JP2010529299A - Deposition of metal ions on the surface of a conductive substrate - Google Patents

Abstract

The present invention provides a composition and method for conditioning metal ions for deposition on and / or in conductive substrates such as metals and substantially eliminating friction from contact between the metals. It is used in the aqueous solution embodiment to form a new metal surface on all metal substrates. This step forms a stable aqueous solution of metal and non-metal ions that can be absorbed or absorbed on and / or in the conductive substrate. The aqueous solution consists of ammonium alkali metal phosphates and / or ammonium alkali metal sulfates mixed with water-soluble metal or nonmetal salts according to groups 1 to 8 of the periodic table of elements. The aqueous solution allows nanoprecipitation of metal ions on and / or in the conductive substrate. The surface formed by the deposited metal ions provides metal passivation and substantially eliminates friction in metal-to-metal contact without the use of hydrocarbon-based lubricants.
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Description

  The present invention relates to a composition and process for coating a metal, and more particularly to a water-containing composition for coating a metal surface and a process for producing these water-containing compositions.

  Many methods have been developed to form new conversion surfaces in metals as primary products such as ferrous metals, steel, stainless steel, aluminum, zinc and titanium. These methods include electroplating, phosphating (conversion surface), chemical vapor deposition, ion sputtering, and other methods. An early electroplating method for silver was developed in the United Kingdom in 1870. Later, a method of plating noble metals, copper and gold, was developed. These metals needed to form an adhesion layer on the substrate metal by forming a complex with cyanide. The use of cyanide is still a preferred method of forming a first noble metal adhesion layer on a substrate. Cyanide, a very toxic substance, is harmful to the environment and dangerous to public health. Many safety measures had to be taken in order to use cyanide, in which case the user could be exposed to toxic vapors. Electroplating methods have been developed for many years, and methods for electroplating other elements such as zinc, cadmium, nickel, and chromium have been developed and widely used in the commercial industry for industrial and decorative purposes.

  Electroplating deposits on the substrate surface do not enter between the metal grids on the substrate surface. Thus, the precipitates are not strong enough to maintain their integrity when the substrates are “cold worked” to the yield point. Zinc electrodeposits are destroyed by cold working 61,000 PSI and cadmium by 69,000 PSI cold working, while steel substrates have a yield point of 80,000 PSI or higher. This has always been an important issue in the electroplating industry. Electroplaters have had to deal with many different parameters in order to create an effective deposition apparatus to achieve the desired finish. Electroplating requires pretreatment, precleaning procedures, a controlled plating bath, and special anode rinsing. Electroplating generally follows the rules of the electrochemical family that can plate a noble metal to a less basic metal, but not the other way around. This limits the ability to plate all the metals of the periodic table onto other metal substrates of the periodic table.

  Another method of surface modification is phosphating, in which a phosphate conversion surface is formed in steel or aluminum. Phosphate conversion surfaces are widely used for corrosion inhibition and as a base for painting. Phosphate treatment is the most widely used method in the commercial industry, and its main use is as a primer for corrosion inhibition in the automotive industry and as a fixture to hold the paint.

  The chemical conversion phosphating method requires a plating bath, is energy intensive, and takes time. The phosphating process requires at least 10 minutes or more to obtain a commercially satisfactory adhesion conversion surface. The industry has developed many reaction promoters to speed up the conversion process over the years.

  In the second half of the 20th century, new and special methods were developed to obtain better surfaces with metals. These methods improved the metal by coating on the substrate by a vapor deposition method such as vacuum deposition, sputtering, magnetron sputtering, or ion plating. These methods can be used to harden metal surfaces such as tungsten carbide inserts, drills, metal tools such as hobbing tools. Chemical vapor deposition is applied in a vacuum chamber, and the metal is ionized in a nitrogen atmosphere, deposited on the substrate, and diffuses into the substrate. Some examples of the results of these methods are titanium nitride and boron nitride. Deposition is generally performed line of sight, and such a process limits the shape, size and placement of the substrate metal. Such a process is expensive and requires the use of special equipment and high energy. The vapor deposition is formed under strict conditions such as temperature and gas composition. These methods provide vapor deposition with a dense, smooth, defect-free surface that is useful as many commercial products.

  Many metals form inert oxide surfaces that are useful to protect the metal from corrosion. Such metals are aluminum and stainless steel and titanium. The oxide film formed on stainless steel is a nanomolecular layer that renders the surface inert. The oxide film formed on carbon steel is harmful to metals and is called rust.

  US Pat. No. 6,755,917 to Hardin et al. Describes a solution for providing a conversion coating on a surface in a metallic material. The solution has a peroxide species and is limited to at least one metal from groups 1B, 2B, 4A, 5A, 6A and 8 of the periodic table. In particular, Hardin also provides a hydrous concentrate of an acidic liquid for replenishment of the conversion coating solution according to the present invention, the concentrate comprising a total rare earth ion: monovalent anion of 1: 200-1 : Rare earth ions and monovalent anions and / or total rare earth ions (as defined herein) in a molar ratio of 6: rare earth ions and divalent in a molar ratio of 1: 100 to 1: 3 Anions and / or concentrates are 1B, 2B, 4A, 5A, 6A and Group 7, preferably Cu, Ag, Au, Cd, Hg, Ni, Pd, Pt, Co, Rh, Ir, At least one metal selected from the group consisting of Ru, Os, Sn, Pb, Sb, Bi, Se and Te and anions, wherein the molar ratio of the sum of these elements to the anion is from 1:50 to : The 10,000. Furthermore, Hardin's method is limited to acidic aqueous solutions.

  It is known that thin molecular monolayer oxide films present on stainless steel can provide excellent surface stabilization to metals. It has been theorized that corrosion can be suppressed in one day by a thin molecular layer on the metal surface. Furthermore, it has been theorized that a significant reduction in friction can be obtained with a thin and strong metal film.

  Jacqueline Krim, PhD published a paper entitled “Friction at the Atomic Scale” at Scientific American, published in October 1996. The research results led to the conclusion that "there is no friction in contact between metals at the atomic level". This surprising work has been questioned by the many beliefs that friction can only be mitigated by the use of lubricants to reduce the heat generated by the metal sliding against each other. Another surprising conclusion is that at the atomic level, “friction comes from lattice vibrations of atoms as atoms close to the surface start to move due to the sliding action of the atoms on the opposite surface. In this case, some of the mechanical energy required to slide from one surface to the other is converted to acoustic energy and ultimately to heat. " is there. Heat causes friction. More mechanical energy needs to be applied to maintain sliding. In addition, Krim says, “Solids vibrate only at specific individual frequencies, so the total amount of mechanical energy depends on the frequency actually excited. Friction increases when reverberating at a frequency of 2. If the opposing surface does not resonate with the frequency of the other surface itself, no sound waves are generated. It opens up the exciting possibility of exhibiting sliding with almost no friction. ”

  Another surprising conclusion of Krim's work is that dry films are more slippery than liquid films. This is intuitively contrary to all current thinking about friction. Further testing by other scientists has demonstrated that contact between metals at the atomic level eliminates friction and causes friction with a "stick / slip" action with liquid lubricants. The liquid enters and leaves the metal gap. As a result, vibrations are generated in the lattice to generate sound waves, which are converted into heat and cause friction.

  According to forecasts, reducing friction can save up to 1.6% of gross national product or over $ 200 trillion annually. For this reason, the process of virtually eliminating daily metal friction is new and useful, but has not been utilized. Such processes are of great value, have great value and purpose pursued by the state for energy self-sufficiency and greatly increase the cost of infrastructure replacement for corroded underground pipelines, storage tanks, bridges and overpasses. It is clear to reduce.

  Phosphate conversion surfaces are used in commercial plants to reduce decibel levels. A high decibel level is an ongoing risk factor at the work site, which is detrimental to human health and results in a loss of hearing early and late. Government regulatory agencies such as OSHA and EPA are constantly asking the industry to improve to lower decibel levels in manufacturing operations. Thus, a diversion surface that reduces the decibel level is beneficial to human health and improves the workplace environment.

  US Pat. No. 7,087,104 to Choi et al. Describes a system and method for storing a solution comprising a portion of the group consisting of metal ions, complexing agents, ammonium salts and strong bases. Yes. Used to form an electroless deposition solution containing the entire group. In one embodiment of the present invention, the metal ion has cobalt ion, the complexing agent has citric acid, the ammonium salt has ammonium chloride, and the strong base is tetramethylammonium hydroxide. have. The base solution can be prepared and then left for 2 days to stabilize prior to use. Another solution needs to be prepared and then mixed with the original solution just before use in the plating bath. This requires complex logistics and skilled workers to produce the final preparation at the factory plating bath site.

  US Pat. No. 5,310,419 issued to McCoy et al. Discloses a method for preparing electrolyte solutions for metal electroplating and other uses. It has been discovered that with the use of an external power source, all metals in the periodic table can be electrodeposited onto a conductive substrate.

  U.S. Pat. No. 5,340,788 to Defalco et al. Discloses a method for adjusting the oil additive applied to parts of an internal combustion engine, using lubricating oil as the carrier fluid. The solution is mixed with polyethylene glycol for introduction into the lubricating oil.

  The present invention provides a composition and process for adjusting metal ions to deposit on and / or in conductive substrates such as metals to substantially eliminate friction due to metal-to-metal contact. It is used in water-soluble embodiments to form a new metal surface on every substrate. This step forms a stable aqueous solution of metal and non-metal ions that can be absorbed or absorbed on and / or in the conductive substrate. The aqueous solution consists of ammonium alkali metal phosphate and / or ammonium alkali metal sulfate mixed with a water-soluble metal or nonmetal salt selected from groups 1 to 8 of the elements of the periodic table. Metal ions can be nano-deposited on and / or in the conductive substrate with an aqueous solution. The surface formed by the deposited metal ions provides metal passivation and substantially eliminates friction due to metal-to-metal contact without the use of hydrocarbon-based lubricants.

  The process of the present invention for producing an ionic complex is carried out in a water-soluble reaction medium, and the ionic complex is used as an aqueous solution when forming a conversion surface on a metal object. In order to prepare the inorganic ion complex, the following reaction is required: a) at least one water-soluble non-alkali metal salt selected from Groups 1 to 8 of the periodic table; b) an alkali metal hydroxide; c) Compounds containing sulfur and / or phosphorus, such as mineral acids; d) ammonium hydroxide; and e) water. When the reactants orthophosphoric acid, water, ammonium hydroxide and alkali metal hydroxide are mixed, the parent solution A is formed. An exothermic reaction occurs and the temperature of the aqueous solution reaches about 100 ° C. Then, a metal salt such as silver nitride and zinc oxide, aluminum salt such as aluminum sulfate and ammonium molybdate, ammonium tungstate or water-soluble metal salt is introduced into a reaction vessel, stirred, and metal Heat until the salt is totally dissolved in the aqueous medium. The parent solution B can be formed by mixing the reactants sulfuric acid, water, ammonium hydroxide and alkali metal hydroxide. An exothermic reaction occurs and the temperature of the aqueous solution reaches about 100 ° C. Then, a certain amount of metal salt such as boric acid, copper sulfate, or ammonium molybdate can be introduced into the reaction vessel and dissolved. Then, the metal ions dissolve in the aqueous solution but do not precipitate and stabilize. Alkali metal hydroxide is basically sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide of Group 1A metal of the periodic table, but potassium hydroxide is a preferred reactant.

  Further, the metal aqueous solution precipitates nitrogen on the metal surface. Abrasion tests show that metal coatings formed by application of aqueous solutions reduce metal wear as effectively as oil-based lubricants.

  An advantage of the present invention is that the solution can be applied to the structure regardless of the disadvantages and limitations of current electroless chemical vapor deposition or electroplating techniques in today's commercial applications.

  Another advantage is a ground stable solution that can be shipped to a location.

  Another advantage is a simple process using an aqueous solution to form a conversion coating on a metallic material.

  Another advantage is the formation of oxide free conversion surfaces for all metal substrates.

FIG. 1 shows silver-phosphorus-potassium deposition on stainless steel. FIG. 2 shows the deposition of silicon-phosphorus-potassium on aluminum. FIG. 3 shows the deposition of silicon-phosphorus-potassium on stainless steel. FIG. 4 shows the deposition of zinc-phosphorus-potassium on aluminum. FIG. 5 shows the precipitation of aluminum-phosphorus-potassium on 1010 carbon steel. FIG. 6 shows the deposition of copper-phosphorus-potassium on 1010 carbon steel. FIG. 7 shows the precipitation of molybdenum-phosphorus-potassium on 1010 carbon steel. FIG. 8 shows the precipitation of molybdenum-phosphorus-potassium on stainless steel. FIG. 9 shows the deposition of silicon-phosphorus-potassium on 1010 carbon steel deposited from the oil phase. FIG. 10 shows the thickness of boron coating on aluminum by scanning electron micrograph. FIG. 11 shows the thickness of the molybdenum coating on the aluminum by scanning electron microscope images. FIG. 12 shows the presence of nitrogen-silicon-potassium on 1010 carbon steel according to EDAX chart 1. FIG. 13 shows the presence of nitrogen-silicon-potassium on aluminum according to EDAX chart 2. FIG. 14 shows the presence of nitrogen-silicon-potassium on stainless steel according to EDAX chart 3.

  The following description details preferred embodiments of the invention, but the invention is illustrated in the accompanying drawings in its application as it is possible in other embodiments and can be implemented in various ways. Note that the details are not limited to the details of the structure and arrangement of the parts made.

  It requires an inexpensive, efficient and simple application method to reduce the friction between metals at the atomic level. Surprisingly, when producing metal ions according to the present invention, the ions so produced diffuse between the metal lattices. Surprisingly, the ions produced do not follow the rules of the electrochemical series. That is, aluminum can be deposited on iron-based metals, but this is not expected in conventional literature. Surprisingly, the silver ions produced in the present invention remain optically stable in aqueous solution in the presence of sunlight. Optically stable silver ions are disclosed in U.S. Pat. No. 6,985,500, which includes complexation by ion sputtering as described in U.S. Pat. No. 5,985,308 or with various solvents such as alcohols and chlorine anion donor compounds. , 897,349, and only through expensive technology. Silver ions have been the subject of much research. There are many known ways to stabilize silver ions, but none of these uses an aqueous solution. Adhesive silver deposits on metal specimens by short dipping, brushing and spraying are of great value. Silver ions that are stable in aqueous solutions will be widely applied in electronics and pharmacy, for example in wound healing bandages due to their antibacterial properties and to form antibacterial surfaces on medical devices.

  The present invention does not require the use of an electromotive force applied from the outside, but forms a thin and strong metal film on the substrate by short-time immersion, brushing, or spraying. The surprising discovery of the present invention is that a new conversion surface can be created to deposit a monolayer on and in the substrate. Most plating properties require a deposition thickness of 1 mil (23-24 microns). The present invention provides a permanent thin film of 0.05 to 10 microns thickness on a conductive substrate.

  The process for producing an ion complex of the present invention is carried out in a water-soluble reaction medium, and the ion complex is used as an aqueous solution when forming a conversion surface on a metal object. In order to prepare the inorganic ion complex, the following reaction is required: a) at least one water-soluble non-alkali metal salt selected from Groups 1 to 8 of the periodic table; b) an alkali metal hydroxide; c) Compounds containing sulfur and / or phosphorus, such as mineral acids; d) ammonium hydroxide; and e) water.

  The non-alkali metal salt reactant is derived from a non-alkali metal of Groups 1 to 8 of the periodic table. Representative non-limiting examples of applicable non-alkaline aqueous metal salts are Group 1B copper, silver, gold; Group 2A beryllium, magnesium; Group 2B zinc, cadmium; Group 3A aluminum, gallium, indium Group 4A silicon, tin, lead; Group 4B titanium, zirconium, hafnium; Group 5A antimony, bismuth; Group 5B vanadium, niobium, tantalum; Group 6A selenium, tellurium; Group 6B chromium, molybdenum, tungsten Group 7B manganese; and Group 8 iron, cobalt, nickel, palladium, rhodium.

  Silicon, a member of Group 4A, is considered a non-metal, but is generally defined as a metal element, while silicon functions as a non-alkali metal in the method of the present invention. Thus, “a non-alkali metal of Groups 1-8 of the Periodic Table” is meant to include all of the above, including silicon and some and corresponding metals. It should be further recognized that the term “non-alkali metal of Groups 1-8 of the Periodic Table” does not include Group 1A alkali metals. Alkaline earth metals, Group 2A calcium, strontium, and barium are likewise not included in the scope of this term. On the other hand, group 2A beryllium and magnesium can be employed as an application example in the practice of the present invention, and these metals are also used herein as “non-alkali metals of groups 1 to 8 of the periodic table”. It is included in the expression. Moreover, you may use the combination of a non-alkali metal salt.

  The parent solution A can be formed by mixing the reactants orthophosphoric acid, water, ammonium hydroxide and alkali metal hydroxide. An exothermic reaction occurs and the temperature of the aqueous solution reaches about 100 ° C. A certain amount of a metal salt such as silver nitride or zinc oxide, an aluminum salt such as aluminum sulfate, ammonium molybdate, ammonium tungstate or a water-soluble metal salt is introduced into a reaction vessel, stirred, and the entire metal salt in an aqueous solvent. Can be heated until dissolved. Alkali metal hydroxides are Group 1A hydroxides of the periodic table, mainly sodium hydroxide, potassium hydroxide, and lithium hydroxide, but the preferred reactant is potassium hydroxide. Moreover, you may use the combination of these alkali metal hydroxides.

Preparation of parent solution A In a reaction vessel, 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. Add 0 liters, about 75% to 85%, preferably about 80% orthophosphoric acid by volume. Then about 0.5 to 1.5 liters, preferably about 1.0 liter, about 15 to 35% by volume, preferably about 26% ammonium hydroxide is added. Then about 0.5 to 1.5 liters, preferably about 1.0 liter, about 20 to 60% by volume, preferably about 49% potassium hydroxide is added.

  Reactant sulfuric acid, water, ammonium hydroxide and alkali metal hydroxide can be mixed to form parent solution B. An exothermic reaction occurs and the temperature of the aqueous solution reaches about 100 ° C. Then, boric acid, copper sulfate, or ammonium molybdate is introduced into the reaction vessel and dissolved. Then, the metal ion becomes soluble in the aqueous solution and is stabilized without being precipitated. Alkali metal hydroxide is a hydroxide of Group 1A metal in the periodic table, mainly sodium hydroxide, potassium hydroxide, and lithium hydroxide, with potassium hydroxide being the preferred reactant. Moreover, you may use the combination of these alkali metal hydroxides.

Preparation of parent solution B About 1-3 liters, preferably about 2 liters of water, and about 0.5-1.5 liters, preferably about 1 liter of concentrated sulfuric acid are added to the reaction vessel. Then about 0.5 to 1.5 liters, preferably about 1 liter, about 15 to 35% by volume, preferably about 26% ammonium hydroxide is added. Then about 0.5 to 1.5 liters, preferably about 1 liter, about 20 to 60% by volume, preferably about 49% potassium hydroxide is added. Care must be taken because the reaction is extremely exothermic.

Example of silver nitride parent solution A For about 80 to 120 ml, preferably about 100 ml of parent solution A, the pH of this solution is adjusted to about 7 using phosphoric acid. About 0.1 to 10 grams, preferably 1 gram of silver nitride is added to this solution. Stir and heat until the silver salt is completely dissolved in the solution. A 1010 steel specimen is immersed in the silver nitride solution for 1 minute. A thin, strong, shiny silver film is formed on a steel specimen. The surface is observed using a scanning electron microscope (SEM). Silver is known to form adhesion deposits on steel when no cyanide solution and externally applied electromotive force are used. Such a process of silver deposition can be performed without the presence of cyanide and externally applied electromotive force to produce a strong non-immersed precipitate. The silver nitride solution is placed in a glass container and exposed to sunlight for several weeks. The insensitivity of silver can be stabilized by the inexpensive process of the present invention which is very useful in areas such as antibacterial action and protection of medical device surfaces. A sheet of Alcoa 2 "x 2 'aluminum foil wrap is brought into contact with the silver nitride solution and rubbed against the surface. The surface of the aluminum foil is coated with a film of silver. 410 stainless steel coupon is nitrided for 1 minute Immerse in a silver solution, a thin and strong silver film forms on stainless steel.

  A cotton gauze bandage is immersed in a silver solution and then exposed to sunlight for several days. The fact that the bandage does not turn black as expected when the silver ions are exposed to sunlight implies the use of the treated bandage as an antibacterial bandage for the hygiene and wound healing . Gauze bandages can be exposed to propane torch flames. Cotton burns when in direct contact with the flame tip, but gauze does not ignite, which means the use of a silver solution as a flame retardant for the fiber.

Example of ammonium molybdate parent solution A Using about 80 to 120 ml, preferably about 100 ml of parent solution A, about 0.1 to 10 grams, preferably about 1 gram of ammonium molybdate is added to the solution. Stir and heat until the ammonium molybdate is completely dissolved. A 1010 steel coupon is immersed in the solution for 1 minute. A thin and strong molybdenum film is formed on the steel specimen. A strip of 2 "x 2" aluminum foil was immersed in the solution for 30 seconds. A thin precipitate of molybdenum formed on the aluminum coupon. “Electroplating” Frederick A Lowenheim, McGraw Hill Book company, page 141, “From an electrode potential perspective, metals such as tungsten and molybdenum can be electroplated with an aqueous solution of about 5 pH. 1), these metals cannot be deposited in the form of pure metals from aqueous solutions. Thus, the present invention provides a surprising method for forming a molybdenum surface on steel and other conductive substrates.

Example of ammonium tungstate parent solution A Using about 80 to 120 ml, preferably about 100 ml of parent solution A, about 0.1 to 10 grams, preferably about 1 gram of ammonium tungstate is added to the solution. Stir and heat until the metal salt is completely dissolved. A 1010 steel coupon is immersed in the solution for 1 minute. A thin, glossy and strong tungsten film is formed on a stainless steel specimen. As with the molybdenum case, the present invention provides a surprising method for forming tungsten on steel.

Example of Copper Sulfate Parent Solution B Using about 80 to 120 ml, preferably about 100 ml of parent solution B, add about 0.1 to 10 grams, preferably about 1 gram of copper sulfate to the solution. Stir and heat until the metal salt is completely dissolved in the solution. Immerse a 1010 steel panel in the solution for a maximum of 2 minutes. Adhesive visible copper deposits form on the steel coupon. The only practical way to deposit adhesive copper plates on active metals such as zinc and steel is to use a cyanide bath. Despite many attempts to dispense with plating baths containing cyanide, due to environmental constraints, no practical alternative to copper cyanide baths has been developed. It is known that copper without cyanide forms a valuable immersion deposit by external electromotive force. A standard ASTM test for adhesion deposition places a plastic adhesive tape on the plate surface and pulls the tape. If the precipitation is immersion precipitation, the copper is peeled off with the tape. If the deposit is adhesive, the copper will not peel off with the plastic adhesive tape. When plastic adhesive tape was applied to the copper surface in these examples, the copper film remained attached.

Example of Aluminum Sulfate Parent Solution B Using about 80 to 120 ml, preferably about 100 ml of parent solution B, about 0.1 to 10 grams, preferably about 2 grams of aluminum sulfate is added to the solution. Stir and heat the solution until completely dissolved. A 1010 steel coupon is immersed in the solution for 1 minute. A thin, strong, glossy aluminum adhesive film is formed on the steel coupon.

Example of Boric Acid Parent Solution B Using about 80 to 120 ml, preferably about 100 ml of Parent Solution B, add about 0.1 to 10 grams, preferably about 2 grams of boric acid to the solution. Stir and heat until completely dissolved. A 1010 steel coupon is immersed in the solution for 1 minute. A thin, strong and glossy boron film is formed on the steel coupon. A 2 "x 2" aluminum foil coupon was immersed in the solution. A thin film of boron was formed on the aluminum. A stainless steel coupon was immersed in the solution and a thin metal film of boron formed on the stainless steel.

Example of ammonium tungstate parent solution B Using about 80-120 ml, preferably about 100 ml of parent solution B, add 2 ml, 12% by volume of ammonium tungstate to the solution. Stir and heat until completely dissolved. A 1010 steel coupon is immersed in the solution for 1 minute. A thin, strong, glossy tungsten metal film is formed on a steel coupon.

Example of combination of parent solution A and parent solution B About 160 ml of parent solution A and about 40 ml of parent solution B are combined. The pH of the combined solution containing potassium hydroxide is raised to about 12 by adding about 10 ml of about 49% potassium hydroxide by weight. Stir and heat until the potassium hydroxide is completely dissolved. This solution can be sprayed into a hydrocarbon stream, such as an internal combustion engine natural gas or volatile gasoline, to facilitate fuel combustion. The solution may be sprayed onto the intake port of the internal combustion engine to increase the volume of air available for combustion and increase combustion efficiency.

Example of Petroleum Derivative Combining Parent Solution A and Ammonium Tungstate Parent Solution B About 160 ml of parent solution A and about 40 ml of ammonium tungstate parent solution B are mixed. Using about 200 ml of highly purified mineral oil, about 20 ml (10% by volume) of a mixed solution of parent solution A and ammonium tungstate parent solution B is mixed with the mineral oil. By raising the temperature to above 100 ° C., the oil agent is dehydrated to remove water and precipitate a salt. When the oil agent becomes clear and transparent, the oil cools and the oil can be transferred. Then, the transferred material can be used as an oil additive or a fuel additive. Tungsten is known to have catalytic properties. By such a method of producing fuel and lubricant additives, metals such as platinum and iron having catalytic properties can be used.

Example of Conversion Surface Three substrate metals were selected: aluminum foil manufactured by ALCOA, 1010 carbon steel, and 400 series stainless steel. These substrate metals were selected as representative examples of the most widely used metals in the world. The metal ion solution was chosen to show that the metal ions produced by the present invention can be deposited on and in various metal substrates to obtain new metal surfaces that have not been known so far. A metal ion solution was prepared according to parent solution A. The samples were not pre-treated to remove oxides, dirt, rust or oil, but were soaked for 30 seconds at their respective ambient conditions and dried using ambient air and paper towels. And the sample was observed by EDS (Electron dispersive spectroscopy) of Vista Engineering of Birmingham, Alabama, US. The results are as shown in the analysis charts of FIGS. FIG. 1 shows silver-phosphorus-potassium deposition on stainless steel. FIG. 2 shows the deposition of silicon-phosphorus-potassium on aluminum. FIG. 3 shows the deposition of silicon-phosphorus-potassium on stainless steel. FIG. 4 shows the deposition of zinc-phosphorus-potassium on aluminum. FIG. 5 shows the precipitation of aluminum-phosphorus-potassium on 1010 carbon steel. FIG. 6 shows the deposition of copper-phosphorus-potassium on 1010 carbon steel. FIG. 7 shows the precipitation of molybdenum-phosphorus-potassium on 1010 carbon steel. FIG. 8 shows the precipitation of molybdenum-phosphorus-potassium on stainless steel. FIG. 9 shows the deposition of silicon-phosphorus-potassium on 1010 carbon steel deposited from the oil phase.

Example of measuring the thickness of a metal coating applied to an aluminum surface Ammonium molybdate parent solution A and boric acid parent solution B were prepared as described above. A coating of each solution was applied to the aluminum surface and the coating could be dried. The thickness of the aluminum coating was measured using known scanning electron microscopy techniques at the NASA Marshall Flight Center. The thickness of the coating was calculated from the scanning electron microscope image. An image of the boron coating is shown in FIG. 10, and an image of the molybdenum coating is shown in FIG. A coating 10 is shown on the surface of the aluminum metal 11 against the background 12. Several measurements were taken along the length of the coating 10. The average coating thickness ± standard error was 1.32 ± 0.11 microns (n = 7) for molybdenum and 1.22 ± 0.25 microns (n = 4) for boron.

Example of Nitrogen Deposition Under the current technology, only nitrogen can be deposited on a metal substrate by CVD (Chemical Vapor Deposition), which is an expensive and very limited method of forming a nitride surface. Further, the method of the present invention deposits nitrogen on the metal substrate together with the deposited metal. The analytical capabilities of SEM are limited to the identification of oxygen and the above-mentioned elements of the periodic table. The atomic weight of oxygen is 8, and the atomic weight of nitrogen is 7. EDAX (electron dispersive analytical x-ray) can identify up to 6 elements of the periodic table. An aqueous solution of silicon was prepared according to the parent solution A described above. Coatings were applied to various metals and samples were subjected to EDAX at the Corrmet laboratory in Houston, Texas: the results are as follows. FIG. 12 shows the presence of nitrogen-silicon-potassium on 1010 carbon steel according to EDAX chart 1. FIG. 13 shows the presence of nitrogen-silicon-potassium on aluminum according to EDAX chart 2. FIG. 14 shows the presence of nitrogen-silicon-potassium on stainless steel according to EDAX chart 3. These analysis results show that an entirely new technique for the nitrogen / metal surface on the substrate can be utilized using the compositions and methods of the present invention.

Abrasion Test Abrasion tests were performed on the coatings of the invention compared to standard oil-based lubricants from Engineered Lubricants, Maryland at the Esilon Linear Precision Test Machine, Tribology Testing Equipment, and the coatings of the present invention. This machine is used to predict wear and extreme pressure properties of fluids and greases. The machine predicts the wear rate throughout the test period and wears all other indicator variables such as torque, friction, coefficient of friction, sample load, RPM, sample temperature, fluid temperature, sample cycle, and test period. And has a performance to compare with in real time. Stainless steel pins and V bars were used with the pins rotating relative to the V bars under conditions of up to 4000 psi. The heat generated by the oil during the test is continuously removed. Stainless steel pins and V-blocks were tested with standard lubricant for 50 minutes. Wear was recorded continuously. A 1A stainless steel pin and V block were immersed in the silicon / phosphorous aqueous solution of the present invention for 1 minute, removed and sent to the laboratory. The abrasion test was performed with precoated pins and V-blocks for 50 minutes. The test results showed that the oil-based lubricant and the dry coating of the present invention were consistent with the 0.06 inch wear of the present invention. Thus, the dry silicon / phosphorus coating of the present invention has the same wear as observed with standard lubricants.

  The above description is limited to specific embodiments of the present invention. However, it will be apparent to those skilled in the art that variations and modifications may be made to the disclosed embodiments of the present invention without departing from the spirit and scope of the invention, while realizing some of its advantages. It is. For example, the present invention is not limited to the above metals, but includes all metals including high melting point gold. The solution does not require the use of peroxides, rare metals or accelerator additives. The pH will be acidic, or neutral or alkaline, depending on the pH being the best solution for precipitation of ions on the conversion surface. Furthermore, 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 buildings such as bridges, overpasses and other metal structures. These applications for forming the conversion surface greatly reduce costs and allow the passivation of already built metal structures. Other metal surface technologies include pinning, glass beading and galvanization.

  Various modifications to the details, materials, and arrangements of parts described and illustrated above to illustrate the nature of the invention depart from the principles and scope of the invention as set forth in the following claims. Note that this may be done by one skilled in the art without.

Claims (21)

A step for producing an aqueous solution of a non-alkali metal for depositing on the surface,
1) forming an aqueous solution containing orthophosphoric acid;
2) adding ammonium hydroxide to the solution of step 1;
3) adding an alkali metal hydroxide in water to the solution produced by steps 1 and 2;
4) adding a non-alkali metal salt to the solution produced by steps 1, 2 and 3;
The process characterized by including. Step 1 further includes forming a solution of 0.5 to 1.5 parts water to 0.5 to 1.5 parts 75% to 85% orthophosphoric acid;
Step 2 further includes adding 0.5 to 1.5 parts of 20-30% ammonium hydroxide to the solution of Step 1;
Step 3 further comprises adding 0.5 to 1.5 parts of alkali metal hydroxide in 40% to 60% water to the solution produced by Steps 1 and 2;
The step 4 further comprises adding 0.1 to 10 grams of non-alkali metal salt to each 80 to 100 ml solution produced by steps 1, 2 and 3. Process.   The non-alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminum, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth, vanadium, niobium, tantalum, selenium. 2. The process of claim 1, wherein the salt is tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, or rhodium, or a combination thereof.   The process according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination thereof. A step for producing an aqueous solution of a non-alkali metal for depositing on the surface,
1) forming a solution of 0.5 to 1.5 parts water to 0.5 to 1.5 parts 75% to 85% orthophosphoric acid;
2) adding 0.5 to 1.5 parts of 20-30% ammonium hydroxide to the solution of step 1;
3) adding 0.5 to 1.5 parts of alkali metal hydroxide in 40% to 60% water to the solution produced by steps 1 and 2;
4) adding 0.1 to 10 grams of non-alkali metal salt to each 80 to 100 ml solution produced by steps 1, 2 and 3;
The process characterized by including.   The non-alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminum, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth, vanadium, niobium, tantalum, selenium. 6. The process of claim 5, wherein the salt is tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, or rhodium, or a combination thereof.   The process according to claim 6, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination thereof. A step for producing an aqueous solution of a non-alkali metal for depositing on the surface,
1) forming an aqueous solution containing sulfuric acid;
2) adding ammonium hydroxide to the solution of step 1;
3) adding an alkali metal hydroxide in water to the solution produced by steps 1 and 2;
4) adding a non-alkali metal salt to the solution produced by steps 1, 2 and 3;
The process characterized by including. Step 1 further includes forming a solution of 0.5 to 1.5 parts water to 0.5 to 1.5 parts concentrated sulfuric acid;
Step 2 further includes adding 0.5 to 1.5 parts of 20-30% ammonium hydroxide to the solution of Step 1;
Step 3 further comprises adding 0.5 to 1.5 parts of alkali metal hydroxide in 40% to 60% water to the solution produced by Steps 1 and 2;
9. Step 4 further comprises adding 0.1 to 10 grams of non-alkali metal salt to each 80 to 100 ml solution produced by steps 1, 2 and 3. Process.   The non-alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminum, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth, vanadium, niobium, tantalum, selenium. 9. The process of claim 8, wherein the salt is tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, or rhodium, or a combination thereof.   The process according to claim 8, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination thereof. A step for producing an aqueous solution of a non-alkali metal for depositing on the surface,
1) forming a solution of 0.5 to 1.5 parts water to 0.5 to 1.5 parts concentrated sulfuric acid;
2) adding 0.5 to 1.5 parts of 20-30% ammonium hydroxide to the solution of step 1;
3) adding 0.5 to 1.5 parts of alkali metal hydroxide in 40% to 60% water to the solution produced by steps 1 and 2;
4) adding 0.1 to 10 grams of non-alkali metal salt to each 80 to 100 ml solution produced by steps 1, 2 and 3;
The process characterized by including.   The non-alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminum, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth, group 5B vanadium, niobium, 13. The process of claim 12, wherein the process is a salt of tantalum, selenium, tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, or rhodium, or a combination thereof.   The process according to claim 13, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination thereof. A water-containing composition of a non-alkali metal salt,
A water-containing composition comprising water, mineral acid, ammonium hydroxide, alkali metal hydroxide, and non-alkali metal salt.   The water-containing composition according to claim 15, wherein the mineral acid is orthophosphoric acid or sulfuric acid.   The non-alkali metal salt is copper, silver, gold, beryllium, magnesium, zinc, cadmium, aluminum, gallium, indium, silicon, tin, lead, titanium, zirconium, hafnium, antimony, bismuth, vanadium, niobium, tantalum, selenium. The water-containing composition according to claim 16, which is a salt of tellurium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, or rhodium, or a combination thereof.   The water-containing composition according to claim 17, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination thereof. The non-alkali metal salt forms a 0.05 to 10 micron thick permanent coating on the surface of the metal when the hydrous composition is applied to the surface;
19. A hydrous composition according to claim 18 wherein the coating reduces wear on the surface of the metal. The non-alkali metal salt forms a 0.05 to 10 micron thick permanent coating on the surface of the metal when the hydrous composition is applied to the surface;
The water-containing composition according to claim 15, wherein the water-containing composition is produced by the process of claim 1. The non-alkali metal salt forms a 0.05 to 10 micron thick permanent coating on the surface of the metal when the hydrous composition is applied to the surface;
The water-containing composition according to claim 15, wherein the water-containing composition is produced by the process of claim 8.

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