WO2008151173A1 - Deposition of metal ions onto surfaces of conductive substrates - Google Patents

Deposition of metal ions onto surfaces of conductive substrates Download PDF

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Publication number
WO2008151173A1
WO2008151173A1 PCT/US2008/065602 US2008065602W WO2008151173A1 WO 2008151173 A1 WO2008151173 A1 WO 2008151173A1 US 2008065602 W US2008065602 W US 2008065602W WO 2008151173 A1 WO2008151173 A1 WO 2008151173A1
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Prior art keywords
hydroxide
solution
metal
water
alkali metal
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PCT/US2008/065602
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English (en)
French (fr)
Inventor
Frank G. Defalco
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Dfhs, Llc
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Application filed by Dfhs, Llc filed Critical Dfhs, Llc
Priority to MX2009013100A priority Critical patent/MX2009013100A/es
Priority to JP2010511270A priority patent/JP5722032B2/ja
Priority to KR1020107000045A priority patent/KR101506360B1/ko
Priority to CA2689437A priority patent/CA2689437A1/en
Priority to BRPI0811366-1A priority patent/BRPI0811366A2/pt
Priority to RU2009145641/02A priority patent/RU2486284C2/ru
Priority to AU2008259858A priority patent/AU2008259858B2/en
Priority to EP08770009.2A priority patent/EP2155927A4/en
Priority to CN200880023345A priority patent/CN101730756A/zh
Publication of WO2008151173A1 publication Critical patent/WO2008151173A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • 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
    • C23C22/02—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 non-aqueous solutions
    • C23C22/03—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 non-aqueous solutions containing phosphorus compounds
    • 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
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates

Definitions

  • the present invention relates to compositions and processes for coating metals and, more particularly, to aqueous compositions of metals for coating metal surfaces, and processes for making these aqueous compositions.
  • Electroplated deposits on a substrate surface do not go into the metal interstices of the surface. As a result the deposits are not tenacious enough to maintain their integrity when the substrate is "cold worked" to yield point. Zinc electrodeposits are destroyed by cold working at 61,000 PSI, cadmium at 69,000 PSI, while the steel substrate will have a yield point of 80,000 PSI or stronger.
  • Electroplating requires procedures for pretreatment, pre-cleaning, and rinsing controlled plating baths, and special anodes. Electroplating generally follows the rules of the Electromotive Series that a more noble metal can be plated on a less noble metal, but not the reverse direction. This limits the ability to plate all the metals in the periodic table onto other metal substrates in the periodic table.
  • Phosphate conversion surfaces are widely used for corrosion inhibition and as a base for paints.
  • Phosphating is one of the most widely used techniques in the commercial world with major uses in the auto industry as an undercoat to inhibit corrosion and as an anchor to retain paint.
  • Conversion coating phosphating methods require large plating baths and are energy intensive and time consuming. Phosphating requires at least ten minutes or longer to get a commercially acceptable, adherent conversion surface.
  • the industry has developed many accelerants over the years to speed up the conversion process. In the latter part of the 20 th century, new and exotic techniques were developed to obtain better surfaces on metals.
  • These methods modified the metals with a coating on a substrate by vapor deposition techniques such as vacuum evaporation, sputtering, magnetron sputtering, or ion plating. These techniques can be used to harden metal surfaces such as metal working tools including tungsten carbide inserts, drills, hobbs, etc. Chemical vapor deposition is applied in a vacuum chamber and the metal is ionized in a nitrogen atmosphere and deposited on and diffuses into the substrates. Some examples of the results of these techniques are titanium nitride and boron nitrides. The deposition is generally by line of sight and the process is limited to the shape, size and configuration of the substrate metals. This process is expensive, requiring special equipment and high energy usage.
  • the deposits are formed under exacting conditions of temperature, gas composition, etc. These techniques result in deposits that have dense, smooth, defect free surfaces useful for many commercial products.
  • Many metals form a passive oxide surface that is beneficial in protecting the metal from corrosion. Such metals are aluminum and stainless steels and titaniums.
  • the oxide film that forms on stainless steel is a mono-molecular layer that renders the surface passive.
  • the oxide layer that forms on carbon steel is deleterious to the metal and is called rust.
  • U.S. Patent 6755917 issued to Hardin, et al. describes a solution for providing conversion coating on the surface of a metallic material. The solution includes a peroxidic species and is limited to at least one metal from Group IB, HB, IVA, VA, VIA and VIII of the periodic table.
  • Hardin also provides a liquid acidic aqueous concentrate for the replenishing of a conversion coating solution according to the invention, wherein the concentrate contains rare earth ions (as herein defined) and monovalent anions in a molar ratio of total rare earth ions: monovalent anions of from 1 :200 to 1 :6 and/or rare earth ions and divalent anions in a molar ratio of total rare earth ions:divalent anions of from 1:100 to 1 :3 and/or the concentrate contains at least one metal selected from Groups IB, HB, IVA, VA, VIA and VII, preferably from the group of Cu, Ag, Au, Cd, Hg, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Sn, Pb, Sb, Bi, Se and Te and anions such that the molar ratio of the sum of the elements in this group: anions is in the range from 1:50 to 1:10,000.
  • rare earth ions as herein defined
  • monovalent anions in
  • Hardin methods are limited to an acidic aqueous solution. It is known that thin mono-molecular oxide films present on stainless steel can provide an excellent passivation surface to metals. It has been theorized that corrosion may one day be conquered by a thin molecular layer on metal surfaces. It has been further theorized that significant reductions in friction could be obtained with thin, tenacious metallic films. In the October 1996 issue of Scientific American, Jacqueline Krim, PhD, published a paper titled "Friction at the Atomic Scale”.
  • US Patent 7087104 issued to Choi et al. describes a system and method for storing a solution containing a subset of a group consisting of a metal ion, a complexing agent, an ammonium salt, and a strong base. Near the time of use, the solution is used to form an electroless deposition solution containing the entire group.
  • the metal ion includes a cobalt ion
  • the complexing agent includes citric acid
  • the ammonium salt includes ammonium chloride
  • the strong base includes tetramethylammonium hydroxide.
  • the base solution is prepared and then set aside for 2 days to allow for stabilization prior to use. Another solution has to be prepared and then mixed with the first solution just prior to use in a plating bath. This requires complex logistics and skilled operators to make the final preparation at the plant bath site.
  • US Patent 5340788 issued to Defalco, et al. discloses a method for preparing an oil additive that is applied to parts of internal combustion engines using the lubricating oil as the carrier fluid.
  • the solution is mixed with a polyethylene glycol for introduction into the lubricating oil.
  • the present invention provides compositions and processes for preparing metallic ions for deposition on and/or into conductive substrates, such as metals, to substantially eliminate friction from metal to metal contact. It is used in the aqueous embodiment to form new metal surfaces on all metal substrates.
  • the processes form stable aqueous solutions of metal and metalloid ions that can be adsorbed or absorbed on and/or into conductive substrates.
  • the aqueous solutions consist of ammonium alkali metal phosphate salts, and/or ammonium alkali metal sulfate salts mixed with a water soluble metal or metalloid salt from Group I through Group VIII of the periodic table of elements.
  • aqueous solutions allow for a nano deposition of the metal ions on and/or into the surfaces of conductive substrates.
  • the surfaces created by the deposited metal ions will provide metal passivation and substantially eliminate friction in metal-to-metal contact without the use of hydrocarbon based lubricants.
  • the process of the present invention for the production of ion complexes is performed in an aqueous reaction medium, and the ion complexes are used as an aqueous solution in the forming of conversion surfaces on metallic objects.
  • the following reactants are required: (a) at least one water soluble non-alkaline metal salt selected from Groups I-VIII of the Periodic Table; (b) an alkali metal hydroxide; c) a sulfur-containing compound and/or a phosphorous containing compound, such as mineral acids; d) ammonium hydroxide; and e) water.
  • a parent solution A can be produced when the reactants orthophosphoric acid, water, ammonium hydroxide and an alkali metal hydroxide are mixed together. An exothermic reaction occurs and the temperature of the aqueous solution is approximately 100 0 C. A measured amount of a metallic salt such as silver nitrate, zinc oxide, aluminum salts such as aluminum sulfate, ammonium molybdate, ammonium tungstate or any water soluble metal salt can then be introduced into the reaction vessel, stirred and heated until the metallic salt is totally dissolved in the aqueous medium.
  • a parent solution B can be produced when the reactants sulfuric acid, water, ammonium hydroxide and the alkali metal hydroxide are mixed together.
  • the alkali metal hydroxide can be any hydroxide of a metal in Group IA of the Periodic Table, principally sodium hydroxide, potassium hydroxide, lithium hydroxide, with potassium hydroxide being the preferred reactant.
  • aqueous solutions of metals also deposit nitrogen on the surface of metals. Wear tests show that metal coatings created by application of the aqueous solutions reduce wear of metal as effectively as oil-based lubricants.
  • An advantage of the present invention is that the solution can be applied to any structure, regardless of configuration with none of the disadvantages and limitations of the current electroless, chemical vapor or electroplating technology in commercial use today. Another advantage is a ground stable solution that can be shipped to any location.
  • Another advantage is a simplified process using an aqueous solution for forming a conversion coating on a metallic material.
  • Another advantage is the creation of an oxide free conversion surface to all metallic substrates.
  • Fig. 1 shows deposits of silver-phosphorous-potassium on stainless steel.
  • Fig. 2 shows deposit of silicon-phosphorous- potassium on aluminum.
  • Fig. 3 shows deposit of silicon-phosphorous-potassium on stainless steel.
  • Fig. 4 shows deposit of zinc-phosphorous-potassium on aluminum.
  • Fig. 5 shows deposit of aluminum-phosphorous-potassium on 1010 carbon steel.
  • Fig. 6 shows deposit of copper-phosphorous-potassium on 1010 carbon steel.
  • Fig. 7 shows deposit of molybdenum-phosphorous-potassium on 1010 carbon steel.
  • Fig. 8 shows deposit of molybdenum-phosphorous-potassium on stainless steel.
  • Fig. 9 shows deposit of silicon-phosphorous-potassium on 1010 carbon steel panel deposited from oil phase.
  • Fig. 10 shows the thickness of a boron coating on aluminum from scanning electron microscope images.
  • Fig. 11 shows the thickness of a molybdenum coating on aluminum from scanning electron microscope images.
  • Fig. 12 shows the presence of nitrogen-silicon-potassium on 1010 carbon steel in EDAX chart I.
  • Fig. 13 shows the presence of nitrogen-silicon-potassium on aluminum in
  • Fig 14 shows the presence of nitrogen-silicon-potassium on stainless steel in EDAX chart III.
  • Ionic photo stable silver can be achieved only through expensive techniques by ion sputtering, as described in US Patent 5,985,308 or by methods described in US Patent 6897349 involved with complexing with different solvents such as alcohols and a chloride anion donating compound.
  • Ionic Silver has been the subject of much research. Although there are many known methods of stabilizing ionic silver, none of these use an aqueous solution. Deposition of an adherent silver surface on metallic pieces by mere immersion, brushing, or spraying would be of great value. Ionic silver that is stable in aqueous solution would have wide applications in electronics and in medicine, for example, for its antimicrobial properties in bandages for wound healing and for forming an anti-microbial surface on medical instruments.
  • the present invention does not require the use of applied external electromotive force, but forms a thin tenacious metallic film on substrates by mere immersion, brushing or spraying.
  • the surprising finding of this invention is that the new conversion surface can be made to deposit in a monomolecular layer onto and into the substrate. Most plating specifications require thickness of the deposits of one mil (23-24 microns).
  • the present invention provides permanent thin films on conductive substrates, from 0.05 to 10 microns thickness.
  • the process of the present invention for the production of ion complexes is performed in an aqueous reaction medium, and the ion complexes are used as an aqueous solution in the forming of conversion surfaces on metallic objects.
  • the following reactants are required: a) at least one water soluble non-alkaline metal salt selected from Groups I-VIII of the Periodic Table; b) an alkali metal hydroxide; c) a sulfur-containing compound and/or a phosphorous containing compound, such as mineral acids; d) ammonium hydroxide; and e) water.
  • the non-alkaline metal salt reactant may be from any non-alkaline metal of Groups I- VIII of the Periodic Table.
  • Non-limiting examples of applicable non-alkaline water soluble metals salts include those derived from: Group I-B: copper, silver, gold; Group H-A: beryllium, magnesium; Group H-B: zinc, cadmium; Group III-A: aluminum, gallium, indium; Group IV-A: silicon, tin, lead; Group IV-B: titanium, zirconium, hafnium; Group V-A: antimony, bismuth; Group V-B: vanadium, niobium, tantalum; Group VI-A: selenium, tellurium; Group VI-B: chromium, molybdenum, tungsten; Group VII-B: manganese; and Group VIII: iron, cobalt, nickel, palladium rhodium.
  • non-alkaline metal of Groups I- VIII of the Periodic Table is meant to embrace any and all of the above and equivalent metals, including silicon.
  • non-alkaline metal of Groups I- VIII of the Periodic Table does not embrace the alkali metals of Group I-A.
  • the alkaline earth metals, calcium, strontium, and barium of Group H-A are similarly not within the scope of the term.
  • beryllium and magnesium of Group II-A can be applicably employed in the practice of this invention and these metals also fall within the scope of the expression "non-alkaline metal of Groups I- VIII of the Periodic Table" as used herein. Combinations of the non-alkaline metal salts may also be used.
  • a parent solution A can be produced when the reactants orthophosphoric acid, water, ammonium hydroxide and an alkali metal hydroxide are mixed together. An exothermic reaction occurs and the temperature of the aqueous solution is approximately 100 0 C. A measured amount of a metallic salt such as silver nitrate, zinc oxide, aluminum salts such as aluminum sulfate, ammonium molybdate, ammonium tungstate or any water soluble metal salt can then be introduced into the reaction vessel, stirred and heated until the metallic salt is totally dissolved in the aqueous medium.
  • a metallic salt such as silver nitrate, zinc oxide, aluminum salts such as aluminum sulfate, ammonium molybdate, ammonium tungstate or any water soluble metal salt
  • the alkali metal hydroxide can be any hydroxide of a metal in Group IA of the Periodic Table, principally sodium hydroxide, potassium hydroxide, lithium hydroxide, with potassium hydroxide being the preferred reactant. Combinations of these alkali metal hydroxides may also be used.
  • Into a reaction vessel add about 0.5 to 1.5 liters, preferably about 1.0 liter, of water and about 0.5 to 1.5 liters, preferably about 1.0 liter, of orthophosphoric acid, about 75% to 85%, preferably about 80%, by volume. Then add about 0.5 to 1.5 liters, preferably about 1.0 liter, of ammonium hydroxide, about 15-35%, preferably about 26%, by volume. Then add about 0.5 to 1.5 liters, preferably about 1.0 liter, of potassium hydroxide, about 20-60%, preferably about 49%, by volume.
  • a parent solution B can be produced when the reactants sulfuric acid, water, ammonium hydroxide and the alkali metal hydroxide are mixed together. An exothermic reaction occurs and the temperature of the aqueous solution is approximately 100 0 C. A measured amount of a non-alkaline metal salt, such as boric acid, or copper sulfate, or ammonium molydate can then be introduced into the reaction vessel and dissolved. The metallic ions then become soluble in the aqueous solution and do not precipitate and remain stable.
  • the alkali metal hydroxide can be any hydroxide of a metal in Group IA of the Periodic Table, principally sodium hydroxide, potassium hydroxide, lithium hydroxide, with potassium hydroxide being the preferred reactant. Combinations of these alkali metal hydroxides may also be used.
  • Into a reaction vessel add about 1 to 3 liters, preferably about 2 liters, of water and about 0.5 to 1.5 liters, preferably about 1 liter, of concentrated sulfuric acid. Then add about 0.5 to 1.5 liters, preferably about 1 liter, of ammonium hydroxide, about 15-35%, preferably about 26%, by volume. Then add about 0.5 to 1.5 liters, preferably about 1.0 liter, of potassium hydroxide, about 20-60%, preferably about 49%, by volume. Care must be taken as the reaction is highly exothermic.
  • the present process of silver deposition can be performed without the presence of cyanide and applied external electromotive force to produce a tenacious non-immersion deposit.
  • the silver nitrate solution can be placed in a glass container and exposed to sunlight for several weeks. The silver does not become photosensitive, indicating that silver can be stabilized by the inexpensive process of the present invention which would be widely useful in areas such as antimicrobial activity and protection of the surfaces of medical instruments.
  • a 2"X2' sheet of Alcoa aluminum foil wrap can be contacted with the silver nitrate solution and then rubbed into the surface. The surface of the aluminum foil will be coated with a film of silver.
  • a 410 stainless steel coupon can be immersed in the silver nitrate solution for one minute. A thin tenacious film of silver will be formed on the stainless steel.
  • a cotton gauze bandage can be immersed in the silver solution and then exposed to sunlight for several days.
  • the bandage will not turn black as expected when ionic silver is exposed to sunlight, indicating the usefulness of the treated bandage use as an anti-microbial bandage for health and wound healing.
  • the gauze treated bandage can be subjected to a flame from a propane torch. The cotton will be charred when in direct contact with the flame tip, but the gauze does not ignite, indicating a use of the silver solution as a flame retardant for fabrics.
  • Example of an ammonium molvbdate Parent Solution A Using about 80 to 120 ml, preferably about 100 ml, of Parent solution A add about 0.1-10 grams, preferably about 1 gram, of ammonium molybdate to the solution. Stir and heat until the ammonium molybdate is completely dissolved. Immerse a 1010 steel coupon in the solution for one minute. A thin, tenacious film of molybdenum is formed on the steel coupon. A strip of aluminum foil 2"X2" was immersed in the solution for 30 seconds. A thin deposit of molybdenum formed on the aluminum coupon.
  • a standard ASTM test for an adherent deposit is to place plastic adhesive tape on the plated surface and pull the tape. If the deposit is an immersion deposit, the copper will peel off with the tape. If the deposit is adherent, then the copper will not peel off with the plastic adhesive tape. When plastic adhesive tape was applied to the copper surface in this example, the copper film remained adherent.
  • Parent solution B Using about 80 to 120 ml, preferably about 100 ml, of Parent solution B add about 0.1-10 grams, preferably about 2 grams, of aluminum sulfate to the solution. Stir and heat the solution until completely dissolved. Immerse a coupon of 1010 steel in the solution for 1 minute. A thin, tenacious, shiny adherent film of aluminum is formed on the steel coupon.
  • Parent solution B Using about 80 to 120 ml, preferably about 100 ml, of Parent solution B add about 0.1-10 grams, preferably about 2 grams, of boric acid to the solution. Stir and heat until completely dissolved. Immerse a 1010 steel coupon in the solution for one minute. A thin, tenacious bright film of boron is formed on the steel coupon. A coupon of aluminum foil 2"X2" was immersed in the solution. A thin film of boron formed on the aluminum. A stainless steel coupon was immersed in the solution and a thin metallic film of boron formed on the stainless steel.
  • Example of an ammonium tungstate Parent Solution B Using about 80 to 120 ml, preferably about 100 ml, of Parent solution B add
  • This solution can be misted into a hydrocarbon stream such as natural gas or vaporized gasoline in an internal combustion engine to enhance fuel combustion.
  • the solution may be misted into the air intakes of internal combustion engines to increase the volume of air available for combustion to enhance fuel economy.
  • tungsten has catalytic properties. Any metal such as platinum, iron, etc, that has catalytic properties can be used by this technique for manufacturing a fuel and lubricant additive.
  • the metal ion solutions were chosen to show that any metal ion produced by this invention can be deposited on and into various metal substrates, resulting in new metallic surfaces heretofore unknown.
  • the metal ion solutions were prepared according to parent solution A. Samples were not pretreated to remove oxides, soils, rust or oils, but were immersed for 30 seconds each at ambient conditions and dried using ambient air and a paper towel. Samples were then examined by EDS (Electron dispersive spectroscopy) by Vista Engineering of Birmingham, Alabama, US. These results are as shown on the analytical charts in Figs 1-9. Fig.
  • Fig. 1 shows deposits of silver-phosphorous-potassium on stainless steel.
  • Fig. 2 shows deposit of silicon-phosphorous- potassium on aluminum.
  • Fig. 3 shows deposit of silicon- phosphorous-potassium on stainless steel.
  • Fig. 4 shows deposit of zinc- phosphorous-potassium on aluminum.
  • Fig. 5 shows deposit of aluminum- phosphorous-potassium on 1010 carbon steel.
  • Fig. 6 shows deposit of copper- phosphorous-potassium on 1010 carbon steel.
  • Fig. 7 shows deposit of molybdenum-phosphorous-potassium on 1010 carbon steel.
  • Fig. 8 shows deposit of molybdenum-phosphorous-potassium on stainless steel.
  • Fig. 9 shows deposit of silicon-phosphorous-potassium on 1010 carbon steel panel deposited from oil phase.
  • Wear testing was run on a dry film coating of the present invention, in comparison with a standard oil-based lubricant at Engineered Lubricants, Maryland Heights, Mo. On an Epsilon Linear Precision Test Machine, Tribology Testing Equipment.
  • the machine is used to evaluate wear and extreme pressure properties of fluids and greases.
  • the machine has the ability to evaluate the rate of wear throughout the test duration and compare wear in real time to all other indicated variables such as torque, friction, coefficient of friction, load specimen, RPM, specimen temperature, fluid temperature, specimen cycles, and test duration.
  • Stainless steel pins and V Bars were used with the pins rotating against the V Bars under conditions up to 4,000 psi. The heat generated in the oil during the test is drawn off continuously.
  • a stainless steel pin and V block were run in standard lubricating oil for 50 minutes. Wear was continuously recorded.
  • a IA stainless steel pin V block were immersed in the aqueous silicon/phosphate solution of the present invention for one minute, extracted and mailed to the testing laboratory. The wear test was run with the pre-coated pin and block for 50 minutes. The test results showed that wear using the oil-based lubricant and the dry film of the present invention were identical with 0.06 of an inch wear pattern. Thus, the dry film of silicon/phosphorous of the present invention has the same wear pattern as that observed using a standard lubricant.
  • the foregoing description has been limited to specific embodiments of this invention. It will be apparent, however, that variations and modifications may be made by those skilled in the art to the disclosed embodiments of the invention, with the attainment of some of all of its advantages and without departing from the spirit and scope of the present invention.
  • the present invention is not limited to the metals listed above, but is inclusive of all metals, including refractory metals.
  • the solutions do not require the use of a peroxidic compound, a rare earth or an accelerator additive.
  • the pH can be acidic, or neutral or alkaline depending upon which pH is the best solution for deposition of the ions for conversion surfaces. Further, the solution can be applied at ambient temperature without the pre-treatment and pre-cleaning steps required in the Hardin process.
  • the solution can be applied to standing objects such as bridges, overpasses and other metallic structures in situ. These methods of application for forming conversion surfaces greatly decrease costs and allow for passivation of metal structures already built. Other metal surface techniques include pinging, glass beading, galvanizing.

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PCT/US2008/065602 2007-06-05 2008-06-03 Deposition of metal ions onto surfaces of conductive substrates WO2008151173A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
MX2009013100A MX2009013100A (es) 2007-06-05 2008-06-03 Deposicion de iones metalicos encima de las superficies de substratos conductores.
JP2010511270A JP5722032B2 (ja) 2007-06-05 2008-06-03 導電性基板の面への金属イオンの析出
KR1020107000045A KR101506360B1 (ko) 2007-06-05 2008-06-03 전도성 기판의 표면상에 금속 이온의 증착
CA2689437A CA2689437A1 (en) 2007-06-05 2008-06-03 Deposition of metal ions onto surfaces of conductive substrates
BRPI0811366-1A BRPI0811366A2 (pt) 2007-06-05 2008-06-03 "processo para a produção de soluções aquosas de metais não alcalinos para deposição em superfícies, composição aquosa de um sal de metal não alcalino e processo para a deposição permanente de um metal não alcalino na superfície de um metal recipiente"
RU2009145641/02A RU2486284C2 (ru) 2007-06-05 2008-06-03 Осаждение ионов металлов на поверхности электропроводных подложек
AU2008259858A AU2008259858B2 (en) 2007-06-05 2008-06-03 Deposition of metal ions onto surfaces of conductive substrates
EP08770009.2A EP2155927A4 (en) 2007-06-05 2008-06-03 DEPOSITION OF METALLIC IONS ON SURFACES OF CONDUCTIVE SUBSTRATES
CN200880023345A CN101730756A (zh) 2007-06-05 2008-06-03 金属离子在导电基材表面上的沉积

Applications Claiming Priority (4)

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US93324207P 2007-06-05 2007-06-05
US60/933,242 2007-06-05
US12/025,506 US20080302267A1 (en) 2007-06-05 2008-02-04 Compositions and processes for deposition of metal ions onto surfaces of conductive substrates
US12/025,506 2008-02-04

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EP (1) EP2155927A4 (enrdf_load_stackoverflow)
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BR (1) BRPI0811366A2 (enrdf_load_stackoverflow)
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US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions

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US6863825B2 (en) 2003-01-29 2005-03-08 Union Oil Company Of California Process for removing arsenic from aqueous streams
US8066874B2 (en) 2006-12-28 2011-11-29 Molycorp Minerals, Llc Apparatus for treating a flow of an aqueous solution containing arsenic
US8317909B2 (en) * 2007-06-05 2012-11-27 Dfhs, Llc Compositions and processes for deposition of metal ions onto surfaces of conductive substrates
US20080302267A1 (en) 2007-06-05 2008-12-11 Defalco Frank G Compositions and processes for deposition of metal ions onto surfaces of conductive substrates
US8252087B2 (en) 2007-10-31 2012-08-28 Molycorp Minerals, Llc Process and apparatus for treating a gas containing a contaminant
US8349764B2 (en) 2007-10-31 2013-01-08 Molycorp Minerals, Llc Composition for treating a fluid
US8563487B1 (en) 2009-12-09 2013-10-22 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings
US8252734B1 (en) 2009-12-09 2012-08-28 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Friction modifier using adherent metallic multilayered or mixed element layer conversion coatings
US8420582B2 (en) * 2011-02-15 2013-04-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Friction and wear modifiers using solvent partitioning of hydrophilic surface-interactive chemicals contained in boundary layer-targeted emulsions
US9023773B1 (en) 2011-02-15 2015-05-05 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Friction and wear management using solvent partitioning of hydrophilic-surface-interactive chemicals contained in boundary layer-targeted emulsions
KR101678514B1 (ko) * 2015-08-31 2016-12-06 전북대학교산학협력단 실버 나노덴트라이트를 포함하는 셀룰로오스 박막 전극 및 그 제조방법
CN108474118B (zh) * 2016-01-19 2020-05-08 蒂森克虏伯钢铁欧洲股份公司 具有Zn镀层和施加在其上的摩擦作用层的钢产品的生产方法以及相应所得的钢产品
CN114083230A (zh) * 2021-11-05 2022-02-25 徐州万达回转支承有限公司 一种用于齿面自润滑的新型回转支承及其制备方法

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US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
US10577259B2 (en) 2014-03-07 2020-03-03 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions

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EP2155927A4 (en) 2016-01-13
JP2014159643A (ja) 2014-09-04
RU2486284C2 (ru) 2013-06-27
RU2009145641A (ru) 2011-07-20
JP2010529299A (ja) 2010-08-26
EP2155927A1 (en) 2010-02-24
JP5926317B2 (ja) 2016-05-25
KR101506360B1 (ko) 2015-03-26
CN101730756A (zh) 2010-06-09
AU2008259858B2 (en) 2013-01-24
KR20100040832A (ko) 2010-04-21
JP5722032B2 (ja) 2015-05-20
CA2689437A1 (en) 2008-12-11
BRPI0811366A2 (pt) 2015-06-23
MX2009013100A (es) 2010-08-18
AU2008259858A1 (en) 2008-12-11
US20080302267A1 (en) 2008-12-11

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