JP2008523166A - Process for welding ionic complex mixtures and coatings to surfaces - Google Patents

Abstract

  Compositions and methods for providing a wear-resistant and fuel-saving coating on metal, particularly metal surfaces in internal combustion engines. The ammonium ion source, the alkali metal in the aqueous solution and the coating metal used on the surface are mixed to prepare an electrolyte solution containing a complex mixture of ions. The electrolyte solution will be used to deposit the coating metal on the conductive substrate. The coating metal will include phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof. The electrolyte solution will be dehydrated in a hydrocarbon solvent, thus providing a new material for use as a lubricating oil additive and fuel additive. These new surfaces, when used in internal combustion engines, will significantly reduce the coefficient of friction, smooth the flame front, reduce corrosion, improve fuel efficiency, and reduce hydrocarbon emissions.

Description

CROSS REFERENCE TO RELATED APPLICATIONS N / A STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT N / A BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to the field of aqueous solutions containing mixtures of inorganic and organic ions, their preparation and use. More particularly, the present invention relates to compositions and methods for the preparation of surfaces that improve performance, including surface modifications of phosphorus, sulfur, carbon, boron or bismuth, where the surface modification is a metal part of an internal combustion engine. Extend the life of metal parts containing The new modified surface improves fuel efficiency and reduces hydrocarbon contamination by using an aqueous complex mixture of ions.

2. Description of Related Art Successful silicon deposition has long been sought in the field of coatings. For example, Merkl, US Pat. No. 4,029,747, entitled “Method of Preparing Inorganic And Polymeric Complexes And Products So Produced” , New compositions and methods of making multimetal amides are disclosed. Merckl describes that these composites are suitable for “production of soaps and detergents” and “coating various substrates with one or more of the various metals of the I-VIII group of the periodic table”.

  The characteristics of Merckl's coatings of inorganic polymer compositions, according to the description, indicate that the use of these compositions makes it difficult to use titanium, tantalum, niobium as well as certain metals that could not be previously coated, such as silicon. Soluble metal can be coated. Although silicon has been previously reported to be deposited by vacuum deposition and sputtering, Merck does not appear to have a successful record of silicon metal coating.

  Merckl describes some experiments where silicon is placed in a solution containing ammonium hydroxide, alkali metal hydroxide and non-alkali metal. Several analytical methods described in the Merck patent suggest that nitrogen can be stabilized in alkaline solvents. Merck describes a process that requires an endothermic and exothermic stage to form a polymer composite. Melkull teaches that if the reaction does not become as described, a silicate forms and cannot be reversed, resulting in a result that cannot be used for polymerization purposes. As will be shown later, this is not already true according to the present invention.

  Silicon is a rich and brittle non-metallic substance, found in sand, clay, bauxite, granite and many other minerals. Silicon chemistry first developed in the 1860s and has since found wide application in many industrial uses as sodium silicate, potassium silicate, ferrosilicon and high purity silicon. Sodium and potassium silicates are used as additives in steel production to harden the desiccants, detergent components, flame retardants in cement and steel. See generally Silicon Chemistry: From the Atom to Extended Systems, P. Jutzi and U. Schubert (eds.) (2003) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, ISBN3-527-30647-1.

  Ropp U.S. Pat. No. 4,634,540 describes several methods for producing sodium silicate and / or potassium by reacting silica stone with an alkali metal hydroxide. Ammonium ions were not used in the rop reaction.

  In the past, many attempts have been made to improve the surface properties of metals with the aim of expanding their applications. For example, Teng et al., US Pat. No. 4,533,606, describes a method and aqueous composition that is said to be suitable for electrodeposition of zinc, silicon and phosphorus co-deposition on metal substrates. Has been. However, only the co-deposition containing phosphorus and zinc with silicon has been described, and electro-deposition is time consuming.

  Although McCoy et al., US Pat. Nos. 5,084,263 and 5,310,419, describe the faster electro-deposition of many metallic “inorganic polymeric water complexes”. Silicon is not included there. Dephalco et al. US Pat. No. 5,540,788 describes the formation of an in situ iron-phosphate modified surface in an internal combustion engine. However, the method described by both McCoy et al. And Defalco et al. Requires the use of a strong acid component for its preparation.

  Silicon nitride was developed in the 1960s and 70s in an attempt to develop a sufficiently dense and high strength ceramic, especially as a steel replacement in internal combustion engines. Studies on silicon nitride have revealed high temperature properties to retain high strength and oxidation resistance. Silicon nitride falls into at least three categories. That is, 1) bind and react with silicon nitride, 2) heat compress silicon nitride, and 3) sinter silicon nitride. Sintered silicon nitride has a high density and is more widely used than the other two methods. Important properties of the silicon nitride surface include sufficient density, high temperature strength, excellent thermal shock resistance, excellent wear resistance, sufficient fracture toughness, mechanical fatigue and deformation prevention, sufficient oxidation resistance, and improvement Lubricity.

  However, difficulty in the manufacturing process has prevented this material from becoming a major product as a metal replacement for many applications. The manufacture of silicon nitride ceramic bodies will be relatively complex. For example, Komatsu et al., US Pat. No. 6,678,431, describes a silicon nitride sintered material that constitutes a wear resistant material, which is formed by at least the following procedure. Mixing a specified amount of sintering aid, the necessary additives such as organic binders, and a composition such as Al, Mg, AlN, Ti into a fine powder of silicon nitride; With an average particle size and a very small amount of oxygen. And forming into a molded body having a predetermined shape by a forming method such as uniaxial pressing method, die pressing method or doctor blade method, rubber pressing method, CIP (cold isostatic pressing), etc. Stage to do. Multiple heating steps to remove additives and binders, sintering at reduced pressure and high temperature, and high temperature curing follow the forming phase.

  Despite the manufacturing process has some drawbacks, silicon nitride is nevertheless an example of a glow plug for quick start, a pre-combustion chamber for low emissions, and a turbocharger for delay reduction and emission control It can be used for internal combustion engine parts. The wide use of silicon nitride can only be achieved by better manufacturing methods that produce parts that are cost-effective and competitive. Therefore, the ability to deposit a silicon nitride surface on a metal using an aqueous solution would have very great commercial value in the automotive industry, not to mention the aerospace industry.

  The search for ways to improve fuel efficiency and reduce toxin emissions has been the driving force behind the development of silicon nitride coatings for small parts for internal combustion engines. Recently, regulations on automobiles, such as regulations on fuel consumption and exhaust gas, have become increasingly strict. The reasons behind this are well known, environmental protection, such as air pollution, acid rain, and concerns about fossil fuel depletion, protection of finite hydrocarbon sources around the world and minimization of greenhouse gas Policies are included. Reducing fuel consumption as a counter measure is at least almost certainly the most cost-effective solution at the present time.

  However, many material science approaches that have historically been available to improve effectiveness and improve performance are also constrained. For example, as described in US Pat. No. 6,784,143 to Locke et al., There has been a greater need for less toxic emissions from exhaust gases, mainly hydrocarbons, carbon monoxide. And environmental problems such as emission of pollutants, such as nitric oxide. Catalytic converters in automotive exhaust systems have been used for quite some time to date to reduce pollutant emissions. Such converters are typically used in combination with a metal catalyst such as platinum or a variant thereof and a metal oxide, and are installed in an exhaust stream, such as an automobile exhaust pipe, to remove toxic gases. To a new gas. Decomposed products of zinc dithiophosphate additive for wear reduction and phosphorus components, such as effective anti-wear oil additives, are thought to contaminate the catalyst in these converters. The sulfur component also appears to contaminate the catalyst component used to reduce nitric oxide. Despite the foregoing, the Rock patent invention, although reduced, still requires significant phosphorus and sulfur concentrations.

  Thus, there is a clear pressure in the automotive industry aimed at reducing phosphorus and sulfur content, and phosphorus and sulfur content is an emission consideration rather than increasing them for wear reduction purposes. Therefore, it is a component added to fuel and lubricating oil. Reducing the concentration of phosphorus will definitely be easily achieved by reducing the tolerance of zinc dithiophosphate. However, this comes at the price of reducing the antiwear and antioxidant capacity of the oil (and fuel) components. As is well known in the art, engine manufacturers have already experienced considerable difficulties due to premature engine failure as a result of changing fuel and oil specifications to reduce the concentration of known anti-wear components (especially sulfur). Have experienced.

Thus, methods that provide in situ silicon and nitrogen electroless deposition on metal friction surfaces, including but not limited to internal burning metals, have become a breakthrough in engine technology and have considerable commercial importance. Would both have.
U.S. Pat.No. 4,029,747 U.S. Pat.No. 4,634,540 U.S. Pat. No. 4,533,606 US Pat. No. 5,084,263 U.S. Pat.No. 5,310,419 U.S. Pat. No. 6,784,131 U.S. Pat. No. 6,784,143 Silicon Chemistry: From the Atom to Extended Systems, P. Jutzi and U. Schubert (eds.) (2003) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, ISBN3-527-30647-1 Electroplating: Fundamentals of Surface Finishing, Frederick A Lowenheim (1977) McGraw-Hill BookCompany (TX), ASIN 0070388369

Brief Summary of Some Preferred Embodiments Thus, solving the disadvantages of the prior art, ie providing unique and novel applications for silicon, silicon nitride / alkali or silicon nitride bimetallic metal chemical compositions It is an object of the present invention.

  In certain embodiments, compositions and methods are provided for providing a wear-resistant and fuel-saving coating on a metal, particularly a metal surface in an internal combustion engine. In a preferred embodiment, an ammonium ion source, an alkali metal in an aqueous solvent and a coating metal applied to the surface are combined to produce an electrolyte solution comprising a complex of ionic mixtures. In other embodiments, an electrolyte solution will be used to deposit the coating metal on the conductive substrate. In certain preferred embodiments, the coating metal will include phosphorus, sulfur, carbon, bismuth, boron, silicon and mixtures thereof. In other preferred embodiments, the electrolyte solution will be dehydrated in a hydrocarbon solvent, thereby providing a new material for use as a lubricant and fuel additive. In other preferred embodiments, these new surfaces, when used in internal combustion engines, significantly reduce the coefficient of friction, smooth the flame front, reduce corrosion, improve fuel efficiency, and / or carbonize. Will reduce hydrogen emissions.

  As described in detail below, we have sodium and / or potassium silicate dissolved in water, ammonium hydroxide is placed in an aqueous solution, and is not limited to sodium hydroxide and water. We have found that an alkali metal hydroxide containing potassium oxide is added to an aqueous solution that is subsequently heated to form a new ionic mixture complex, which we assume contains a silicon complex. It is preferred that the temperature rise rapidly when heated to 180 ° F. (82 ° C.) or higher. The reaction is preferably allowed to proceed by its own further exotherm and will produce a clear viscous solution with a pH of 14 and a specific gravity of 1.1. A panel of 1010 steel was immersed in the solution for 30 seconds, after which a very slippery visible film was formed on the metal. The soaked and untreated panels were then immersed in a 3% sodium chloride solution for 3 days, removed and dried. The untreated panel showed red corrosion, but the treated panel had no corrosion. This indicates that the new surface provided excellent corrosion resistance. As will be appreciated by those skilled in the art, other silicates will of course be used without departing from the scope of the present invention. The present invention is not limited to sodium silicate and potassium silicate, but the reaction of metasilicate (inosilicate) cyclosilicate, orthosilicate (nesosilicate) and other silicate minerals. Including the silicate produced by

The above mentioned Merkle patents, in column 10, ll. 57-64, “On the other hand, if the supply of alkali hydroxide is too slow, the resulting formation of NH ₂ groups and the release of hydrogen become insufficient and eroded. Non-alkali metals tend to bind with metals in the form of salts such as sodium silicate, and once this occurs, it may not be possible to return the reaction to obtain the desired complex product. ". Thus, Merck teaches that alkali metal silicates cannot be used to form inorganic polymer composites. Merck does not envisage that new polymer composites can be formed using sodium or potassium silicate.

  In Merckle Example 1 a low purity silicon / potassium / ammonia reaction is described. The reaction phase is described with an endothermic phase lasting 6 hours followed by an exothermic reaction lasting 45 minutes. Using the same elements as described in the Merck example, low purity ferrosilicon of 98.5% silicon and 1.5% iron reacted with ammonium hydroxide, potassium hydroxide and water. The solution was heated to 180 ° F. (82 ° C.) and exothermed within 20 minutes. An endothermic reaction was not included. The solution continued to exotherm for a few minutes and then stopped. A viscous, clear solution with a specific gravity of 1.2 resulted. After cooling, a 1010 steel panel was immersed in the solution, and a transparent and thin film of stickiness was formed on the panel. The formed surface was very slippery. The panel was then left in the humid atmosphere of Houston, Texas for 30 days, but no red corrosion was seen. Therefore, the necessity for the endothermic reaction of Merck seems to be unnecessary for the present invention.

  In order to determine if the composite can be used as a lubricant additive and / or fuel additive, we further experimented with the assumed silicon composite described herein. As described in more detail later, the composite was dehydrated in lubricating oil by heating the oil until all moisture was removed and the oil became clear and bright. At some elevated temperature, chemical salts were included in the complex that settled out of the oil solution. A simple test was devised to determine if the active content remains in the oil solution. A 1010 steel panel was immersed in the oil solution for 1 minute. The panel was removed from the oil solution, wiped dry, and a noticeable thin bright film was present on the surface of the panel. This is taken as an indication that the active inclusions can still be used to weld the hydrocarbon solution to the conductive substrate. Inventors have argued that silicon is dissolved in a hydrocarbon solution, and that a composite is used to deposit a silicon / nitrogen or silicon / nitrogen bimetal surface on the conductive substrate of an internal combustion engine. There is no prior literature to do.

  The inventive oil solution was also tested on a small two-cycle engine to determine if silicon would help improve the fuel efficiency of the two-cycle engine. As detailed below, surprisingly, these tests showed a good trend for improved fuel efficiency and reduced emissions from the two-stroke engine.

  One preferred embodiment of the present invention is to dissolve the silicon / nitrogen and silicon / nitrogen bimetallic compositions in hydrocarbons and alcohols and to conduct in the combustion chamber while the engine is running. Using hydrocarbons to carry active silicon / nitrogen to the surface of the substrate. This provides a new, easy and non-obvious way to form a thin film of silicon nitride on a metal surface by cheap processing in engines, gearboxes, differentials, etc.

  Hydrogen is assumed to affect the level of activity that appears in these supposed silicon composites. According to Mercury column 21, ll. 14-19, “In further analysis using mass spectra, it is observed that nitrogen and atomic hydrogen are released by inorganic polymer composites. It is expected to be released widely up to 1550 ° C. Nitrogen is released at 875 ° C. ”According to the present invention, hydrogen preferably affects the fuel efficiency of hydrocarbons as detailed below.

  As noted above, Lop describes a method for preparing sodium and / or potassium silicates, but does not describe the use of ammonium ions. Lop broadly describes the release of hydrogen gas from the silicate complex (in columns 2, 1.63 to columns 3, 1.40) as follows. "The formation of this complex Si (OH) y produces a gas product by allowing the hydrogen component to be hydrogenated with the exchange of hydrogen atoms and electrons between the silicon particle surface and the trapped oil. The resulting soluble silicate has a clear influence on the viscosity of the oil as well as affecting the tendency of certain oil components to reform .... oil improvement The agent is a negatively charged silicon particle surface in a common solvent .... Negatively charged hydroxide ions transfer their charge to the semiconductor silicon surface of the particle and attach themselves to it. When two or more hydroxide ions adhere to the silicon surface, hydrogen gas is generated ... ".

  The Merck patent teaches that by using mass spectral analysis techniques, hydrogen atoms are released from a silicon / ammonium / alkali metal composition in a significant temperature range from ambient temperature to 1550 ° C. Lop teaches that the hydrogen obtained from the alkali silicate solution reforms the crude hydrocarbon. We envision, based on the present invention, that the hydrogen available in our silicate composition will act as a hydrogenation catalyst for refined fuel in the combustion chamber. Decomposing large hydrocarbon molecules into small gaseous molecules would have the effect of improving the combustibility of refined fuels such as diesel and gasoline. Furthermore, the hydrogenation of purified hydrocarbons will have an initiation effect on the combustion process. It is well established that tetraethyl lead provides detonation effects on the combustion process, resulting in better flammability and better combustion efficiency.

We have found that there is a stable charge in our water-based silicon composites. In the literature, free electrons it is well known that there can be no longer than 1/10 ⁴ seconds in water. It is envisioned that silicon acts as a clathrate to hold hydrogen atoms and electrons separately and spaced apart from the electron shell, allowing further chemical reactions in the appropriate state. Treatments for stabilizing hydrogen atoms and solvated electrons in water have broad implications in the chemical world and will lead to many new chemical applications.

  Clay is one of the most abundant minerals on earth. Clay has many uses because of its unique property of hydrogenating in the presence of fresh water. Clay is a complex of mainly aluminum silicon with a small amount of impurities. Clay is used as a first step in zeolites in a refining process for washing and treating crude oil and catalysts. Clay is a charged particle that “swells” in the presence of fresh water and forms solid walls that allow water, oil, and harmful substances to enter the pores of the clay. The expansion of clay presents a major problem in order to slow down the penetration rate by the drilling rig into the soil during oil drilling operations. Clay is also involved in “hard sandstone”. Hard sandstone is solid with various clays, along with bentonite, one of the most common clays found in oil and gas reserves. The presence of clay in many reserves prevents the use of water flood techniques to facilitate oil recovery. As a result, many billions of barrels of crude oil may not be recovered due to clay expansion. For example, the Department of Energy says that over 10 billion barrels of light crude oil still exist in Pennsylvania, West Virginia, Ohio, and Sandstone, a formation that extends from Lake Erie to Lake Ontario, Canada. I have an estimate. These formations are very shallow, ranging in depth from 200 to 1200 feet (61 to 366 meters), but because of fresh water, these formations gain 5% of all oil on the spot. Only. Inexpensive methods to break down the clay present in these shallow formations enable flooding these reserves, add billions of barrels of recoverable oil to the national supply, and make energy independent To help you achieve.

Because the silicon composition of the present invention is water soluble over a wide pH range, we are montmorillonite ((Na, Ca) (Al, Mg) ₆ (Si ₄ ), a clay commonly referred to as “gumbo”. O ₁₀ ) ₃ (OH) ₆ -nH ₂ O, sodium calcium hydride aluminum magnesium silicate hydroxide) can be split into thin layers in fresh water using the silicon composition prepared according to the present invention Decided to test whether. Surprisingly, Gumbo decomposed into constituent particles in fresh water. Thus, the present invention thus provides a novel method for decomposing clays including montmorillonite clay. This discovery should lead to improved enhanced oil recovery technology and use in hard gas sands, especially because montmorillonite is the main component of bentonite, thus increasing the permeability and porosity in their formation. Used for spreading and boring mud. Similarly, improved decomposition of bauxite, a clay-like mineral containing aluminum ore, into its constituents will reduce the high cost of aluminum refining.

  In other preferred embodiments, the present invention also includes mold and mildew treatment and prevention methods. Mold and mildew cause significant problems, especially in the humid regions of the United States and around the world. Indoor mold is thought to cause asthma and other pulmonary diseases. The silicon composition in the aqueous phase according to the present invention was used to spray 18 "x18" x2 "concrete stones with extensive mold growth. Molds die in less than 30 minutes and silicon forms on the concrete The finished surface was then maintained without mold erosion for 60 days.

  Black mold propagates in several windows of the apartment and causes allergic reactions. The silicate composition of the present invention was used to spray aluminum panels to which mold had adhered. The mold was wiped off and the surface of the aluminum panel was smeared with a silicon composition. After 90 days, there was no mold re-growth, suggesting a very long term application for mold prevention indoors.

  In another preferred embodiment, the present invention includes a concrete sealing method. A piece of concrete was dipped into the silicon composition and then placed in a Mason jar of glass containing 18 API grade crude oil. Oil sticks to concrete and cannot be removed easily even by steam cleaning. Surprisingly, when the treated concrete pieces are removed from the oil and placed in a mason jar containing only fresh water, the oil immediately leaves the concrete and the water remains without being seen on and in the concrete pieces. Floated on top. A coating that seals concrete and forms an oleo-phobic surface would have commercial use.

  In a preferred embodiment, a sticky smooth surface formed on a metal by the silicon / nitrogen composition of the present invention is used on cutting edges such as knives, razor blades, saws, etc. to extend the life of the edges. I showed what I could do. A stainless steel razor blade sold under the Walgreen label was used as the test member. A drop of silicon solution was applied to the blade surface. The blades became more slippery and it soon became clear that the shaving worked very well and was comfortable. These blades have a life of about 5 shaves before being discarded. The treated blades shave smoothly for 30 days, and then treated again, extending the edge life for another 30 days. Thus, a coating was found that could be applied inexpensively and easily to razor blades and all other sharp edges such as saws, knives, and medical devices.

  Similarly, two knives made from 410 stainless steel were used for testing. One knife was coated with a silicon / nitrogen complex and the other knife remained untreated. And when the butane torch was held against an untreated knife, the metal turned bright red in a minute. When cooled, the surface changed to a bluish color, suggesting that high temperatures affected the properties of stainless steel. The same treatment was applied to the treated knife, but the metal did not turn bright red in a few minutes. Even when the knife was cooled, there was no change in the color of the stainless steel. Stainless steel is an inert material and is considered very difficult to have a surface applied either by electroless or electrocoating. Accordingly, the present invention also includes a preferred embodiment having a novel method for enhancing the properties of stainless steel. The ability to form a thin silicon nitride coating on a medical device would assist in attempts to reduce medical costs worldwide. The mixing of microorganisms into the metal gaps of medical devices requires extensive cleaning operations in the autoclave to kill the microbial contaminants. The silicon nitride composition forms a thin coating on the metal surface and on the metal interstices, thereby filling the holes and preventing microorganisms from being present on the metal. This property will provide a cheaper method of sterilization of operating room instruments.

  Other preferred embodiments of the present invention include ice release treatment compositions and methods. Two 6061T6 aluminum 3 "x3" x1 / 8 "panels were used, one coated with a thin film of silicon / nitrogen composition according to Example 2A of the present invention (below), while another The panel remained untreated, the silicon / nitrogen coating was identified by EDAX (Energy Dispersive X-Ray Analysis), and the two panels were formed thick on the surface It had a film of water and was placed in a freezer at −18 ° C. (0 ° F.) One hour later, the panel was removed from the freezer and subjected to a light refraction test on a frozen surface. The panel with the surface quickly dissociated from the cracked nearly unitary sheet of ice, the untreated panel would not dissociate from the ice sheet by cracking, and the ice melted from the surface of the aluminum substrate. Aircraft industry, airplane wing A lot of time and money is spent deicing with ethylene glycol, a toxic chemical, which will prevent water from adhering to the aluminum and forming sticky ice crystals, It will have commercial value and will also alleviate environmental problems caused by deicers.

  Silicates have been widely used as flame retardants since they were discovered in the 1860s. The property of expanding in the presence of a silicate flame and the property of providing a septum are well established. However, the use of silicates for flame protection has been limited in the prior art because silicates do not adhere firmly to the surface of wood, cloth or steel. Accordingly, another preferred embodiment of the present invention is to provide a flameproofing composition and method suitable for solving the problems associated with the prior art. An old dry wood preparation was dipped in a silicate solution according to the present invention and dried. Then it was soaked in water, removed and dried. A butane torch was used to hold the flame in front of the dry wood surface. The fire was held against the wood for 5 minutes, but only a slight charring effect was observed. Wood never helped fire. We envision that the silicate composition will not only make the wood less flammable, but will also serve as a surface to prevent mold and white mold formation and the possibility of termite spread. Two 1010 steel 12 gauge panels were used to test the effect of the preferred embodiment of the invention, including a method to prevent heat conduction. One panel was immersed in the silicate composition for 1 minute and then removed. The other panel was untreated. A butane torch was used to heat the metal to "bright". The panel was held by hand and a fire was applied to the panel. It took less than a minute for the untreated panel to become bright red, and heat was transferred down the full length of the panel, making it too hot to hold. Although the treated panel required about twice as long to reach a bright red state, the heat transfer was significantly inhibited. The silicate foamed and prevented heat conduction to the metal substrate. The panel could be held for a few minutes before the heat eventually made the steel too hot to hold. The nature of silicon compositions that form a thin film on the metal and prevent heat conduction to the base metal has wide application in various commercial fields. For example, steel columns treated with a silicon composition according to the present invention can sufficiently increase the time that they can withstand distortion and fracture by preventing heat conduction as well as possible.

  Ethanol is an alcohol that is a product of organic fermentation. Ethanol reduces emissions by being used as an additive to fuel to improve cleaner burning. In some countries, such as Brazil, ethanol is used exclusively as a renewable energy source. Ethanol is also designated as one of the additives for oxidizing fuel in the United States. The use of ethanol has broad political and environmental support. However, the main obstacle to the further use of ethanol is that ethanol is highly corrosive to metals. Treatments that reduce the corrosive activity of ethanol will find very large markets in the United States and around the world. Accordingly, another preferred embodiment of the present invention is a composition and method that reduces the corrosivity of ethanol to metal surfaces. This embodiment is performed by placing 100 grams of ethanol in a glass beaker. Then, as described in Example 1A (below), 5 grams of a silicon complex according to an embodiment of the present invention was added to ethanol. Salts immediately precipitated from the solution and they seemed incompatible. Ethanol was decanted from salt to another beaker. The 1010 steel panel was immersed in an ethanol solution for 1 minute and then removed. A thin sticky film was formed on the steel panel. The panel was left in the open air of Houston, Texas, where it was wet for 30 days. No corrosion was found on the coated part of the panel. Surprisingly, the active material in the silicon composition is clearly soluble in alcohol and maintains its electrochemical activity, allowing it to be deposited on a metal substrate using ethanol. did. Since ethanol is very corrosive, it is transported in stainless steel trucks and pipelines. The corrosive nature of ethanol prevents its wide use as an oxidant for fuels. Thus, products that can be added to ethanol to prevent corrosion will have significant commercial value.

  Thus, in some preferred embodiments, the present invention provides for adding ammonium hydroxide to a solution of sodium silicate to which potassium hydroxide is added.

  In other preferred embodiments, ammonium hydroxide is added to a solution of sodium silicate to which sodium hydroxide is subsequently added.

  In other preferred embodiments, the above process will be modified by maintaining the temperature of the resulting reaction mixture above 180 ° F. (82 ° C.) for a predetermined time. Without limitation, in certain preferred embodiments, the predetermined time will preferably be 10 minutes or more.

  In other preferred embodiments, ammonium hydroxide is added to a solution of sodium silicate to which potassium hydroxide or sodium hydroxide is added, whereby the resulting solution is dehydrated in gas oil, resulting in All solids are removed by decanting.

  In another preferred embodiment, ammonium hydroxide is added to a solution of potassium silicate to which potassium hydroxide and / or sodium hydroxide is added, whereby the resulting solution is dehydrated in gas oil, resulting in All solids are removed by decanting.

  In another preferred embodiment, ammonium hydroxide is added to a solution of sodium or potassium silicate to which potassium hydroxide or sodium hydroxide is added, whereby the resulting solution is dehydrated in gas oil, resulting in All solids are removed by decanting. The liquid phase is then added to the crankcase (as an oil additive) or to the combustion chamber of a 2-cycle or 4-cycle engine (as a 4-cycle fuel additive or 2-cycle fuel or oil additive). .

  In another preferred embodiment, an aqueous solution of the ionic mixture can be prepared by adding ammonium hydroxide to a solution of sodium or potassium silicate to which potassium hydroxide and / or sodium hydroxide is added, thereby The resulting liquid is dehydrated in light oil and all resulting solids are removed by decanting.

  In other embodiments, ammonium hydroxide is added to a sodium or potassium silicate solution to which potassium hydroxide or sodium hydroxide is added to prepare an aqueous solution of the ionic mixture, whereby the resulting liquid is Dehydrated in light oil, all resulting solids are removed by decanting, and the resulting liquid is added to either the lubricating oil or fuel of the internal combustion engine.

  In another preferred embodiment, an aqueous solution of an ionic mixture can be prepared by adding ammonium hydroxide to a solution of sodium or potassium silicate to which potassium hydroxide or sodium hydroxide is added. The resulting liquid is dehydrated in light oil, all resulting solids are removed by decanting, and the resulting liquid is added to either a gasoline internal combustion engine lubricant or fuel.

  In another preferred embodiment, ammonium hydroxide is added to a solution of sodium or potassium silicate to which potassium hydroxide or sodium hydroxide is added to prepare an aqueous solution of the ionic mixture and the resulting liquid Is dehydrated in light oil, all resulting solids are removed by decanting, and the resulting liquid is added to either the diesel engine lubricant or fuel.

  In another preferred embodiment, a thin sticky film comprising silicon and nitrogen is prepared by a combination of a water soluble ionic solution obtained from a mixture of sodium or potassium silicate with ammonium hydroxide and alkali metal hydroxide. Is applied electrolessly to a metal friction surface by using a precursor that produces an aqueous inorganic composite with light oil at a sufficient temperature on the membrane, after which the composite is added to the lubricating oil or fuel. It is done.

  In other preferred embodiments, additives to the lubricating oil that significantly reduce the coefficient of friction are applied based on the means described by the present invention.

  Another preferred embodiment includes a fuel additive for the introduction of a composite for welding a silicon-nitrogen surface to the internal friction portion of an internal combustion engine. Another related preferred embodiment includes a lubricating oil additive for the introduction of a composite for welding a silicon-nitrogen surface to the internal friction portion of an internal combustion engine.

  Another preferred embodiment includes an additive for ethanol with improved corrosion resistance.

  Other preferred embodiments include the addition of the above composition and application of the above method to provide a composition for use in delamination of clays, particularly montmorillonite clays associated with the recovery of petroleum hydrocarbons. .

  Still other preferred embodiments include treatments and materials to prevent corrosion, mildew, mold, heat and fire, resulting in improvements and thus extending the life of the dangerous object.

  It is well known in the chemical field that ammonia can produce volatile compounds (such as sodium azide) in the presence of alkali metals. Ammonium is released from the aqueous solution by the presence of alkali metals in the solution. Therefore, the ability to synthesize ammonia in a strong alkaline solution near pH 14 would create a new chemical complex with a wide range of commercial applications. Surprisingly, it has now been found that ammonium is maintained in solutions at pH 12 and above when ammonium / alkali metal reacts with selected elements. The formed composite exhibits unique electrochemical properties such as forming a new surface on a metal substrate without using the applied external electromotive force.

  Accordingly, it is an object of the present invention to provide unique and novel ionic alkaline chemical complexes, which in some embodiments comprise a mixture of salts.

In certain embodiments, a composite combination (Y) _X H (NH ₄ ) ₂ HPO ₄ comprising ammonium phosphate is provided, where Y may be any cation with potassium being the preferred cation. In other embodiments, a composite combination (Y) _X (H ₈ N ₂ ) ₄ S comprising ammonium sulfate is provided, where Y may be any cation with the preferred cation sodium. In other embodiments, a composite combination (Y) _X C ₂ H ₇ NO ₂ comprising ammonium acetate is provided, where Y will be any cation. In other embodiments, a composite combination (Y) _X CH ₅ NO ₃ comprising ammonium bicarbonate is provided, where Y will be any cation. In other embodiments, a composite combination (Y) _X B ₄ H ₈ N ₂ O ₇ comprising ammonium borate is provided, where Y may be any cation. In another embodiment, a composite combination (Y) _X H ₂ SO ₄ (BiNH ₄ ) _X is provided. In other embodiments, a composite combination (Y) _X (NH ₄ ) Si _X is provided.

Detailed Description of the Preferred Embodiments The present disclosure is herein considered to be exemplary of the principles of the invention, and with the understanding that it is not intended to limit the invention to what has been described and described in this disclosure. The preferred embodiment of the present invention will be described in detail. The present invention is susceptible to different forms or types of preferred embodiments and should not be construed as limited to the specifically described methods or compositions included in this disclosure. In particular, the various preferred embodiments of the present invention provide a number of different forms and uses of the inventive methods, compositions and their applications.

Examples Composition 1
Example 1A
The following equipment: 4000 ml Kimax beaker, Thermoline Cimarec 2 equipped with magnetic stirrer, Acculab V600 weigher capable of reading 0.1 gram, Accurite A 100 ° -400 ° F. (38-204 ° C.) thermometer was used in the following experiment.

  A solution containing a complex mixture of ions is made up of the following reagents, 200 ml of water, 50 grams of sodium silicate (solid), 25 grams of ammonium hydroxide (29 ° Baume (specific gravity 2.44)), 50 Prepared by the procedure of adding grams of potassium hydroxide (flaked) to a beaker.

A slight ammonia odor was detected. The solution was forced to exotherm by being heated while being stirred. Heating was stopped after the temperature was maintained above 180 ° F. (82 ° C.) for 10 minutes. The solution continued its exotherm for several more minutes, after which it could cool. The solution was analyzed by liquid phase ²⁹ Si NMR (nuclear magnetic resonance) spectroscopy, which identified SiO ₄ as illustrated by the spectrum in FIG.

Example 1B
A solution containing a complex mixture of ions was produced based on Example 1A except that sodium hydroxide was changed to potassium hydroxide. The solution was analyzed by ²⁹ Si NMR (nuclear magnetic resonance) spectroscopy, which identified SiO ₄ as illustrated by the spectrum in FIG.

Example 2A
A 1010 steel coupon includes a complex mixture of ions prepared according to Example 1A when the temperature is less than 140 ° F. (60 ° C.) without the required external electromotive force. Soaked in liquid. A visible sticky film was formed on the steel panel. The panel is analyzed by XPS (X-ray photoelectron spectroscopy) and is illustrated by FIG. 3 (simple scan spectrum), FIG. 4 (high resolution spectrum of Si2p peak) and FIG. 5 (high resolution spectrum of N1s peak). As such, the presence of silicon and nitrogen on the surface of the panel was detected. The solution to another steel panels immersed is analyzed by EDAX, showed results as shown in the spectrum of FIG ^1. An aluminum panel immersed in this solution was analyzed by EDAX and showed results as illustrated in the spectrum of FIG.
¹ Table 4 presents a semi-quantitative, ZAF correction and standardized EDAX results (atomic%).

Example 2B
A 1010 steel specimen is immersed in a liquid containing a complex mixture of ions prepared according to Example 1B when the temperature is below 140 ° F. (60 ° C.) without the required external electromotive force. It was done. A visible sticky film was formed on the steel panel. The panel was analyzed by XPS and silicon on the surface of the panel as illustrated by Fig. 8 (simplified scan spectrum), Fig. 9 (high resolution spectrum of Si2p peak) and Fig. 10 (high resolution spectrum of N1s peak). And the presence of nitrogen was detected.

Example 3
In each of the two glass beakers, 70 grams of montmorillonite I clay was soaked in 100 grams of fresh water. In one beaker, 5 ml of a solution containing a complex mixture of ions prepared according to Example 1A was added to fresh water. Both beakers were closely observed. In the beaker to which the inventive solution was added, the clay slowly delaminated and began to settle to the bottom of the beaker as finely divided particles. In the other beaker, no delamination of the clay was observed. After 24 hours, the clay in the treated beaker had completely separated into components. In the other beaker, the clay was still intact and there were slight signs of clay expansion.

Example 4—Preparation of “Stock Solution 1 (Con1)” 600 grams of Penreco® (Drakeol®) 5 from Penreco® is based on Example 1A. It was added to a glass beaker containing 120 grams of solution containing the prepared ionic complex mixture. The heater was turned on with continuous stirring. The temperature of the mixture rose above 265 ° F. (129 ° C.) and boiled at that temperature for 20 minutes. In 20 minutes, a salt formed and settled from the solution to the bottom of the beaker. The oil phase was bright and transparent. This solution is hereinafter referred to as “preservation stock solution 1”.

Example 5-Preparation of "Additive 1" 5 grams of stock solution for storage 1 prepared according to the procedure described in Example 4 was mixed with 100 grams of Drakeol®. , Stirred. The resulting solution is referred to hereinafter as “Additive 1”. 10 ml of additive 1 was mixed with 200 ml of diesel fuel. Additive 1 was fully incorporated into the diesel fuel.

Example 6
4 grams of additive 1 and 225 grams of unleaded gasoline were mixed in a beaker. Additive 1 was mixed in gasoline.

Two-cycle engine test The mixture prepared according to Example 6 was used for experiments to test fuel efficiency measurements and “do no harm” in a two-cycle engine. . The engine selected for testing was a Homelite 2-cycle leafblower with a 30 cc (ml) engine. The requirement to rotate the blower at high speed (high rpm) places a load on a small engine. The engine is always driven in the range of 7200 rpm with a constant load. Two-cycle engines typically use a 50: 1 ratio of fuel and oil and are difficult to lubricate and have poor fuel efficiency. Two-cycle lubricants that are currently widely used to lubricate and protect engines from damage are large quantities of “brightstock”, a highly toxic and contaminating heavy component in oil. Included. This type of two-cycle engine will typically stop within 20 minutes if not properly lubricated. Thus, a lubricant made of a silicon-containing material will provide 2-cycle engine protection against shutdown and failure.

Example 7 (comparison)
The fuel was prepared using standard 2-cycle oil at a 50: 1 fuel: oil mix ratio. Two control runs were performed on the new engine, each run using 225 grams of gasoline mixed with 4.5 grams of standard 2-cycle oil. The “baseline” control run length (eg, time to run out of fuel) was determined by the average of the two run lengths, resulting in a baseline of 29 minutes 45 seconds. A 1 pint (0.473 liter) treated 2-cycle oil was then prepared containing 5% (by weight) of the stock solution 1 for storage prepared according to Example 4. Thereafter, four identical operational tests were performed. Each used 225 grams of gasoline mixed with 4.5 grams of treated 2-cycle oil and the test engine was run until it stopped due to fuel depletion. In each of the four tests, the time to run out of fuel was measured. The results obtained from the four runs are shown in Table 1 below.

  The average of four operational tests (using preservation stock solution 1 as an additive) was 33 minutes and 13 seconds compared to 29 minutes and 45 seconds in the control operation (reference-no addition), The use of fuel for operation has decreased. A significant reduction in particulate emissions was also seen with the test mixture prepared with the stock solution 1 additive for storage. The engine did not stop and actually seemed to run more smoothly with the test mixture prepared with stock solution 1 for storage. This test showed that stock stock 1 additive for storage improves fuel efficiency, reduces emissions and does not harm the engine.

Example 8
300 grams of methyl ester (Soy Methyl Ester from Columbus Foods, Chicago, Ill.) Is placed in a beaker and contains a complex mixture of ions prepared according to Example 1A 15 grams of solution was added there. The solution started to form bubbles when heated to 200 ° F. (93 ° C.) or higher, and cooled to form soap. This example mixture was considered not to be a candidate for fuel or lubricant additives.

Example 9
5 grams of stock solution 1 was added to 100 grams of methyl ester, which was thoroughly mixed therein. The resulting mixture was used as a fuel additive at a ratio of 1 ounce (28 grams) of fuel additive to approximately 10 gallons (38 liters) of automotive gasoline or diesel fuel.

Example 10
0.1 grams of ammonium paratungstate (solid) was added to the 40 grams ionic complex mixture produced according to Example 1A with stirring until the solid dissolved. A 1010 steel panel was then immersed in the resulting solution and removed after one minute. A visible thin firm adherent film was formed on the metal substrate. The surface of the panel is analyzed by EDAX and the results obtained are illustrated by the spectrum shown in FIG. The presence of tungsten and silicon was detected on the metal surface.

  The solution of ammonium paratungstate described above is then generally described in Example 4 by heating to 300 ° F. (149 ° C.) or higher with stirring until a salt forms and settles to the bottom of the glass beaker. Using a simple procedure, it was dehydrated with Drakeol® 5. When the temperature was about 180 ° F. (82 ° C.) and a 1010 steel panel was inserted into the resulting solution, a visible thin film was present on the panel. This panel was then analyzed by EDAX. The results obtained are illustrated by the spectrum provided in FIG. The presence of tungsten and silicon was detected at the surface.

Example 11
0.1 grams of ammonium molybdate (solid) was added to the 40 grams ionic complex mixture produced according to Example 1A with stirring until the solid dissolved. A 1010 steel panel was then immersed in the resulting solution and removed after one minute. A visible thin firm adherent surface was formed on the metal. The panel surface was then analyzed by EDAX. The result is illustrated by the spectrum provided in FIG. Silicon and molybdenum were detected on the metal surface.

  Electroless deposition of tungsten and molybdenum from an aqueous solution is another new feature of the present invention. The prior art teaches that such welding is not possible. For example, Frederick A Lowenheim's traditional textbook “Electroplating: Fundamentals of Surface Finishing”, 1977, McGraw-Hill Book Company , Texas, ASIN0070388369 (page 141) "From the perspective of their electrode potential, it would be possible to electrocoat metals such as tungsten and molybdenum from an aqueous solution at a pH of about 5. Nonetheless. (Despite claims in the literature, these metals are not capable of depositing only that material from aqueous solutions. ”Therefore, electroless deposition from aqueous solutions of tungsten and molybdenum along with other flame retardant metals is new in the industry. It is. Silicon / flame retardant metal surfaces will find a wide range of commercial applications. For example, the metal surface is protected, the friction coefficient is reduced, the corrosion is prevented, and the metal is hardened. As described above, high heat resistance can be imparted. Other specific areas of possible applications include fuel additives for jet turbine engines in airplanes in addition to the use of ground turbine equipment. Temperature barriers are readily formed by the method of the present invention for use in components designed for thermal environments such as superalloy turbine and gas turbine engine combustor and booster components. Let's go. The silicon-nitrogen will diffuse to the surface of the jet turbine components and form a heat resistant (and possibly reflective) coating. There were no known methods for coating jet turbine engine components today, including either keeping away from the engine and using either component replacement or metallizing sprays. Currently used methods impose a clear economic burden on turbine owners due to both downtime and replacement costs for parts and materials.

Other parts of the commercial applications have significant potential value is a burner for industrial combustion systems for a gas fired furnace and low NO _X Industrial pyrolysis furnace for heat treatment as in Example. Combustion of natural gas to generate a substantial amount of nitric oxide to improve the natural gas burner design, much time and money to more reduce them of the NO _X emission are spent. A new low NO _X burner will reduce NO _X emissions over time. However, the volume ratio of 10 parts per billion of about metals in natural gas, gradually accumulate in the nozzle of the burner, will increase the NO _X by affecting the flow pattern (flowpattern). Heat resistant to industrial burners extend significantly the useful life of the burner, to sustain low NO _X emissions. Such a heat-resistant coating has the further advantage that it may allow the use of less expensive burner materials. A thin coating of silicon nitride, for example, der that the flow characteristics of the combustion gas, and less emissions NO _X, can be improved so as to impart a further advantage with respect to optional burner design to improve the performance of the burner Let's go.

4-cycle engine test Example 12 (comparison)
For this example test, a 2000 Lincoln Town Car with a 4.6 liter engine and automatic transmission was used. The baseline fuel consumption value was initially determined by running the car continuously over 300 miles (480 km) at about 72 MPH (115 km / h) with normal unleaded fuel. The resulting reference average fuel consumption was 22.4 MPG (9.4 km / l). Thereafter, the fuel tank is based on the invention described above in Example 9 (1 ounce (28 grams) fuel additive to 10 gallon (38 liters) Diamond Shamrock brand regular unleaded fuel). Refilled with additives. The test vehicle ran on almost the same highway at almost the same speed (72 MPH (115 km / h)) in almost the same environment. The onboard computer showed that the car achieved 25.9 MPG (10.9 km / l) with fuel treated with additives. This corresponds to a reduction in the use of 3.5 gallons (13.3 liters) of fuel per tank or an increase in fuel efficiency of 15.6%.

Example 13 (comparison)
It has a 4.9 liter engine and a standard 5-speed manual transmission, uses 325,000 miles (520,000 km), and uses the standard unleaded fuel to 15.5 MPG (6.51 km / l) Ford's 1991 Ford F150 pickup truck defined by Additive 1 prepared according to the procedure described above in Example 5, which is 1 ounce (28 oz.) For 10 gallons (38 liters) of conventional unleaded fuel Gram) of Additive 1 was tested. Under the same test conditions as described above for Example 12, this test vehicle has a fuel efficiency of 19.67 MPG (8.26 km / l), which is a fuel efficiency gain of 26.9%.

Example 14 (comparison)
A 1998 Chevrolet CK3500 four-wheel drive vehicle (4x4) with a 6.5 liter engine running 184,165 miles (294,664 km) was used as a test vehicle. The standard fuel efficiency was set to 14.7 MPG (6.17 km / l). A single test run was then performed on the test vehicle to set the standard. Thereafter, three test runs were performed using Additive 1 to normal ground vehicle diesel fuel. The rate of addition was 1 ounce (28 grams) of Additive 1 for 10 gallons (38 liters) of diesel fuel. The results are listed in Table 2 below.

Example 15 (Comparison)
For the examples below, a diesel generator with a 150 KW Fiat engine was used. The Fiat engine was used for 13,850 hours before testing. The purpose of the test is to determine the effect on fuel efficiency and environmental emissions of any additive prepared in accordance with the present invention. In general, the engine emitted significant particulates when it started, and continued to emit visible smoke during normal operation. The generator was set to a maximum load of 33% for this test. The reference value for fuel use was determined by filling the fuel tank to the top of the tank. The diesel engine was then started and the generator operated with a load of 33% in 8 hours. Subsequently, the fuel tank was refilled and the fuel efficiency was determined by examining the amount used to fill the tank. The volume of the fuel tank was 100 gallons.

  As described in Table 3, the fuel consumption of the test with additive 1 described above was 3.634 gallons (13.8 liters) per hour, whereas the fuel (without additive 1) The standard of consumption was 4.075 gallons (15.5 liters) per hour. This corresponds to a fuel consumption reduction of about 9.24%.

As further described, the test engine produced relatively severe particulate emissions during start-up for baseline operation. That is no exception for diesel engines. After the engine was treated, there was a very significant reduction in particulates seen at start-up, suggesting an improved combustion process.

Composition 2
An analysis of low purity silicon / potassium is described in the Merck patent (see Example 1 of Merkul in column 23). As mentioned above, the Merkuru method used an endothermic phase lasting 6 hours before an exothermic phase lasting 45 minutes. According to an embodiment of the invention, the reaction scheme is used with new modifications, where the addition rate of alkali metal is changed and no endothermic reaction is used.

Example 16
In this example, 616 grams of ferrosilicon rock containing about 75% silicon and about 25% iron was used, and the rock size was about 1 cm (about inches). Other reagents included 2000 grams of ammonium hydroxide (26 ° Baume (specific gravity 2.18)) and 616 grams of potassium hydroxide (flaked). The raw material was added as quickly as possible and then pushed to an exothermic reaction by applying heat to the vessel. The exothermic reaction lasted for 45 minutes resulting in a clear viscous fluid. And specific gravity was measured with 1.2. The resulting solution was decanted from unreacted ferrosilicon rock.

Example 17
Approximately one hour after the preparation of the solution described in Example 16, a 1010 steel panel was immersed in the solution for 30 seconds and then removed. The panel was then analyzed by EDAX. The result of the analysis is shown in the spectrum presented in FIG. Silicon was detected on the surface of the metal.

Example 18—Preparation of “Stock Solution 2 (Con2)” In a 4000 ml beaker, 600 grams of Drakeol® 5 was added, and 120 grams of ferrosilicon solution prepared according to Example 16 was added. It was. The solution was heated with stirring. The salt settled above 300 ° F. (149 ° C.), leaving a clear and bright solution, suggesting that all water was removed. The heater was turned off and the temperature dropped to 180 ° F. (82 ° C.) when a 1010 steel panel was immersed in the oil solution for 1 minute. When the panel was removed, a thin adherent film was observed on the metal. The panel was then analyzed by EDAX. The results are presented in the spectrum shown in FIG. Silicon is detected on the metal surface, which suggests that one of the soluble silicon in the oil is deposited on the metal from an oil-based solution. This solution is hereinafter referred to as “preservation stock solution 2”.

  Stock stock solution 2 was prepared at 150 neutral solvent BP901 base oil at a ratio of 1 gram stock solution 2 to 20 grams neutral solvent oil to produce oil and lubricating oil additives. ). Although 150 neutral solvent BP901 base oil was used in this example, those skilled in the art will recognize any base oil made from solvent refined paraffinic lubricating fractions or any similar oil, for example US350H Group 2 oil. It will be understood that using it will have satisfactory results.

4-Cycle Engine Test Example 19
5 grams of stock solution 2 for storage prepared according to Example 18 was stirred into 100 grams of Drakeol® 5. The resulting mixture, hereinafter referred to as “Additive 2”, is placed in a 2000 Lincoln Town Car fuel tank already mentioned in the text relating to Example 12, with a ratio of 10 One ounce (28 grams) of Additive 2 to gallon (38 liters) of regular diamond shamrock brand unleaded fuel. As described with respect to Example 12, the vehicle's baseline fuel consumption was previously set at 22.4 MPG (9.4 km / l). The test vehicle traveled 310 miles (496 km) at an average speed of 72 MPH (115 km / h). During the first 100 miles (160 km), the onboard computer recorded 24.5 MPG (10.3 km / l). For the remainder of the test, the onboard computer recorded 27.4 MPG (11.5 km / l), and an improvement in fuel efficiency of 5 MPG (2.1 km / l) or 22.3% was seen. This represents a further improvement in fuel efficiency over the results of Example 12 using 3.5 MPG (1.47 km / l) or 15.6% stock stock 1 for storage.

Example 20
In this example, Additive 2 is used at a rate of 1 ounce (28 grams) to 10 gallons (38 liters) of diamond shamrock brand unleaded fuel (currently 334,000 miles (534,400 km)) Tested on a Ford 150 pickup truck of Example 13). The car traveled 220 miles (352 km) and achieved 19.37 MPG (8.14 km / l). This is similar to the result achieved in Example 13.

Additional Metal Testing Example 21
In this example, a stoichiometric amount of monobasic ammonium phosphate is dissolved in water. The pH of the solution is raised to 14 by the addition of alkali metal hydroxide. The resulting solution is then heated to 180 ° F. (82 ° C.) or higher and maintained at an elevated temperature for 20 minutes or until there is no ammonia odor. Then, when a 1010 steel panel is immersed in the solution for 20 seconds, a thin adherent film is formed on the metal. A stainless steel knife was immersed in the solution for 30 seconds, removed and dried. A thin adherent film was formed on the stainless steel. Stainless steel is a passivating metal alloy, and to obtain a new surface, it is important to accept a new surface without putting it in a plating bath with an enormous preparation in a thin nitric acid solution and the power that immediately follows it. No. The solution contains ammonium / alkali metal / phosphorus and water. Thereafter, the solution is dehydrated by heating in hydrocarbon oil. A 1010 steel panel was soaked in an oil solution for 30 seconds and a thin adherent film was formed on the steel panel.

Example 22
In this example, a stoichiometric amount of ammonium sulfate is dissolved in water. The pH of the aqueous solution is raised to 12 or higher, after which the solution is heated to 180 ° F. (82 ° C.) or higher and maintained at that temperature until there is no ammonia odor. A stainless steel knife is then immersed in the solution, and a thin adherent film is formed on the stainless steel portion. The solution contains ammonium / alkali metal / sulfur and water. The solution is then dehydrated by heating in hydrocarbon oil. A 1010 steel panel was immersed in the oil solution for 30 seconds, and a thin adherent film was formed on the steel panel.

Example 23
In this example, ammonium acetate is dissolved in water. Thereafter, the pH of the solution is raised to 12 or higher and maintained at a temperature of 180 ° F. (82 ° C.) or higher until the ammonia odor disappears. The solution contains ammonium / alkali metal / carbon and water. The solution is then dehydrated by heat in the hydrocarbon oil.

Example 24
In this example, a stoichiometric amount of ammonium borate is dissolved in water. Thereafter, the pH of the solution is raised to 12 or more by adding an alkali metal and heated for 20 minutes or until there is no ammonia odor. The solution contains ammonium / alkali metal / boron. When a stainless steel panel is immersed in the solution, a thin adherent film is formed on the stainless steel. The solution is then dehydrated by heat in hydrocarbon oil. When the 1010 steel panel was immersed in the oil solution, it formed a thin adherent film on the metal.

Example 25
In this example, 54.4 grams of bismuth BB's are mixed with boiling sulfuric acid and water. The solution is decanted and the bismuth BB bullet is washed with water, dried and weighed. A total of 2.4 grams of bismuth dissolved in the solution having a pH of 2 or lower. The solution was raised to pH 8 by adding ammonium hydroxide and further raised to 12 or more by adding potassium hydroxide. The solution was then heated to 180 ° F (82 ° C) or higher until the ammonia odor disappeared. When a 1010 steel panel was immersed in the solution, a thin adherent film formed on the steel panel. The solution was then heated in hydrocarbon oil and dehydrated. When the 1010 steel panel was immersed in the oil solution for 30 seconds, a thin adherent film formed on the steel panel.

Example 26
In this example, ferrosilicon (75% silicon (Si)) is placed in a reaction vessel. Then, ammonium hydroxide, alkali metal hydroxide and water are placed in the reaction vessel. The vessel is then heated to 180 ° F. (82 ° C.) to cause an exothermic reaction that continues until the solution is too viscous to support further reaction.

  An ethanol / methanol solution is placed in a glass beaker. A weighed amount of an aqueous solution of silicon is poured into the alcohol mixture. Immediate salt settling occurs. Then, when a 1010 steel panel is immersed in the solution for 30 seconds, a thin adherent film is formed on the steel panel.

  Thereafter, the aqueous solution of silicon is heat dehydrated in hydrocarbon oil, and some silicon is partially solubilized in the oil. The sulfur oil of Example 22 (above) is then mixed with silicon oil and the oil is mixed. A beaker of ethanol / methanol is added to the vessel and sulfur / silicon oil is added to the ethanol / methanol solution. A 1010 steel panel is then immersed in a sulfur / silicon oil solution for 30 seconds and then removed. A thin adherent film formed on the steel panel. Currently, ethanol is recommended as a way to reduce dependence on petroleum resources. Ethanol has limitations in solution transport and handling. Ethanol is very corrosive and therefore any system capable of forming a film on a metal in contact with ethanol will have high value.

Example 27
Biodiesel is also recommended as a way to reduce dependence on oil. For example, biodiesel is a mixture of 80% hydrocarbon diesel fuel and 20% methyl ester. Methyl esters are derived from vegetable oils, primarily soybean oil, and are processed to remove glycerin. The methyl ester can then be added to the hydrocarbon diesel in any proportion and used for combustion purposes. The aqueous solution of Example 1A is first heat dehydrated in hydrocarbon oil. The resulting solution is then added to the methyl ester and mixed thoroughly. A 1010 steel panel is immersed in the modified methyl ester for 30 seconds. A thin adherent film is deposited on the steel substrate. Thus, the methyl ester will be used to provide a thin adherent film on all metal parts in the internal combustion engine.

  While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described in this disclosure are illustrative only and not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of the invention is not limited by the description set forth above, but only by the following claims, which include all equivalents of the subject matter of the claims.

  The examples provided in this disclosure are presented for purposes of illustration and description only and are not intended to limit the claims or embodiments of the invention. While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. Processing criteria, accessory processing equipment, etc. for any given implementation of the invention will be apparent to those skilled in the art based on the disclosure herein. The embodiments described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. The use of the term “optionally” with respect to any element of the invention is intended to mean that the element in question is needed or not needed. Both options are intended to be within the scope of the invention.

  Citation of references in the Description of the Related Art, in particular any discussion of references that would have a publication date after the priority date of the present application, is an admission that it is prior art to the present invention. Absent. The disclosures of all patents, patent applications, and publications cited herein are incorporated by reference in their entirety to the extent that they provide examples, procedures, or other details that supplement those described herein. Introduced during the present disclosure.

It is a spectrum figure by ²⁹ SiNMR of the aqueous solution containing the complex mixture of the ion based on this invention. It is a spectrum figure by ²⁹ SiNMR of the aqueous solution containing the complex mixture of the ion based on this invention. 1 is a spectrum diagram by simple scanning XPS of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. FIG. 3 is a high resolution XPS spectrum diagram of the Si2p peak of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. 4 is a high resolution XPS spectral diagram of the N1s peak of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. 2 is an EDAX spectrum diagram of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. 2 is an EDAX spectrum diagram of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. 1 is a spectrum diagram by simple scanning XPS of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. FIG. 3 is a high resolution XPS spectrum diagram of the Si2p peak of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. 4 is a high resolution XPS spectrum diagram of the N1s peak of a steel panel treated with an aqueous solution containing a complex mixture of ions according to the present invention. FIG. 2 is an EDAX spectrum diagram of a steel panel treated with an aqueous solution containing a complex mixture of ions comprising silicon and tungsten according to the present invention. FIG. 6 is a spectrum diagram by EDAX treated with a solution containing an oil containing silicon according to the present invention. FIG. 3 is a spectrum diagram by EDAX of a steel panel treated with an aqueous solution of a complex of ions containing silicon and molybdenum according to the present invention. FIG. 2 is an EDAX spectrum diagram of a steel panel treated with a solution made from ferrosilicon according to the present invention. FIG. 6 is a spectrum diagram by EDAX treated with a solution containing an oil containing silicon according to the present invention.

Claims (45)

It is an additive for improving the performance of the engine, and contains ammonium, an alkali metal, and a coating component in an aqueous solution.
An additive wherein the coating component is selected from the group consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof.   The additive according to claim 1, further comprising a hydrocarbon oil.   An engine additive consisting essentially of an ammonium ion source, an alkali metal ion source, a coating component and a hydrocarbon.   4. The additive of claim 3, wherein the coating component is selected from the group consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof.   4. The additive of claim 3, wherein the coating component is selected from the group consisting of ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium borate, metallic bismuth dissolved in sulfuric acid solution, ferrosilicon, and combinations thereof.   4. The additive of claim 3, wherein the hydrocarbon comprises an oil selected from the group consisting of neutral solvent oil, synthetic oil, mineral oil, vegetable oil, methyl ester and combinations thereof. A method for preparing an additive for improving fuel performance comprising:
Preparing an aqueous mixture comprising ammonium, an alkali metal and a coating component and heating the aqueous mixture;
The method wherein the coating component is selected from the group consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof.   The method of claim 7, further comprising the step of dehydrating the aqueous mixture.   The method of claim 8 further comprising the step of precipitating the salt.   The method of claim 9, further comprising dissolving in a hydrocarbon oil. An aqueous composition having a pH greater than 9 and capable of being dissolved in a hydrocarbon to improve fuel efficiency,
The aqueous composition is formed by a combination of an alkali metal, an ammonium ion source, and a coating component;
An aqueous composition wherein the coating component is selected from the group consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof.   The aqueous composition according to claim 11, wherein the alkali metal is sodium.   The aqueous composition according to claim 11, wherein the alkali metal is potassium.   12. The aqueous composition of claim 11, wherein the ammonium ion source is selected from the group consisting of ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium borate, ammonium hydroxide, and combinations thereof.   The aqueous composition is dissolved in a hydrocarbon oil selected from the group consisting of neutral solvent oil, synthetic oil, mineral oil, vegetable oil, methyl ester and combinations thereof, and the dissolved composition is miscible in diesel fuel. The aqueous composition according to claim 11, which is stable and stable.   Providing an ammonium ion source; providing an alkali metal ion source; providing a coating component; dissolving the mixture in a liquid hydrocarbon to form an additive; Using the composition for an internal friction surface of an engine.   The method of claim 16, wherein the coating component is selected from the group consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon and combinations thereof.   18. The method of claim 17, wherein the liquid hydrocarbon is selected from the group consisting of neutral solvent oil, synthetic oil, mineral oil, vegetable oil, methyl ester, and combinations thereof.   19. The method of claim 18, wherein the ammonium ion source is selected from the group consisting of ammonium phosphate, ammonium sulfate, ammonium acetate, ammonium borate, ammonium hydroxide, and combinations thereof.   20. The method of claim 19, further comprising dehydrating the aqueous mixture and precipitating the salt.   20. The method of claim 19, wherein at least one additional metal of group I-VIII of the periodic table is also dissolved in the additive.   20. The method of claim 19, further comprising electrolessly depositing a silicon surface on at least one conductive substrate.   The method of claim 16, wherein the internal combustion engine comprises a diesel engine.   The method of claim 16, wherein the internal combustion engine comprises a gasoline engine.   The method according to claim 16, wherein the fuel consumption of the internal combustion engine is improved by at least 5%. A method of preparing an additive that improves the performance of an internal combustion engine, comprising:
Preparing an aqueous solution of silicate, mixing an alkali metal hydroxide with the solution, mixing a hydrocarbon with the solution, and heating to remove water and precipitate the salt;
The method wherein the silicate is selected from the group consisting of sodium silicate, potassium silicate, ferrosilicon and combinations thereof, and the alkali metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide and combinations thereof.   27. The method of claim 26, wherein the silicate is sodium silicate or potassium silicate.   27. The method of claim 26, wherein the silicate is ferrosilicon.   27. The method of claim 26, wherein the alkali metal hydroxide is sodium hydroxide.   27. The method of claim 26, wherein the alkali metal hydroxide is potassium hydroxide.   28. The method of claim 27, wherein the alkali metal hydroxide is potassium hydroxide.   27. The method of claim 26, wherein the hydrocarbon is selected from the group consisting of neutral solvent oils, synthetic oils, mineral oils, penleco dragaches, methyl esters, and combinations thereof.   The method of claim 32, wherein the hydrocarbon is a neutral solvent oil.   The method of claim 32, wherein the hydrocarbon is a synthetic oil. A composition for changing a metal surface,
Providing an aqueous solution comprising silicate, ammonium hydroxide, and alkali metal hydroxide, mixing the hydrocarbon with the resulting solution, and heating to remove water and precipitate the salt Prepared by stages,
The silicate is selected from the group consisting of sodium silicate, ferrosilicon, potassium silicate and combinations thereof, and the alkali metal hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide and combinations thereof;
A composition that forms a coating upon contact with a metal surface.   36. The composition of claim 35, wherein the preparation of the composition further comprises combining the composition with a lubricating oil.   36. The composition of claim 35, wherein the preparation of the composition further comprises combining the composition with a fuel.   Preparing a composite mixture of ions comprising a silicon ion source, an ammonium ion source, and an alkali metal ion source, dissolving the mixture in a hydrocarbon liquid to form an additive, and converting the additive into an internal combustion A method of preparing an inorganic aqueous composition comprising applying to an internal friction surface of an engine.   40. The method of claim 38, wherein at least one additional metal of Group I-VIII of the periodic table is also dissolved in the additive.   40. The method of claim 38, further comprising electrolessly depositing a silicon surface on at least one conductive substrate.   40. The method of claim 38, further comprising electrolessly depositing the bimetallic silicon surface on at least one conductive substrate.   42. The method of claim 41, wherein the internal combustion engine comprises a diesel engine.   42. The method of claim 41, wherein the internal combustion engine comprises a gasoline engine.   43. The method of claim 42, wherein the fuel efficiency of the internal combustion engine is improved by at least 5%.   44. The method of claim 43, wherein the fuel efficiency of the internal combustion engine is improved by at least 5%.

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