CN101730756A - deposition of metal ions onto surfaces of conductive substrates - Google Patents
deposition of metal ions onto surfaces of conductive substrates Download PDFInfo
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- CN101730756A CN101730756A CN200880023345A CN200880023345A CN101730756A CN 101730756 A CN101730756 A CN 101730756A CN 200880023345 A CN200880023345 A CN 200880023345A CN 200880023345 A CN200880023345 A CN 200880023345A CN 101730756 A CN101730756 A CN 101730756A
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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
- C23C22/40—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
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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
- 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
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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
- C23C22/02—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
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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
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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
- C23C22/07—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
Abstract
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. The 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.
Description
Technical field
The present invention relates to be used for the composition and the technology of metallizing, and more particularly, relate to the aqueous composition and the technology that is used to prepare these aqueous compositions of the metal that is used for coating metal surfaces.
Background technology
Having developed many methods to form new conversion surfaces on such as the commercial metal of ferrous metal, steel, stainless steel, aluminium, zinc and titanium.These methods comprise plating, phosphatization (conversion surfaces), chemical vapour deposition, ion sputtering and other technologies.Britain in 1870 have proposed the early stage electrochemical plating of silver.Afterwards, the plating precious metal had been proposed, i.e. the method for copper and gold.These metals must with the prussiate complexing on substrate material, to form adherent settling.Use prussiate to remain the preferred method that on base material, forms the initial adhesion deposition thing of precious metal.Prussiate is the extremely strong material of a kind of toxicity, and its harm environment also threatens public health.Must take many security measuress when using prussiate, nonetheless, user's deleterious flue gas that still may incur danger.Along with the electroplating technology years of development, the technology of other elements of plating such as zinc, cadmium, nickel and chromium has all obtained development, and is widely used in engineering and decorative purpose in business circles.
The electroplating sediment of substrate surface can not enter in the metal gap on surface.Therefore, when base material was arrived yield-point by " cold working ", sedimental clinging power was not enough to keep its integrity.61, carry out the electrodeposit that cold working has destroyed zinc under the 000PSI, cadmium is 69,000PSI, and steel substrate will have 80,000PSI or stronger yield-point.This is a problem deserving of attention in the electroplating industry always.The plating personnel must handle many different parameters to set up the net result that effective deposition step reaches expectation.Electroplate the step that needs pre-treatment, pre-washing and the plating bath of rinsing control and special anode are arranged.Electroplate and follow the electromotive series rule usually, promptly more expensive metal can be electroplated onto on the inferior expensive metal, but opposite direction is not all right.This has limited the ability on other metal bases in the periodic table of elements of all Metal platings in the periodic table of elements.
The another kind of method of surface modification is a phosphatization, wherein, has formed iron-phosphate conversion surfaces on steel and aluminium.Iron-phosphate conversion surfaces is widely used in suppressing corroding and as the substrate of paint.Phosphatization is one of most widely used technology in the business circles, is applied to automotive industry mainly as undercoat and suppresses corrosion and keep paint as fixture.
The conversion coating method for bonderizing needs huge plating bath, and be energy-intensive and consuming time.Phosphatization needed 10 minutes at least or the longer time obtains commercial acceptable, adherent conversion surfaces.The sector has been developed many promotor for many years and has been quickened conversion process.
The second half in 20th century, developed new better surperficial on metal, to obtain with external technology.These methods form coating by the gas phase deposition technology such as vacuum-evaporation, sputter, magnetron sputtering or ion plating and come modified metal on base material.These technology can be used for the surface, hardening metal, such as the metal machining tool, comprise tungsten carbide blade, drill bit, hobboing cutter etc.Chemical vapour deposition is carried out in vacuum chamber, and metal is ionized in nitrogen atmosphere, and deposits on the base material and diffuse in the base material.Some examples of the result of these technology are titanium nitride and boron nitride.Deposition is normally carried out according to sight line, and technology is subject to shape, size and the configuration of substrate metal.This technology is expensive, needs special equipment and high energy consumption.Settling forms under the condition of strictnesses such as temperature, gas composition.These technology cause settling to have being applied to closely knit, smooth, the flawless surface of many commerical prods.
Many metals have formed and have benefited the passivating oxide surface that prevents metallic corrosion.Such metal is aluminium, stainless steel and titanium.The oxide film that is formed on the stainless steel is the unimolecular layer that makes surface passivation.The zone of oxidation that is formed on the carbon steel is harmful to metal, and is called as iron rust.
The United States Patent (USP) that licenses to people such as Hardin has been described a kind of solution that is used for providing conversion coating on metal material surface No. 6755917.This solution comprises a kind of superoxide material, and is subject at least a in IB, IIB, IVA, VA, VIA and the VIII family metal in the periodic table of elements.Particularly, Hardin also provides a kind of acidic aqueous enriched material that is used for replenishing according to the liquid state of conversion coating solution of the present invention, wherein, enriched material comprises the total rare earth (TRE) ion: the mol ratio of monovalent anion is 1: 200 to 1: 6 rare earth ion (as definition herein) and a monovalent anion, and/or total rare earth (TRE) ion: the mol ratio of dianion is 1: 100 to 1: 3 rare earth ion and a dianion, and/or enriched material comprises and is selected from IB, IIB, IVA, VA, VIA and VII family, be preferably and be selected from Cu, Ag, Au, Cd, Hg, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Sn, Pb, Sb, Bi, at least a metal and the negatively charged ion of the group of Se and Te, make element summation in this group and anionic mol ratio at 1: 50 to 1: 10, in 000 the scope.And the method for Hardin is subject to acidic aqueous solution.
The thin unit molecule oxidation film that exists on the known stainless steel can provide splendid passive surface for metal.Corrosion may be conquered by the thin unimolecular layer on the metallic surface in some day, and this has become a kind of theory.Further think theoretically, can obtain significantly reduced friction by metallic membrane thin, that clinging power is strong.
Jacqueline doctor Krim has delivered the paper that is entitled as " friction of atomic scale " on the Scientific American (Scientific Beauty compatriots) of in October, 1996 distribution.The conclusion that her discovery draws is " on atomic level, not friction of metal to metal contact ".Many facts of taking it seriously have been queried in this surprising discovery, i.e. friction is a kind ofly only with lubricator to reduce by the metal condition that the heat that produced can be weakened of sliding on another kind of metal by making.Another surprising conclusion is, on atomic level, " sources of friction is from when the atomic lattice vibration during because of the slip effect setting in motion of the atom among the apparent surface near the atom on surface.These vibrations are real sound waves.Like this, make a surface some the required mechanical energy of on another surface, sliding be converted into acoustic energy, and finally be converted to heat." thermal conductance causes friction.In order to keep slip, must increase more mechanical energy.Krim points out that further " solid is only with some different frequency vibration, so the amount of mechanical energy depends on the actual frequency that excites.If the atom among the apparent surface and another surperficial frequency resonance then can cause friction.But,, then can not produce sound wave if any in the frequency on apparent surface and other surfaces self do not resonate.These characteristics have disclosed infusive possibility, and the very little solid that promptly has less relatively resonant frequency may show that almost frictionless slides.”
Another surprising result in the work of Krim is that dry film is more smooth than liquid membrane.This has overturned current cognition all about friction thought.The further testing authentication that other scientists carry out the metal to metal contact on the atomic level can eliminate friction, and liquid lubricant causes friction by " sticking/sliding " effect.Liquid will be bonded in the intrametallic gap, skid off then.This causes the vibration of lattice and produces sound wave that sound wave is converted to heat, thereby causes friction.
According to estimates, reduce that friction is annual can save up to 1.6% gross national product or above 2,000 hundred million dollars.Therefore, the technology of almost having eliminated the friction on the commercial metal will be new and useful, but but never available.Clearly, this technology has very big value, and it is independent to help country to seek the energy, and greatly reduces the cost that Infrastructure that the corrosion because of metal construction, underground pipeline, hold-up vessel, bridge and viaduct causes substitutes.
Iron-phosphate conversion surfaces is used for business equipment to reduce decibel level.The high-decibel level is the persistence harm of working space, and is detrimental to health, and causes early stage hearing loss.Often urge industry in manufacturing operation, to produce lower decibel level such as the government regulation mechanism of OSHA and EPA.Therefore, any conversion surfaces that reduces decibel level will help HUMAN HEALTH, and improve the working space environment.
The United States Patent (USP) that licenses to people such as Choi has been described a kind of system and method for storage solutions for No. 7087104, and this solution comprises the subclass of the group of being made up of metal ion, complexing agent, ammonium salt and highly basic.When soon using, solution is used to form the electroless deposition solution that comprises whole group.In one embodiment of the invention, metal ion comprises cobalt ion, and complexing agent comprises citric acid, and ammonium salt comprises ammonium chloride, and highly basic comprises Tetramethylammonium hydroxide.The preparation alkaline solution, and placed before use subsequently 2 days so that it is stable.Must prepare another kind of solution, and only before being used for plating bath, mix then with first kind of solution.This needs complicated logistics and skilled operator, to carry out final preparation at the plating bath place.
The United States Patent (USP) that licenses to people such as McCoy discloses the method for electrolyte that preparation is used for Metal plating and other purposes for No. 5310419.Find that use outside emf source, all metals in the periodic table of elements can both be by galvanic deposit on conductive base.
The United States Patent (USP) that licenses to people such as Defalco discloses for No. 5340788 and has adopted lubricating oil to prepare the method for the oil additive that is applied to internal combustion engine component as carrying object.Solution and polyoxyethylene glycol are mixed for being incorporated in the lubricating oil.
The disclosure of the Invention content
The invention provides to be used to prepare and deposit to such as on the conductive base of metal and/or be deposited into metal ion in the conductive base with the composition and the technology of the friction of eliminating metal to metal contact basically.The present invention uses in aqueous embodiment, to form new metallic surface on all metal bases.This technology has formed can adsorb or absorb on the conductive base and/or absorption or absorb metal ion in the conductive base and the stable aqueous solution of nonmetallic ion.This aqueous solution by with form to the water-soluble metal salt of group VIII or non-metal salt blended ammonium alkali metal phosphoric acid salt and/or ammonium alkali metal vitriol from the I family of the periodic table of elements.Aqueous solution allows the metal ion nano-precipitation to surfaces of conductive substrates and/or in the surfaces of conductive substrates.The surface that is formed by deposited metal ions will provide metal passivation, and eliminate the friction in the metal to metal contact basically, and need not to use the lubricant based on hydrocarbon.
The technology that is used for producing ionic complex of the present invention is carried out at water-containing reacting medium, and is used as aqueous solution in the conversion surfaces of ionic complex on forming metal object.In order to prepare the mineral ion complex compound, need following reactant: at least a water-soluble non-an alkali metal salt that (a) is selected from the I-VIII family of the periodic table of elements; (b) alkali metal hydroxide; (c) sulfocompound and/or P contained compound are such as mineral acid; (d) ammonium hydroxide; And (e) water.When mixing, reactant ortho-phosphoric acid, water, ammonium hydroxide and alkali metal hydroxide can produce mother solution A.Thermopositive reaction takes place, and the temperature of aqueous solution is about 100 ℃.The metal-salt of measuring vol can be incorporated in the reaction vessel afterwards, stir and heating, be dissolved in the water-bearing media metal-salt such as Silver Nitrate, zinc oxide, aluminium salt, ammonium molybdate, ammonium tungstate or any water-soluble metal salt fully such as Tai-Ace S 150 up to metal-salt.When mixing, reactant sulfuric acid, water, ammonium hydroxide and alkali metal hydroxide can produce mother solution B.Thermopositive reaction takes place, and the temperature of aqueous solution is about 100 ℃.Afterwards, the metal-salt with measuring vol is incorporated into also dissolving in the reaction vessel, metal-salt such as boric acid or copper sulfate or ammonium molybdate.So metal ion is soluble, and can not precipitate and keep stable in aqueous solution.Alkali metal hydroxide can be any oxyhydroxide of metal in the IA family of the periodic table of elements, mainly contain sodium hydroxide, potassium hydroxide, lithium hydroxide, and potassium hydroxide is preferred reactant.
The aqueous solution of metal also deposits nitrogen on the metallic surface.Wearing test shows, by using the wearing and tearing that metallic coating that aqueous solution forms has alleviated metal, just as the lubricant based on oil effective.
Advantage of the present invention is that this solution can be applied on any structure, and does not consider configuration, and does not have the shortcoming and the limitation of existing electroless plating, chemical gas phase or the electroplating technology of current commercial use.
Another advantage is the solution that can be transported to the base fixed in any place.
Another advantage is to adopt aqueous solution to form the simplification technology of the conversion coating on the metallic substance.
Another advantage is the conversion surfaces that all metal bases has been formed oxide-free.
The accompanying drawing summary
Fig. 1 has shown the silver-phosphorus on the stainless steel-potassium settling.
Fig. 2 has shown the silicon-phosphorus on the aluminium-potassium settling.
Fig. 3 has shown the silicon-phosphorus on the stainless steel-potassium settling.
Fig. 4 has shown the zinc-phosphorus on the aluminium-potassium settling.
Fig. 5 has shown the aluminium-phosphorus-potassium settling on 1010 carbon steels.
Fig. 6 has shown the copper-phosphorus-potassium settling on 1010 carbon steels.
Fig. 7 has shown the molybdenum-phosphorus-potassium settling on 1010 carbon steels.
Fig. 8 has shown the molybdenum-phosphorus on the stainless steel-potassium settling.
Fig. 9 has shown by the silicon-phosphorus-potassium settling on sedimentary 1010 carbon steel sheet of oil phase.
Figure 10 has been shown the thickness of the boron coating on the aluminium by scanning electron microscope image.
Figure 11 has been shown the thickness of the molybdenum coating on the aluminium by scanning electron microscope image.
Figure 12 has shown on 1010 carbon steels in EDAX figure I and has had nitrogen-silicon-potassium.
Figure 13 has shown on the aluminium in EDAX figure II and has had nitrogen-silicon-potassium.
Figure 14 has shown on the stainless steel in EDAX figure III and has had nitrogen-silicon-potassium.
Implement optimal mode of the present invention
Though the preferred embodiments of the invention have been described in following description in detail, it should be understood that, the present invention is limited in its application to the configuration of the each several part that accompanying drawing explains and the details of layout, because the present invention can be other embodiments and can implement in a different manner.
Need a kind of cheap, effectively, the technology that is easy to use reduces the friction of the metal to metal on the atomic level.Surprisingly, when producing metal ion according to the present invention, the ion diffusion that is produced is gone in the metal gap.Surprisingly, the ion of generation is not followed the electromotive series rule, and promptly aluminium can be deposited on the ferrous metal, and this is that any previous document is unexpected.Surprisingly, the silver ions that the present invention produces keeps light stable in aqueous solution in the presence of sunlight.The stable ionization silver of light can only obtain by expensive technology, by ion sputtering, as United States Patent (USP) the 5th, describe in 985, No. 308, or the method by describing in No. the 6897349th, the United States Patent (USP), this method comprises the solvent that complexing is different, such as the compound of pure and mild supply chlorine negative ion.Ionization silver is the theme of a lot of researchs always.Though have the method for many known stabilizing ion silver, use aqueous solution without any a kind of method in this method.Only just on metal parts, deposit adherent silver surface and will have great value by submergence, brushing or spraying.In aqueous solution stable ionization silver will electronics and medical aspect have widely and use, for example because its antimicrobial characteristic is used for wound healing and forms antimicrobial surface on medicine equipment in bandage.
The present invention does not need to use the foreign electromotive force that applies, but only just forms the thin strong metallic membrane of clinging power by submergence, brushing or spraying on base material.Surprising discovery of the present invention is can prepare new conversion surfaces, to deposit to unimolecular layer on the base material and to deposit in the base material.It is 1 mil (23-24 micron) that most of electroplating standard requires thickness of deposits.The invention provides thickness on the conductive base and be 0.05 micron to 10 microns permanent film.
The technology that is used for producing ionic complex of the present invention is carried out at water-containing reacting medium, and during the conversion surfaces of ionic complex on forming metal object as aqueous solution.In order to prepare the mineral ion complex compound, need following reactant: at least a water-soluble non-an alkali metal salt that (a) is selected from the I-VIII family of the periodic table of elements; (b) alkali metal hydroxide; (c) sulfocompound and/or P contained compound, for example mineral acid; (d) ammonium hydroxide; And (e) water.
Non-an alkali metal salt reactant can be any non-basic metal from the I-VIII family of the periodic table of elements.Source metal that representational, the unrestriced example of non-buck soluble metal salts applicatory comprises is from I-B family: copper, silver, gold; II-A family: beryllium, magnesium; II-B family: zinc, cadmium; III-A family: aluminium, gallium, indium; IV-A family: silicon, tin, lead; IV-B family: titanium, zirconium, hafnium; V-A family: antimony, bismuth; V-B family: vanadium, niobium, tantalum; VI-A: selenium, tellurium; VI-B family: chromium, molybdenum, tungsten; VII-B family: manganese; And group VIII: iron, cobalt, nickel, palladium, rhodium.
Though silicon is considered to nonmetal and is not defined as metallic element usually as a member of IV-A family, silicon is in the method for the invention as non-basic metal.Therefore, the statement of " the non-basic metal of the I-VIII family of the periodic table of elements " means and comprises any and above all and metal that be equal to, comprises silicon.To recognize further that term " the non-basic metal of the I-VIII family of the periodic table of elements " does not comprise the basic metal of I-A.Similarly, the alkaline-earth metal of II-A family, calcium, strontium and barium be not all in the scope of this term.On the other hand, the beryllium of II-A family and magnesium can be adopted when of the present invention suitably implementing, and these metals have also fallen in the scope of statement of " the non-basic metal of the I-VIII family of the periodic table of elements " that herein adopts.Can also use the combination of non-an alkali metal salt.
When mixing, reactant ortho-phosphoric acid, water, ammonium hydroxide and alkali metal hydroxide can produce mother solution A.Thermopositive reaction takes place, and the temperature of aqueous solution is about 100 ℃.Afterwards, the metal-salt of measuring vol can be incorporated in the reaction vessel, stir and heating, be dissolved in the water-bearing media metal-salt such as Silver Nitrate, zinc oxide, aluminium salt, ammonium molybdate, ammonium tungstate or any water-soluble metal salt up to metal-salt fully such as Tai-Ace S 150.Alkali metal hydroxide can be any oxyhydroxide of metal in the IA family of the periodic table of elements, mainly contain sodium hydroxide, potassium hydroxide, lithium hydroxide, and potassium hydroxide is preferred reactant.Can also use the combination of these alkali metal hydroxides.
The preparation of mother solution A
In reaction vessel, add about 0.5 and be raised to 1.5 liters, be preferably about 1.0 liters water and about 0.5 and be raised to 1.5 liters, be preferably about 1.0 liters approximately by volume 75% to 85%, be preferably about 80% ortho-phosphoric acid.Then, add about 0.5 and be raised to 1.5 liters, be preferably about 1.0 liters about by volume 15%-35%, be preferably about 26% ammonium hydroxide.Then, add about 0.5 and be raised to 1.5 liters, be preferably about 1.0 liters about by volume 20%-60%, be preferably about 49% potassium hydroxide.
When mixing, reactant sulfuric acid, water, ammonium hydroxide and alkali metal hydroxide can produce mother solution B.Thermopositive reaction takes place, and the temperature of aqueous solution is about 100 ℃.Afterwards, the non-an alkali metal salt with measuring vol is incorporated into also dissolving in the reaction vessel, non-an alkali metal salt such as boric acid or copper sulfate or ammonium molybdate.So it is solvable that metal ion becomes, and can not precipitate and keep stable in aqueous solution.Alkali metal hydroxide can be any oxyhydroxide of metal in the IA family of the periodic table of elements, mainly contain sodium hydroxide, potassium hydroxide, lithium hydroxide, and potassium hydroxide is preferred reactant.Also can use the combination of these alkali metal hydroxides.
The preparation of mother solution B
In reaction vessel, add about 1 and be raised to 3 liters, be preferably about 2 liters water and about 0.5 and be raised to 1.5 liters, be preferably about 1 liter vitriol oil.Then, add about 0.5 and be raised to 1.5 liters, be preferably about 1 liter about by volume 15%-35%, be preferably about 26% ammonium hydroxide.Then, add about 0.5 and be raised to 1.5 liters, be preferably about 1.0 liters about by volume 20%-60%, be preferably about 49% potassium hydroxide.Must be careful, because reaction is the height heat release.
The example of Silver Nitrate mother solution A
Use about 80ml to 120ml, be preferably the mother solution A of about 100ml, with phosphoric acid with the pH regulator of solution to about 7.In solution, add about 0.1 gram-10 grams, be preferably the Silver Nitrate of about 1 gram.Stir and heating, the Silver Nitrate in solution dissolves fully.1010 steel samples are submerged in the silver nitrate solution 1 minute.Thin, silverskin that clinging power is strong, bright on the steel sample, have been formed.Use scanning electron microscope (SEM) to check this surface.Except the foreign electromotive force that uses cyanide solution and apply, also there is not known method on steel, to form the adhesion deposition thing of silver.This technology need not the existence of prussiate and foreign electromotive force that nothing applies just can carry out deposition of silver and produce the strong non-submergence settling of clinging power.Silver nitrate solution can be positioned in the Glass Containers and expose several weeks in the sun.Silver does not become light activated, and this shows that silver can be stabilized in cheap technology of the present invention, and the present invention will be widely used in the field such as anti-microbial activity and protection medical apparatus surface.U.S. aluminium (Alcoa) 2 " X2 ' aluminium foil packing thing sheet can contact with silver nitrate solution, and be rubbed in the surface then.Aluminium foil surface will be coated on silverskin.410 stainless steel samples can be submerged in the silver nitrate solution 1 minute.To form the thin strong silverskin of clinging power on the stainless steel.
The cotton gauze bandage can be submerged in the silver-colored solution, and be exposed to sunlight following a couple of days subsequently.When ionization silver was exposed to sunlight, bandage can be as blackening as the expection, and this shows that the bandage usefulness after the processing acts on the validity of the antimicrobial bandages of healthy and healing wounds.Gauze bandage after the processing can stand the flame of propane torch.When direct contact flame top, cotton can being burnt, but gauze can not lighted, this shows that silver-colored solution has been used as the fire retardant of fabric.
The example of ammonium molybdate mother solution A
Use about 80ml to 120ml, be preferably the mother solution A of about 100ml, with about 0.1 gram-10 grams, the ammonium molybdate that is preferably about 1 gram adds in this solution.Stir and heating, dissolve fully up to ammonium molybdate.1010 steel samples are submerged in the solution 1 minute.On the steel sample, formed the thin strong molybdenum film of clinging power of one deck.With aluminium foil 2 " X2 " band is submerged into 30 seconds in the solution.Formed the thin molybdenum settling of one deck on the aluminium sample.In " Electroplating (plating) ", Frederick A Lowenheim, McGraw Hill Book company has stated for the 141st page and " from their angle of electrode potential, should electroplate the metal such as tungsten and molybdenum from the aqueous solution of pH about 5.Even now (no matter claim herein), these metals can't precipitate from aqueous solution with pure form." like this, the invention provides the beyond thought method that on steel and other conductive bases, forms the molybdenum surface.
The example of ammonium tungstate mother solution A
Use about 80ml to 120ml, be preferably the mother solution A of about 100ml, with about 0.1 gram-10 grams, the ammonium tungstate that is preferably about 1 gram adds in this solution.Stir and heating, dissolve fully up to metal-salt.1010 steel bars are submerged in the solution 1 minute.On steel band, formed thin, the tungsten film bright, that clinging power is strong of one deck.The same with the example of molybdenum, the invention provides the beyond thought method that on steel, forms the tungsten surface.
The example of female copper sulfate mother solution B
Use about 80ml to 120ml, be preferably the mother solution B of about 100ml, with about 0.1 gram-10 grams, the copper sulfate that is preferably about 1 gram adds in this solution.Stir and heating, be dissolved in the solution fully up to metal-salt.1010 steel plates were submerged in the solution up to 2 minutes.Formed on the steel sample that one deck is adherent, the visible copper deposit.Unique practical methods that deposition adheres to copper coin on such as the reactive metal of zinc and steel is to use cyanide bath.Although paid the plating bath that many effort abandon containing prussiate because of environmental restraint, still do not develop the surrogate of the reality of copper cyanide bath.Known, the copper of cyanide-free and the foreign electromotive force that applies will form useless submergence settling.The standard A STM test that is used for the adhesion deposition thing is to place plastic adhesive tape and this band of tearing on plate surface.If settling is the submergence settling, then copper will be peeled off with band.If settling is adherent, copper will can not peeled off with plastic adhesive tape so.When plastic adhesive tape is applied to copper when surface among this embodiment, copper film keeps adhering to.
The example of Tai-Ace S 150 mother solution B
Use about 80ml to 120ml, be preferably the mother solution B of about 100ml, with about 0.1 gram-10 grams, the Tai-Ace S 150 that is preferably about 2 grams adds in this solution.Stir and heated solution, up to dissolving fully.1010 steel samples are submerged in the solution 1 minute.On the steel sample, formed thin, that clinging power is strong, the bright aluminium adhesive film of one deck.
The example of boric acid mother solution B
Use about 80ml to 120ml, be preferably the mother solution B of about 100ml, with about 0.1 gram-10 grams, the boric acid that is preferably about 2 grams adds in this solution.Stir and heating, up to dissolving fully.1010 steel samples are submerged in the solution 1 minute.On the steel sample, formed thin, the boron film that clinging power is strong, bright of one deck.With aluminium foil sample 2 " X2 " be submerged in the solution.On aluminium, formed the thin boron film of one deck.The stainless steel sample is submerged in the solution, then on stainless steel, has formed the thin metal boron film of one deck.
The example of ammonium tungstate mother solution B
Use about 80ml to 120ml, be preferably the mother solution B of about 100ml, 12% the ammonium tungstate by volume of 2ml is added in this solution.Stir and heating, up to dissolving fully.1010 steel samples are submerged in the solution 1 minute.On the steel surface, formed thin, the metal tungsten film that clinging power is strong, bright of one deck.
The example of the combination of mother solution A and mother solution B
The mother solution A of about 160ml and the mother solution B of about 40ml are combined.Improve the pH of solution by about by weight 49% the potassium hydroxide that adds about 10ml, make to be increased to be higher than 12 with the pH of solution after potassium hydroxide combines.Heating is also stirred, and dissolves fully up to potassium hydroxide.This solution can be atomized into hydrocarbon, such as the Sweet natural gas in the oil engine or gasification gasoline to strengthen fuel combustion.Solution can be atomized that air inlet port into oil engine can be used for the volume of incendiary air with increase and the saving that improves fuel.
The example of the oily derivative of the combination of mother solution A and ammonium tungstate mother solution B
The mother solution A of about 160ml and the ammonium tungstate mother solution B blend of about 40ml are in the same place.Use the height purified mineral oil of about 200ml, in mineral oil, be blended into the mother solution A of about 20ml (by volume 10%) and the mixing solutions of ammonium tungstate mother solution B.The dehydration of this oil solution is anhydrated to remove, and by elevated temperature to 100 ℃ with the deposited salt that comes up.When oil solution becomes bright and during clarification, makes oil cooling decanted oil then.Decant liquid can be used as oil additive subsequently or be used as fuel dope.As everyone knows, tungsten has catalysis characteristics.Any metal with catalysis characteristics such as platinum, iron etc. can be used to make fuel and lubricating oil additive in this technology.
The example of conversion surfaces
Select three kinds of substrate materials: the aluminium foil of U.S. aluminium production, 1010 carbon steels and 400 are stainless steel.These substrate metals of selecting have been represented the most widely used metal in the world.Any metal ion of selecting metal ion solution to produce with demonstration the present invention can be deposited on the different metal base material and in it, this brings unknown so far new metallic surface.A prepares metal ion solution according to mother solution.Sample is not removed the pre-treatment of oxide compound, dust, iron rust or oil, but makes 30 seconds of each submergence under envrionment conditions, and utilizes ambient air and paper towel dried.Pass through Vista Engineering ofBirmingham, Alabama, the EDS of US (electronic dispersion spectrum) sample for reference then.These results are presented on the analysis chart of Fig. 1-9.Fig. 1 has shown the silver-phosphorus on the stainless steel-potassium settling.Fig. 2 has shown the silicon-phosphorus on the aluminium-potassium settling.Fig. 3 has shown the silicon-phosphorus on the stainless steel-potassium settling.Fig. 4 has shown the zinc-phosphorus on the aluminium-potassium settling.Fig. 5 has shown the aluminium-phosphorus-potassium settling on 1010 carbon steels.Fig. 6 has shown the copper-phosphorus-potassium settling on 1010 carbon steels.Fig. 7 has shown the molybdenum-phosphorus-potassium settling on 1010 carbon steels.Fig. 8 has shown the molybdenum-phosphorus on the stainless steel-potassium settling.Fig. 9 has shown the silicon-phosphorus-potassium settling on sedimentary 1010 carbon steel sheet of oil phase.
Be applied to the example of thickness measurement of the metallic coating on aluminium surface
According to ammonium molybdate mother solution A and the boric acid mother solution B of preparing recited above.On the aluminium surface, use the coating of every kind of solution and make the coating drying.Adopt known scanning electron microscope technology to measure the thickness of aluminum coating in NASA Marshall flight center.Calculate the thickness of coating from scanning electron microscope image.The pictorial display of boron coating and is the image of molybdenum coating among Figure 11 in Figure 10.Contrast background 12, coating 10 is presented on the surface of aluminum metal 11.Carried out measuring several times along the length of coating 10.Mean thickness+the standard error of molybdenum coating is 1.32+0.11 micron (n=7), and that boron is 1.22+0.25 micron (n=4).
The example of nitrogen retention thing
According to present technology, nitrogen can only be deposited on the metal base by CVD (chemical vapour deposition), and this technology is the expensive and very limited method that forms nitride surface.Method of the present invention is also with nitrogen and treat that sedimentary metal deposits on the metal base together.The analysis ability of SEM is subject to elemental oxygen and the above element of oxygen in the recognition element periodictable.The nucleidic mass of oxygen is 8, and the nucleidic mass of nitrogen is 7.EDAX (electronic dispersion analyze x-ray) can the recognition cycle table in less than 6 element.The aqueous solution for preparing silicon according to above-mentioned female sample A.Coating is applied to different metals and sample is moved on the breadboard EDAX of the Corrmet in the Houston city of Texas, the result is as follows: Figure 12 has shown in EDAX figure I, has had nitrogen-silicon-potassium on 1010 carbon steels.Figure 13 has shown in EDAX figure II, has had nitrogen-silicon-potassium on the aluminium.Figure 14 has shown in EDAX figure III, has had nitrogen-silicon-potassium on the stainless steel.These analytical resultss show, use the compositions and methods of the invention can obtain to be used for the brand new technical of nitrogen/metallic surface on base material.
Wear testing
Compare with the lubricant based on oil of standard, at Engineered Lubricants, MarylandHeights, the Mo. place, with the linear precision measurement machine of Epsilon, tribology tester equipment carries out wear testing on dry film coating of the present invention.Machine is used to assess fluid and greasy wearing and tearing and extreme pressure property.This machine can be assessed wear rate duration of whole test, and relatively wearing and tearing and the every other variable of pointing out in real time, such as moment of torsion, friction, frictional coefficient, load sample, RPM, sample temperature, fluid temperature (F.T.), sample cycle and test extended period.Up to 4, under the condition of 000psi, use stainless steel needle and V rod, and pin is against the rotation of V rod.The heat that produces in the test period oil is constantly discharged.Stainless steel needle and V piece move 50 minutes in standard lubricating oil.Record wearing and tearing continuously.IA stainless steel needle V piece is submerged in moisture silicon/phosphorus solution of the present invention 1 minute, and lixiviate is also posted to test laboratory.Carried out wear testing 50 minutes with the pin and the piece that apply in advance.Test result demonstrates, and uses to have 1 inch 0.06 identical wear pattern based on the lubricant of oil and the wearing and tearing of dry film of the present invention.Thereby silicon of the present invention/phosphorus dry film has and uses the identical wear pattern of the observed wear pattern of standard lubricant.
The description of front is subject to particular of the present invention.Yet clearly, those skilled in the art can change and revise disclosed embodiment of the present invention, thus obtain in all advantages of the present invention some and and without departing from the spirit and scope of the present invention.For example, the invention is not restricted to top listed metal, but comprise all metals, comprise refractory metal.This scheme does not need to use peroxide compound, rare earth or quickens additive.PH can be a tart, or neutral, or alkalescence, this depends on which kind of pH is the preferred plan of the ion deposition of conversion surfaces.Further, scheme can be used at ambient temperature, and need not pre-treatment required in the Hardin technology and pre-clean step.This scheme can be applied to erect object, such as bridge, viaduct and other on-the-spot metal constructions.The metal construction generation passivation that these application methodes that form conversion surfaces have greatly reduced cost and allowed to have built up.Other metallic surface technology comprise sound pulse (pinging), beading (glassbeading) and zinc-plated.
Will be understood that, those skilled in the art can make various variations to details, material and the layout of the each several part of having described and having explained in order to explain character of the present invention in the above, and does not depart from the principle and scope of the present invention of stating in below the claim.
Claims (21)
1. one kind is used to produce the technology that deposits to lip-deep non-alkali-metal aqueous solution, and it comprises the steps:
1) forms water and ortho-phosphoric solution;
2) in the described solution of step 1, add ammonium hydroxide;
3) alkali metal hydroxide in the interpolation water in the described solution of step 1 and step 2 generation; And
4) in the described solution that step 1, step 2 and step 3 produce, add non-an alkali metal salt.
2. technology as claimed in claim 1, wherein, step 1 also comprises 0.5 part to 1.5 parts water of formation and 0.5 part to 1.5 parts ortho-phosphoric solution, wherein, described ortho-phosphoric acid is 75% to 85%; Step 2 also comprises adds 0.5 part to 1.5 parts ammonium hydroxide in the described solution of step 1, wherein, described ammonium hydroxide is 20% to 30%; Step 3 also comprises the alkali metal hydroxide that adds in 0.5 part to the 1.5 parts water in the described solution of step 1 and step 2 generation, wherein, the alkali metal hydroxide in the described water is 40% to 60%; And step 4 also comprises add the 0.1 non-an alkali metal salts that restrain 10 grams in the described solution that every 80ml produces to the step 1 of 100ml, step 2 and step 3.
3. technology as claimed in claim 1, wherein, described non-an alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth; The salt of vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium or rhodium or its combination.
4. technology as claimed in claim 1, wherein, described alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide or its combination.
5. one kind is used to produce the technology that deposits to lip-deep non-alkali-metal aqueous solution, and it comprises the steps:
1) form 0.5 part to 1.5 parts water and 0.5 part to 1.5 parts ortho-phosphoric solution, wherein, described ortho-phosphoric acid is 75% to 85%;
2) add 0.5 part to 1.5 parts ammonium hydroxide in the described solution of step 1, wherein, described ammonium hydroxide is 20% to 30%;
3) alkali metal hydroxide in 0.5 part to 1.5 parts water of interpolation in the described solution of step 1 and step 2 generation, wherein, the alkali metal hydroxide in the described water is 40% to 60%; And
4) in the described solution that every 80ml produces to the step 1 of 100ml, step 2 and step 3, add the 0.1 non-an alkali metal salts that restrain 10 grams.
6. technology as claimed in claim 5, wherein, described non-an alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth; The salt of vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium or rhodium or its combination.
7. technology as claimed in claim 6, wherein, described alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide or its combination.
8. one kind is used to produce the technology that deposits to lip-deep non-alkali-metal aqueous solution, and it comprises the steps:
1) forms water and vitriolic solution;
2) in the described solution of step 1, add ammonium hydroxide;
3) alkali metal hydroxide in the interpolation water in the described solution of step 1 and step 2 generation; And
4) in the described solution that step 1, step 2 and step 3 produce, add non-an alkali metal salt.
9. technology as claimed in claim 8, wherein, step 1 also comprises 0.5 part to 1.5 parts water of formation and 0.5 part of solution to 1.5 parts of vitriol oils; Step 2 also comprises adds 0.5 part to 1.5 parts ammonium hydroxide in the described solution of step 1, wherein, described ammonium hydroxide is 20% to 30%; Step 3 also comprises the alkali metal hydroxide that adds in 0.5 part to the 1.5 parts water in the described solution of step 1 and step 2 generation, wherein, the alkali metal hydroxide in the described water is 40% to 60%; And step 4 also comprises add the 0.1 non-an alkali metal salts that restrain 10 grams in the described solution that every 80ml produces to the step 1 of 100ml, step 2 and step 3.
10. technology as claimed in claim 8, wherein, described non-an alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth; The salt of vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium or rhodium or its combination.
11. technology as claimed in claim 8, wherein, described alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide or its combination.
12. one kind is used to produce the technology that deposits to lip-deep non-alkali-metal aqueous solution, it comprises the steps:
1) forms 0.5 part to 1.5 parts water and 0.5 part of solution to 1.5 parts of vitriol oils;
2) add 0.5 part to 1.5 parts ammonium hydroxide in the described solution of step 1, wherein, described ammonium hydroxide is 20% to 30%;
3) alkali metal hydroxide in 0.5 part to 1.5 parts water of interpolation in the described solution of step 1 and step 2 generation, wherein, the alkali metal hydroxide in the described water is 40% to 60%; And
4) in the described solution that every 80ml produces to the step 1 of 100ml, step 2 and step 3, add the 0.1 non-an alkali metal salts that restrain 10 grams.
13. technology as claimed in claim 12, wherein, described non-an alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth; V family-B family; Vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium or rhodium or its combination.
14. technology as claimed in claim 13, wherein, described alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide or its combination.
15. the aqueous composition of a non-an alkali metal salt, it comprises: water, mineral acid, ammonium hydroxide, alkali metal hydroxide and non-an alkali metal salt.
16. aqueous composition as claimed in claim 15, wherein, described mineral acid is ortho-phosphoric acid or sulfuric acid.
17. aqueous composition as claimed in claim 16, wherein, described non-an alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminium, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth; The salt of vanadium, niobium, tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium or rhodium or its combination.
18. aqueous composition as claimed in claim 17, wherein, described alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide or its combination.
19. aqueous composition as claimed in claim 18, wherein, when described aqueous composition is administered to the metallic surface, described non-an alkali metal salt will form 0.05 micron permanent coating to 10 micron thickness on described surface, wherein, described coating will reduce the wearing and tearing of described metallic surface.
20. aqueous composition as claimed in claim 15, wherein, when described aqueous composition is administered to the metallic surface, described non-an alkali metal salt will form 0.05 micron permanent coating to 10 micron thickness on described surface, wherein, described aqueous composition is produced by the described technology of claim 1.
21. aqueous composition as claimed in claim 15, wherein, when described aqueous composition is administered to the metallic surface, described non-an alkali metal salt will form 0.05 micron permanent coating to 10 micron thickness on described surface, wherein, described aqueous composition is produced by the described technology of claim 8.
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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 | ||
| PCT/US2008/065602 WO2008151173A1 (en) | 2007-06-05 | 2008-06-03 | Deposition of metal ions onto surfaces of conductive substrates |
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| US (1) | US20080302267A1 (en) |
| EP (1) | EP2155927A4 (en) |
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| MX (1) | MX2009013100A (en) |
| RU (1) | RU2486284C2 (en) |
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| CN114083230A (en) * | 2021-11-05 | 2022-02-25 | 徐州万达回转支承有限公司 | Novel slewing bearing for tooth surface self-lubricating and preparation method thereof |
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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 |
| US20080302267A1 (en) | 2007-06-05 | 2008-12-11 | Defalco Frank G | Compositions and processes for deposition of metal ions onto surfaces of conductive substrates |
| US8317909B2 (en) * | 2007-06-05 | 2012-11-27 | Dfhs, Llc | Compositions and processes for deposition of metal ions onto surfaces of conductive substrates |
| US8349764B2 (en) | 2007-10-31 | 2013-01-08 | Molycorp Minerals, Llc | Composition for treating a fluid |
| US8252087B2 (en) | 2007-10-31 | 2012-08-28 | Molycorp Minerals, Llc | Process and apparatus for treating a gas containing a contaminant |
| 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 |
| 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 |
| 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 |
| US9233863B2 (en) | 2011-04-13 | 2016-01-12 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
| WO2015134981A2 (en) | 2014-03-07 | 2015-09-11 | Molycorp Minerals, Llc | Cerium (iv) oxide with exceptional arsenic removal properties |
| KR101678514B1 (en) | 2015-08-31 | 2016-12-06 | 전북대학교산학협력단 | Cellulose thin film electrode comprising silver nanodendrites and fabrication method for the same |
| KR20180102163A (en) * | 2016-01-19 | 2018-09-14 | 티센크루프 스틸 유럽 악티엔게젤샤프트 | METHOD FOR MANUFACTURING A STEEL PRODUCT WITH A ZINC COATING AND A TIRE TECNOLOGY ACTIVE LAYER APPLIED ON THE COATING, AND A METALLICALLY PRODUCED STEEL PRODUCT |
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| US4672007A (en) * | 1984-08-16 | 1987-06-09 | Kollmorgen Technologies Corporation | Electrodeposition composition and process for providing a Zn/Si/P coating on metal substrates |
| US4533606A (en) * | 1984-08-16 | 1985-08-06 | Kollmorgan Technologies Corp. | Electrodeposition composition, process for providing a Zn/Si/P coating on metal substrates and articles so coated |
| JPH01100281A (en) * | 1987-10-13 | 1989-04-18 | Nippon Parkerizing Co Ltd | Chemical conversion coating liquid for surface of metal |
| US5084263A (en) * | 1989-07-24 | 1992-01-28 | Mccoy/Defalco Electrochemics, Inc. | Method of preparing inorganic polymeric water complexes and products so produced |
| GEP20002074B (en) * | 1992-05-19 | 2000-05-10 | Westaim Tech Inc Ca | Modified Material and Method for its Production |
| US5540788A (en) * | 1995-02-24 | 1996-07-30 | Mdechem, Inc. | Method of preparing iron-phosphate conversion surfaces |
| US6605751B1 (en) * | 1997-11-14 | 2003-08-12 | Acrymed | Silver-containing compositions, devices and methods for making |
| DE60118910T2 (en) * | 2000-01-31 | 2007-03-01 | Henkel Kgaa | PHOSPHATE CONVERSION PROCESSING AND COMPOSITION |
| AUPQ633300A0 (en) * | 2000-03-20 | 2000-04-15 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metallic surface ii |
| RU2207400C1 (en) * | 2001-12-17 | 2003-06-27 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Method of application of protective coating to article from magnesium alloy |
| US7087104B2 (en) * | 2003-06-26 | 2006-08-08 | Intel Corporation | Preparation of electroless deposition solutions |
| CN101006142B (en) * | 2004-06-14 | 2011-03-30 | 皮格门坦涂料用防腐蚀颜料有限公司 | Method for depositing anti-corrosive coating onto metal surface |
| 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 |
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| CN114083230A (en) * | 2021-11-05 | 2022-02-25 | 徐州万达回转支承有限公司 | Novel slewing bearing for tooth surface self-lubricating and preparation method thereof |
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| KR101506360B1 (en) | 2015-03-26 |
| JP2014159643A (en) | 2014-09-04 |
| AU2008259858A1 (en) | 2008-12-11 |
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| US20080302267A1 (en) | 2008-12-11 |
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| RU2009145641A (en) | 2011-07-20 |
| CA2689437A1 (en) | 2008-12-11 |
| MX2009013100A (en) | 2010-08-18 |
| RU2486284C2 (en) | 2013-06-27 |
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