final products that will not be normally subjected to subsequent forming, and where coating weights may approach 5,000 milligrams per square foot of pulverulent metal, the weight ratio of chromium to pulverulent metal in the coating may be as low as about 0.02:l.
- compositions should be substantially resin-free and can be substantially pigment free, i.e., contain little, if any, pigment or resin such as 10 grams per liter total of both or less and should preferably be resin free. It may however be desirable to include, within such total of 10 grams per liter, substances that can thicken the coating composition.
- these substances e.g., water soluble cellulose ethers such as hydroxycthylcellulose
- these agents may be considered as resinous substances, they will be used for their thickening ability.
- such agents do not impart a resin film to the coating composition residue.
- Other such agents include xanthan gum hydrophilic colloids, as well as additional gums, e.g., guar gum and karaya gum.
- These other compounds further include inorganic salts and acids as well as organic substances, often typically employed in the metal coating art for imparting some corrosion resistance or enhancement in corrosion resistance for metal surfaces.
- Such materials include zinc chloride, magnesium chloride, various chromates, e.g. strontium chromate, molybdates, glutamic acid, succinic acid, zinc nitrate, and succinimide and these are all preferably avoided, but if present, are most usually employed in the liquid composition in a total maximum amount of less than 5 grams per liter.
- the preferred temperature for the subsequent heating which is also often referred to as curing and which may be preceded by drying such as air drying, is within the range from about 400F. but more typically from about 450F. at a pressure of 760 mm. Hg up to not essentially above about l,000F.
- Such an elevated substrate temperature may be attained by preheating the metal prior to application of the liquid composition.
- curing temperatures do not often exceed a temperature within the range of about 450700F.
- the heating can be carried out in as rapidly as about one second or less but is often conducted for several minutes at a reduced temperature.
- Degreasing may be accomplished with known agents, for instance, with agents containing sodium metasilicate, caustic soda, carbon tetrachloride, trichloroethylene, and the like.
- Commercial alkaline cleaning compositions which combine washing and mild abrasive treatments can be employed for cleaning, e.g., an aqueous trisodium phosphate-sodium hydroxide cleaning solution.
- the substrate may undergo cleaning plus etching.
- the resulting coated substrate of the present invention can be further topcoated with any suitable paint. i.e., a paint, primer. including electrocoating primers, and weldable primers such as the zincrich primers that can be applied before, typically, electrical resistance welding. and paints such as enamel, varnish. or lacquer. Since the coated metal surfaces of the present invention can exhibit a desirable upgrading in topcoat adhesion when compared, for example, to the uncoated substrate metal, paints are often applied over such coated substrates.
- paints may contain pigment in a binder or can be unpigmented, e.g., generally cellulose lacquers, rosin varnishes, and oleoresinous varnishes, as for example tung oil varnish.
- paints can be solvent reduced or they may be water reduced, e.g., latex or watersoluble resins, including modified or soluble alkyds, or the paints can have reactive solvents such as in the polyesters or polyurethanes.
- Additional suitable paints which can be. used include oil paints, including phenolic resin paints, solvent-reduced alkyds, epoxys, acrylics, vinyl, including polyvinyl butyral and oil-wax-type coatings such as linseed oilparaffin wax paints.
- the paints may be applied as mil! finishes.
- the weldability of coated substrates is of particular interest in regard to electrical resistance welding that can be exemplified by electrical resistance spot welding wherein opposing electrodes are closed against weldable substrates maintained for welding within the gap between the electrodes. For this spot welding the opposing electrodes are closed onto the substrate to be welded under pressure, for example of a 500-600 pound load, and for a weld heat that is measured in ampseconds. Also of particular interest is the application of the coating composition to weldable metal studs that are typically solid, cylindrical metallic articles having a length of a few inches or less and are used in a welding gun for electrically resistance welding to a metal substrate.
- the coatings of the present invention on the surface of these steels in addition to providing the other coating characteristics, offer reduced sputtering during welding that can be a problem at the weld when studs are used that have a galvanized protective surface coating.
- Coating weights for parts are determined by selecting a random sampling of parts of a known surface area and weighing the sample before coating. After the sample has been coated, it is reweighed and the coating weight per selected unit of surface area, most always presented as milligrams per square foot (mgms./sq.ft. is arrived at by straightforward calculation.
- CORROSION RESISTANCE TEST (ASTM B-l 17-64) AND RATING Corrosion resistance of coated parts is measured by means of the standard salt spray (fog) test forv paints and varnishes ASTM B-1l7-64. In this test, the parts are placed in a chamber kept at constant temperature where they are exposed to a fine spray (fog) of a 5% salt solution for specified periods of time, rinsed in water and dried. The extent of corrosion on the test parts are then compared one with the other by visual inspection. 7
- the efficacy of the corrosion resistance obtained on coated parts is, in part, quantatively evaluated on a numerical scale from 0 to 10.
- the parts are visually inspected and compared with one another and the system is used for convenience in the reviewing of results.
- the rating system the following numbers are used to cover the following results:
- EXAMPLE 1 Sufficient Zinc flake having particle thickness of about 0.1-0.2 micron and a longest dimension of discrete particles of about 15 microns is dispersed in diethylene glycol monoethyl ether (DGME) together with 3 milliliters (mls.) of wetter which is a nonionic, modified polyethoxy adduct having a viscosity in centiposes at 25C. of I and a density at 25C. of 8.7 pounds per gallon, to provide in a final mixed dispersion 300 grams per liter (g./l.) of the D.G.M.E. Separately there is added to deionized water sufficient chromic acid to provide 60 g./l. of CrO in the final mixture.
- DGME diethylene glycol monoethyl ether
- chromic, acid solution is slowly added to the metal flake dispersion to form the final mixture. During the addition, a slight evolution of heat is observed and some surface foam is formed which is removed by skimming.
- An additional blend is prepared in the same manner but the blend contains 250 mis./l. of tripropylene glycol monomethyl ether (TGME) in place of the DGME and only 2 mls. of wetter.
- TGME tripropylene glycol monomethyl ether
- Each bath is used to coat five grade 8 bolts which are 11/16 inches long by about A inch in diameter at the threaded end and have [3 inch of threading on the shaft topped by a /8 inch smooth shaft section that terminates in the bolt head.
- each bath is used to coat five No. IO-A clips, sometimes referred to as speed clips, that are formed by doubling over an about 0.5 inch by 1.75 inch strip of thin sheet metal to provide a clip type configuration when viewed on edge, followed by punching a hole through the doubled configuration and leaving opposing, outwardly extending flanges around one outer clipsection of the hole.
- speed clips that are formed by doubling over an about 0.5 inch by 1.75 inch strip of thin sheet metal to provide a clip type configuration when viewed on edge, followed by punching a hole through the doubled configuration and leaving opposing, outwardly extending flanges around one outer clipsection of the hole.
- EXAMPLE 2 Various coating compositions are prepared in the manner of Example 1 and using 300 grams per liter in each composition of the zinc flake described in Example 1. Each composition also contains milliliters of the Example 1 wetter and contains a concentration of chromic acid as shown in Table 2 below. Also as shown in the table below. the compositions contain various amounts of organic compound.
- MEE diethylene glycol monethyl ether
- MME dipropylene glycol monomethyl ether
- Bath No. 7 and 8 are aged one day prior to use.
- Bath No. 8 is very viscous prior to use but is readily mixed to a smooth consistency.
- Bath No. 7 is smooth and viscous without noticeable viscosity change during the one day ageing.
- Bath No. 3 has a lower viscosity than 4 and both stir up very readily.
- Example 1 lO-A clips, as have been described in Example 1 and the coated parts are cured as described in Example I for curing times up to 14 minutes at a temperature of 475F.
- the adhesion for the cured coating on the parts is rated as good except for the adhesion on the parts coated in Bath No. 8 where it does not exhibit the good coating adhesion of the other baths.
- adhesion is determined simply by holding the part firmly in the hand and scratching with a thumbrail and comparing many parts under such scratch test.
- the coating appearance for all such parts from the baths is metallic.
- Coating weights per bolt for coatings obtained from each bath are determined, in the manner described hereinbeforc, based upon a five bolt sample from each bath and the results are reported in Table 2 below. Also shown in the table below are the results of salt spray testing for both the bolts and the clips.
- EXAMPLE 3 Various coating compositions are prepared in the manner of Example 1 and using 300 grams per liter (g/l) in each composition of zinc flake. Each composition is also prepared to contain 40 g/l of chromic acid. Further, with one exception, each composition is prepared with 3 milliliters per liter (m/./l) of the wetter described in Example 1. The one compositional exception. as shown in Table 3 below, is the last formulation reported in the table. In this last formulation, test results are obtained from a composition wherein the dis persing agent is used in an amount supplying 21 volume percent of the coating bath. This coating blend is prepared to determine the suitability of the dispersing agent as a complete replacement for the high boiling organic liquid substance that would otherwise be present. As above noted. all of the other compositions that are represented in the table, include the 3 ml./] of dispersing agent. including the composition first reported in the table. This formulation first reported then contains no further organic liquid substance and is used for comparative purposes.
- the other coating blends listed in the table contain, as shown in the table. either 10 volume percent of tetraethylene glycol (TEG) or 10, 11 or 21 volume percent, of dipropylene glycol (DPG). Each coating composition is then employed for the coating of inch inch hex head screws or for the coating of A X /8 SAE grade 2 hex bolts. The coating is conducted in a manner and the coated parts are cured as described in Example I. Coating weights for the parts, as are shown in the table below, are determined in the manner as described hereinabove.
- Test results are reported, as determined for various submersion times, all as shown in the table below; such a showing underscores the achievement of significant results in a short elapsed time.
- parts are rated in accordance with the system as described hereinabove for salt spray testing and the results as reported in the table are an average for the parts subjected to the test.
- dispersing agent which also can lead to significant coating weights, will also yield a very undesirable corrosion resistant coating.
- the 10-1 1 volume percent of high boiling organic liquid substance is insufficient toachieve coatings that will assure excellent corrosion resistance.
- Example 4 The coating compositions of Example 3, with the exception of the formulation containing ll volume percent DPG, are used in the manner of Example 3 to coat screws or bolts all in the manner of Example 3. Coated parts, selected at random, are then subjected to a coating adhesion test. This test, which may be conveniently termed a wipe adhesion test, is manually conducted with the bolt or screw and a paper towel.
- the electrocoat paint is a commercial waterbased, blackpigmented polyester-based paint. lt-is anodically deposv 'ited with animpressed voltage of 100-150 volts for a TABLE 5 Part A: Panels Compound Coating Compound Cone. Weight Salt Spray Type Vol.7: mgmsJft.
- An aqueous coating composition for application to, and curing on, a metal substrate, thereby preparing an adherent water insoluble, alkali and corrosion resistant as well as substantially resinfree coating on said B. above 50 but below about 500 grams per liter of liquid medium of pulverulent metal selected from the group consisting of zinc, aluminum, mixtures thereof and alloys of same, said composition having a weight ratio of chromium, expressed as CrO to pulverulent metal of between about 1:1 and 1:15;
- organic liquid substance is selected from the group consisting of dipropylene glycol, tripropylene glycol monomethyl ether, tetraethylene glycol, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and mixtures of the foregoing.
- a pulverulent metal containing precursor constituent adapted for blending into chromium-containing aqueous blend for preparing a substantially resin-free, liquid coating composition for metal substrates, said coating composition having a ratio of chromium, expressed as C r0 to pulverulent metal of between about 1:1 and 1:15, wherein said precursor constituent consists of pulverulent metal the preponderance of which is zinc flake. water soluble organic liquid substance that maintains liquidity at 100C.
- the coating composition precursor constituent of claim 6 wherein said organic liquid substance is selected from the groupconsisting of dipropylene glycol, tripropylene glycol monomethyl ether, tetraethylene glycol, diethylene glycol monoethylether, dipropylene glycol monomethyl ether, and mixtures of the foregoing.
- the method of preparing a coated metal substrate having on the surface thereof an adherent, alkali and corrosion resistant, water insoluble and substantially resin-free coating comprises:
- hexavalent-chromiumcontaining aqueous coating composition of hexavalent-chromium-providing substance supplied by about 80 to 100 weight percent chromic acid, said composition containing above about 0.0005 volume percent, basis total composition liquid, of dispersing agent and below about 50 volume percent but substantially above 15 volume percent, same basis, of water-soluble organic liquid substance that maintains liquidity above l0OC and is selected from the group consisting of tri, and tetraethylene glycol, di-, and tripropylene glycol, and
- composition being applied in an amount sufficient 'to provide not above about 500 milligrams per square foot of coated substrate of chromium, said composition also containing pulverulent metal selected from the group consisting of zinc, aluminum,
- mixtures-thereof, and'alloys of same in sufficient amount to provide not substantially above about 5,000 milligrams per square foot of coated substrate of said pulverulent metal'and to provide said coating with a weight ratio of chromium, as chromium' to pulverulenfmetal of not substantially above' about 05:1, and
- said coated metal substrate is from a substantially resinfree hexavalent-chromium-containing aqueous coating composition containing a hexavalent-chromium-providing substance, between below about 50 volume percent, but substantially above 15 volume percent, basis total composition liquid, of water-soluble organic liquid substance that maintains liquidity above C and is selected from the group consisting of tri-, and tetraethylene glycol, di-, and tripropylene glycol, and the water soluble low molecular weight ethers of all such foregoing glycols, diacetone alcohol, the water soluble low molecular weight ethers of diethylene glycol, and mixtures of the foregoing, and above about 0.0005 volume percent, same basis, of dispersing agent, and said coating composition providing said residue with not above about 500 milligrams per square foot of coated substrate of chromium, wherein said coating contains a weight ratio of chromium, as chromium to
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Abstract
Description
Claims (27)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US370437A US3907608A (en) | 1971-08-19 | 1973-06-15 | Coated metal and method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US17324371A | 1971-08-19 | 1971-08-19 | |
US370437A US3907608A (en) | 1971-08-19 | 1973-06-15 | Coated metal and method |
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US370437A Expired - Lifetime US3907608A (en) | 1971-08-19 | 1973-06-15 | Coated metal and method |
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Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5249935A (en) * | 1975-10-20 | 1977-04-21 | Kito Kk | Production method of corrosionnresistant abrasion resistant link chain |
US4026710A (en) * | 1975-01-27 | 1977-05-31 | Diamond Shamrock Corporation | Preparation of zinc flake coating composition |
US4052231A (en) * | 1974-09-09 | 1977-10-04 | Diamond Shamrock Corporation | Stable colloid solution and method of making same |
US4157924A (en) * | 1978-08-25 | 1979-06-12 | The Dow Chemical Company | Process of applying weldable coating compositions to a metallic substrate |
US4162244A (en) * | 1978-08-25 | 1979-07-24 | The Dow Chemical Company | Coating compositions |
US4186036A (en) * | 1978-08-25 | 1980-01-29 | The Dow Chemical Company | Weldable coating compositions |
EP0017243A1 (en) * | 1979-04-06 | 1980-10-15 | Diamond Shamrock Corporation | Anticorrosive coating composition |
US4318754A (en) * | 1978-10-03 | 1982-03-09 | Kawasaki Steel Corporation | Surface treatment method for tin-free steel |
US4365003A (en) * | 1981-01-12 | 1982-12-21 | Diamond Shamrock Corporation | Silicate treatment for coated substrate |
US4487815A (en) * | 1983-03-07 | 1984-12-11 | Diamond Shamrock Chemicals Company | Temperature resistant coating composite |
US4698269A (en) * | 1986-05-08 | 1987-10-06 | Narusch Jr Michael J | Sintered, corrosion-resistant powdered metal product and its manufacture |
US4975330A (en) * | 1983-11-28 | 1990-12-04 | Sermatech International, Inc. | Coating compositions containing unreacted hexavalent chromium, a method of applying and an article |
US5066540A (en) * | 1987-01-23 | 1991-11-19 | Sermatech International, Inc. | Flake materials in coating compositions |
US5259884A (en) * | 1989-11-06 | 1993-11-09 | Compagnie Francaise De Produits Industriels | Process adapted to provide on a metallic substrate a protective coating based on hexavalent chromium, bath used in the said process and commercial form of the components of the bath |
US5360639A (en) * | 1992-09-01 | 1994-11-01 | Kenji Kawabata | Method of providing a decorative pattern on a screw head |
US5393567A (en) * | 1990-11-27 | 1995-02-28 | Sika Chemie Gmbh | Powder mixture for making an undercoating agent for steel surfaces |
US5486414A (en) * | 1994-07-18 | 1996-01-23 | Henkel Corporation | Dual coated metal substrates and method of making |
EP0808883A2 (en) * | 1996-05-20 | 1997-11-26 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
US6270884B1 (en) | 1999-08-02 | 2001-08-07 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
EP1233043A2 (en) * | 2001-02-14 | 2002-08-21 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US20040191555A1 (en) * | 2003-02-06 | 2004-09-30 | Metal Coatings International Inc. | Coating systems having an anti-corrosion layer and a powder coating layer |
US20040206266A1 (en) * | 2001-02-14 | 2004-10-21 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
EP1500686A1 (en) | 2003-07-22 | 2005-01-26 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
US20050256658A1 (en) * | 2004-05-12 | 2005-11-17 | Anderson Keith F | Multi-port scattering parameter calibration system and method |
US20090078155A1 (en) * | 2001-02-14 | 2009-03-26 | Metal Coatings International, Inc. | Particulate metal alloy coating for providing corrosion protection |
WO2012003843A1 (en) | 2010-07-05 | 2012-01-12 | Holger Blum | Polyurethane coating agent |
CN106221345A (en) * | 2016-08-08 | 2016-12-14 | 常熟市常力紧固件有限公司 | A kind of corrosion-resistant bolt of car shock mitigation system |
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US3189488A (en) * | 1960-10-10 | 1965-06-15 | Amchem Prod | Solutions and method for coating metal surfaces |
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Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4052231A (en) * | 1974-09-09 | 1977-10-04 | Diamond Shamrock Corporation | Stable colloid solution and method of making same |
US4026710A (en) * | 1975-01-27 | 1977-05-31 | Diamond Shamrock Corporation | Preparation of zinc flake coating composition |
JPS5249935A (en) * | 1975-10-20 | 1977-04-21 | Kito Kk | Production method of corrosionnresistant abrasion resistant link chain |
US4157924A (en) * | 1978-08-25 | 1979-06-12 | The Dow Chemical Company | Process of applying weldable coating compositions to a metallic substrate |
US4162244A (en) * | 1978-08-25 | 1979-07-24 | The Dow Chemical Company | Coating compositions |
US4186036A (en) * | 1978-08-25 | 1980-01-29 | The Dow Chemical Company | Weldable coating compositions |
US4318754A (en) * | 1978-10-03 | 1982-03-09 | Kawasaki Steel Corporation | Surface treatment method for tin-free steel |
EP0017243A1 (en) * | 1979-04-06 | 1980-10-15 | Diamond Shamrock Corporation | Anticorrosive coating composition |
US4266975A (en) * | 1979-04-06 | 1981-05-12 | Diamond Shamrock Corporation | Anticorrosive coating composition |
US4365003A (en) * | 1981-01-12 | 1982-12-21 | Diamond Shamrock Corporation | Silicate treatment for coated substrate |
US4487815A (en) * | 1983-03-07 | 1984-12-11 | Diamond Shamrock Chemicals Company | Temperature resistant coating composite |
US4975330A (en) * | 1983-11-28 | 1990-12-04 | Sermatech International, Inc. | Coating compositions containing unreacted hexavalent chromium, a method of applying and an article |
US4698269A (en) * | 1986-05-08 | 1987-10-06 | Narusch Jr Michael J | Sintered, corrosion-resistant powdered metal product and its manufacture |
US5066540A (en) * | 1987-01-23 | 1991-11-19 | Sermatech International, Inc. | Flake materials in coating compositions |
US5259884A (en) * | 1989-11-06 | 1993-11-09 | Compagnie Francaise De Produits Industriels | Process adapted to provide on a metallic substrate a protective coating based on hexavalent chromium, bath used in the said process and commercial form of the components of the bath |
US5393567A (en) * | 1990-11-27 | 1995-02-28 | Sika Chemie Gmbh | Powder mixture for making an undercoating agent for steel surfaces |
US5360639A (en) * | 1992-09-01 | 1994-11-01 | Kenji Kawabata | Method of providing a decorative pattern on a screw head |
US5486414A (en) * | 1994-07-18 | 1996-01-23 | Henkel Corporation | Dual coated metal substrates and method of making |
WO1996002384A1 (en) * | 1994-07-18 | 1996-02-01 | Henkel Corporation | Dual coated metal substrates and methods of making the same |
CN1090558C (en) * | 1994-07-18 | 2002-09-11 | 亨凯尔公司 | Dual coated metal substrates and methods of making the same |
EP0808883A3 (en) * | 1996-05-20 | 1998-08-26 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
EP0808883A2 (en) * | 1996-05-20 | 1997-11-26 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
US5868819A (en) * | 1996-05-20 | 1999-02-09 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
US6270884B1 (en) | 1999-08-02 | 2001-08-07 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
US20040206266A1 (en) * | 2001-02-14 | 2004-10-21 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
EP1233043A3 (en) * | 2001-02-14 | 2003-08-27 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
EP1233043A2 (en) * | 2001-02-14 | 2002-08-21 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US20070172680A1 (en) * | 2001-02-14 | 2007-07-26 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US7740947B2 (en) | 2001-02-14 | 2010-06-22 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US7678184B2 (en) | 2001-02-14 | 2010-03-16 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US20090078155A1 (en) * | 2001-02-14 | 2009-03-26 | Metal Coatings International, Inc. | Particulate metal alloy coating for providing corrosion protection |
US7264661B2 (en) | 2001-02-14 | 2007-09-04 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US7078076B2 (en) | 2001-02-14 | 2006-07-18 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US20060208226A1 (en) * | 2001-02-14 | 2006-09-21 | Metal Coatings International Inc. | Particulate metal alloy coating for providing corrosion protection |
US20040191555A1 (en) * | 2003-02-06 | 2004-09-30 | Metal Coatings International Inc. | Coating systems having an anti-corrosion layer and a powder coating layer |
US6960247B2 (en) | 2003-07-22 | 2005-11-01 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
US20050027056A1 (en) * | 2003-07-22 | 2005-02-03 | Hoden Seimitsu Kako Kenyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
EP1500686A1 (en) | 2003-07-22 | 2005-01-26 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
US20050256658A1 (en) * | 2004-05-12 | 2005-11-17 | Anderson Keith F | Multi-port scattering parameter calibration system and method |
WO2012003843A1 (en) | 2010-07-05 | 2012-01-12 | Holger Blum | Polyurethane coating agent |
US9266992B2 (en) | 2010-07-05 | 2016-02-23 | Holger Blum | Polyurethane coating agent |
CN106221345A (en) * | 2016-08-08 | 2016-12-14 | 常熟市常力紧固件有限公司 | A kind of corrosion-resistant bolt of car shock mitigation system |
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