Hybrid vehicle systems

(Cross-reference of related applications) This application is a partial continuation of US Patent Application No. 11 / 963,380 filed on December 21, 2007, and a partial continuation of US Patent Application No. 12 / 167,863 filed on July 3, 2008. A partial continuation of the application, US Patent Application No. 12 / 202,076, filed August 29, 2008, all of which are incorporated herein by reference in their entirety.

The present invention relates to an aqueous hybrid metal oxide polymer vehicle system.

Photocatalytic and self-cleaning aqueous coating compositions and methods are known in the art. Compositions containing metal peroxides have been used to form colorless and transparent adhesive coatings on substrates containing microparticulate substrates. Coating compositions containing nanoparticles have been used to bond nanoparticles to substrates.

In one aspect, the composition comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide. In one embodiment, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some embodiments, the transition metal of the transition metal peroxide is the same as the transition metal of the transition metal oxide. The transition metal can be selected from the group consisting of titanium, zinc, and combinations thereof.

In some practices, the composition comprises an additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, and combinations thereof. In some cases, the composition comprises a filler. The filler may be substantially inert. Fillers include, for example, carbon nanotubes. The weight of the filler may exceed the weight of the transition metal in the composition.

In another aspect, the method of preparing a composition comprises the step of preparing a first mixture and the step of boiling the first mixture at a pressure higher than atmospheric pressure to form a composition. The first mixture contains organic functional silanes, transition metal peroxides, and aqueous carriers. The composition formed comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide.

In some practices, the composition formed by boiling the first mixture at a pressure above atmospheric pressure further comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some cases, the first mixture comprises at least one additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, metal salts, fillers, and combinations thereof. The first mixture may be in the form of a colloidal suspension. The organic functional silane is, for example, bis (triethoxysilyl) methane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, octochloro-trisiloxane, tetraethoxysilane, or any of these. It may be a combination.

In one embodiment, the method further comprises combining an aqueous solution containing a peroxide with a colloidal suspension containing an amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension. The colloidal suspension contains a transition metal peroxide. The method involves combining a transition metal salt and an acid with an aqueous carrier to form a second mixture, substantially neutralizing the second mixture, filtering the second mixture to obtain an amorphous metal hydroxide. It also includes a step of forming and a step of suspending the amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension.

Other practices include compositions prepared by the methods described above.

In another embodiment, the method for preparing the article is a step of preparing a composition containing an aqueous carrier and a condensation product of an organic functional silane and a transition metal peroxide, a step of applying the composition to the surface of a substrate. , And the step of removing the aqueous carrier to form an article with a coating on the surface of the substrate. In some embodiments, the coating is removed from the substrate to form nano-sized particles in powder form.

In some practices, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. The thickness of the coating can be less than about 10 nm. The coating is covalently bonded to the surface of the substrate. In some embodiments, the substrate is porous. In certain embodiments, the substrate is granular.

In one aspect, the composition comprises an aqueous carrier and a condensation product of a silicon peroxide and a transition metal peroxide. In another aspect, the preparation of the composition comprises the step of preparing the first mixture and the step of boiling the first mixture at a pressure higher than atmospheric pressure to form the composition. The first mixture comprises a silicon peroxide, a transition metal peroxide, and an aqueous carrier. The composition formed comprises an aqueous carrier and a condensation product of a silicon peroxide and a transition metal peroxide. In another embodiment, the preparation of the article is a step of preparing a composition containing an aqueous carrier and a condensation product of a silicon peroxide and a transition metal peroxide, a step of applying the composition to the surface of a substrate, and the like. And the steps of removing the aqueous carrier to form an article with a hybrid metal oxide coating on the surface of the substrate.

In one embodiment, the composition comprises crystalline particles less than about 10 nm in diameter. The particles can include hybrid metal oxides, transition metal oxides, or combinations thereof. The composition can include silicon oxide and transition metal oxides. The weight percentage of silicon oxide based on all metal oxides can be at least about 50% by weight, at least about 95% by weight, or at least about 99% by weight. The weight percentage of transition metal oxides based on total metal oxides can be at least about 95% by weight. In some cases, the condensation product comprises silicon, titanium, zirconium, or any combination thereof.

In some practices, the composition formed by boiling the first mixture at a pressure above atmospheric pressure comprises crystalline particles less than about 10 nm in diameter. The crystalline particles can include hybrid metal oxides, transition metal oxides, or any combination thereof. The first mixture can be in the form of a colloidal suspension. In some cases, the peroxide containing aqueous solution is combined with a colloidal suspension containing amorphous metal hydroxide and silicon hydroxide in the aqueous carrier and contains transition metal peroxide and silicon peroxide. Form a colloidal suspension. In some embodiments, silicon chloride, transition metal chloride, and acid are combined with aqueous carriers to form a mixture. The mixture is neutralized and filtered to form amorphous metal hydroxides and silicon hydroxides. The amorphous metal hydroxide and silicon hydroxide are suspended in an aqueous carrier to form a colloidal suspension containing the amorphous metal hydroxide and silicon hydroxide.

In some practices, the preparation of the composition comprises the step of preparing a mixture containing a silicon peroxide, a transition metal peroxide, and an aqueous carrier. The mixture can be boiled at a pressure higher than atmospheric pressure to form a composition comprising an aqueous carrier and a condensation product of a silicon peroxide and a transition metal peroxide. In one embodiment, the composition comprises crystalline nanosized particles containing transition metal oxides.

In one aspect, the composition comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide. In one embodiment, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some embodiments, the transition metal of the transition metal peroxide is the same as the transition metal of the transition metal oxide. The transition metal can be selected from the group consisting of titanium, zinc, and combinations thereof.

In some practices, the composition comprises an additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, and combinations thereof. In some cases, the composition comprises a filler. The filler may be substantially inert. Fillers include, for example, carbon nanotubes. The weight of the filler may exceed the weight of the transition metal in the composition.

In another aspect, the method of preparing a composition comprises the step of preparing a first mixture and the step of boiling the first mixture at a pressure higher than atmospheric pressure to form a composition. The first mixture contains organic functional silanes, transition metal peroxides, and aqueous carriers. The composition formed comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide.

In some practices, the composition formed by boiling the first mixture at a pressure above atmospheric pressure further comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some cases, the first mixture comprises at least one additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, metal salts, fillers, and combinations thereof. The first mixture may be in the form of a colloidal suspension.

In one embodiment, the method further comprises combining an aqueous solution containing a peroxide with a colloidal suspension containing an amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension. The colloidal suspension contains a transition metal peroxide. The method involves combining a transition metal salt and an acid with an aqueous carrier to form a second mixture, substantially neutralizing the second mixture, filtering the second mixture and amorphous metal hydroxide. Also includes a step of forming the amorphous metal hydroxide and a step of suspending the amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension.

In another embodiment, the method for preparing the article is a step of preparing a composition containing an aqueous carrier and a condensation product of an organic functional silane and a transition metal peroxide, a step of applying the composition to the surface of a substrate. , And the step of removing the aqueous carrier to form an article with a coating on the surface of the substrate. In some embodiments, the coating is removed from the substrate to form nano-sized particles in powder form.

In some practices, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. The thickness of the coating can be less than about 10 nm. The coating is covalently bonded to the surface of the substrate. In some embodiments, the substrate is porous. In certain embodiments, the substrate is granular. In one aspect, the hybrid film-forming composition is prepared by the formation of an aqueous mixture containing organic functional silanes, metal chlorides, and acids. Bases are added to the aqueous mixture, substantially neutralizing the mixture and forming metal hydroxides. A colloidal suspension containing metal hydroxides and siloxy compounds is formed. A peroxide solution is added to the suspension to form a suspension containing a metal peroxide. The suspension is set to equilibrate at room temperature. The suspension is boiled at a pressure higher than atmospheric pressure to form a hybrid film-forming composition containing a condensation product of a siloxy compound and a metal peroxide. In some practices, the aqueous mixture is heated or boiled before the base is added to the mixture.

In some practices, the pH of the aqueous mixture before neutralization is less than 1. Metal chlorides include silicon, titanium, zirconium, tin, vanadium, gallium, germanium, tellurium, hafnium, rhenium, iridium, platinum chloride, or silicon, titanium, zirconium, tin, vanadium, gallium, germanium, tellurium, There are two or more combinations of hafnium, rhenium, iridium, or platinum chloride chlorides. The metal chloride can be a tetrachloride. The organic functional silane is, for example, bis (triethoxysilyl) methane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, octochloro-trisiloxane, tetraethoxysilane, or any of these. It may be a combination.

In another aspect, the preparation of the article comprises the step of preparing a composition comprising an aqueous carrier and a condensation product of a siloxy compound and a metal peroxide. The composition is applied to the surface of the substrate, the aqueous carriers are removed, and an article with a siloxy-peroxy hybrid metal coating on the surface of the substrate is formed.

In one embodiment, the composition comprises crystalline particles having a diameter of less than about 10 nm. The particles can include hybrid metal oxides, transition metal oxides, or combinations thereof. The composition can include silicon oxide and transition metal oxides. The weight percentage of silicon oxide based on all metal oxides can be at least about 50% by weight, at least about 95% by weight, or at least about 99% by weight. The weight percentage of transition metal oxides based on total metal oxides can be at least about 95% by weight. In some cases, the condensation product comprises silicon, titanium, zirconium, or any combination thereof.

In some practices, the composition formed by boiling the first mixture at a pressure above atmospheric pressure comprises crystalline particles less than about 10 nm in diameter. The crystalline particles can include hybrid metal oxides, transition metal oxides, or any combination thereof. The first mixture may be in the form of a colloidal suspension. In some cases, the peroxide containing aqueous solution is combined with a colloidal suspension containing amorphous metal hydroxide and silicon hydroxide in the aqueous carrier and contains transition metal peroxide and silicon peroxide. Form a colloidal suspension. In some embodiments, silicon chloride, transition metal chloride, and acid are combined with aqueous carriers to form a mixture. The mixture can be neutralized and filtered to form amorphous metal hydroxides and silicon hydroxides. The amorphous metal hydroxide and silicon hydroxide can be suspended in an aqueous carrier to form a colloidal suspension containing the amorphous metal hydroxide and silicon hydroxide.

In some practices, the preparation of the composition comprises the step of preparing a mixture containing a silicon peroxide, a transition metal peroxide, and an aqueous carrier. The mixture can be boiled at a pressure higher than atmospheric pressure to form a composition containing an aqueous carrier and a condensation product of a silicon peroxide and a transition metal peroxide. In one embodiment, the composition comprises crystalline nanosized particles containing transition metal oxides.

In one aspect, the composition comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide. In one embodiment, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some embodiments, the transition metal of the transition metal peroxide is the same as the transition metal of the transition metal oxide. The transition metal can be selected from the group consisting of titanium, zinc, and combinations thereof.

In some practices, the composition comprises an additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, and combinations thereof. In some cases, the composition comprises a filler. The filler may be substantially inert. Fillers include, for example, carbon nanotubes. The weight of the filler may exceed the weight of the transition metal in the composition.

In another aspect, the method of preparing a composition comprises the step of preparing a first mixture and the step of boiling the first mixture at a pressure higher than atmospheric pressure to form a composition. The first mixture contains organic functional silanes, transition metal peroxides, and aqueous carriers. The composition formed comprises an aqueous carrier and a condensation product of an organic functional silane with a transition metal peroxide.

In some practices, the composition formed by boiling the first mixture at a pressure above atmospheric pressure further comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. At least some of the nanosized particles are less than about 10 nm in diameter. In some cases, the first mixture comprises at least one additive selected from the group consisting of organometallic compounds, wetting agents, organic compounds, metals, metal salts, fillers, and combinations thereof. The first mixture may be in the form of a colloidal suspension.

In one embodiment, the method further comprises combining an aqueous solution containing a peroxide with a colloidal suspension containing an amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension. The colloidal suspension contains a transition metal peroxide. The method involves combining a transition metal salt and an acid with an aqueous carrier to form a second mixture, substantially neutralizing the second mixture, filtering the second mixture to obtain an amorphous metal hydroxide. It also includes a step of forming and a step of suspending the amorphous metal hydroxide in an aqueous carrier to form a colloidal suspension.

In another embodiment, the method for preparing the article is a step of preparing a composition containing an aqueous carrier and a condensation product of an organic functional silane and a transition metal peroxide, a step of applying the composition to the surface of a substrate. , And the step of removing the aqueous carrier to form an article with a coating on the surface of the substrate. In some embodiments, the coating is removed from the substrate to form nano-sized particles in powder form.

In some practices, the composition comprises crystalline nanosized particles. The nano-sized particles contain transition metal oxides. The thickness of the coating can be less than about 10 nm. The coating may be hydrophilic or hydrophobic. The contact angle of water on the hydrophilic coating can be less than about 20 °, less than about 10 °, or less than about 5 °. The coating is covalently bonded to the surface of the substrate. In some embodiments, the substrate is porous. In certain embodiments, the substrate is granular.

Implementations can include compositions and articles prepared by the methods described above, as well as any combination of the above characteristics.

Other features will become apparent from the description, drawings, and claims.

<figref num="1">It is a flowchart of the procedure for forming an aqueous polymer molecule hybrid nanocrystal.</figref><figref num="2">Shows the hydrolysis reaction of metal alkoxide.</figref><figref num="3">The formation of crosslinked oligomers by condensation of peroxymetal hydroxysilane is shown.</figref><figref num="4">The first coating and the second coating on the substrate are shown.</figref><figref num="5">The first coating and the second coating on the particles are shown.</figref><figref num="6">A model of silicon peroxide in solution is shown.</figref><figref num="7">A model of submesoporous metal peroxide interaction in solution is shown.</figref><figref num="8">It is a graph which shows the purification of the stain given by the hybrid metal oxide coating. Similar reference symbols in various drawings indicate similar elements.</figref>

(Detailed explanation) A solution or aqueous dispersion of polymer molecular hybrid nanocrystals can be prepared according to a series of steps of combining selected reactants and additives under specific reaction conditions. A composition containing a solution of polymer molecular hybrid nanocrystals or an aqueous dispersion is applied to a macro or micro surface (such as microparticle powder) to provide protection and / or protection containing metal oxides, metals, and other optional components. A functional coating can be formed. The coating can include nanofilms and composite films formed from vehicle systems with nanohybrid crystals that can also be used as inorganic vehicle systems to disperse nanoparticles. In addition to coating, the composition can be used to prepare nanopowder and nanocomposite powders, as well as vaporized nanoparticles.

As used herein, "base material" generally means a solid object of any size. For example, the substrate may be a window, a microchip, or a plurality of particles such as nanoparticles or micron-sized particles. In some cases, the compositions described herein change the bulk properties of the substrate, rather than applying the composition to the surface of the substrate, or in addition to the application, being mixed with the substrate. Mixing the composition with the substrate comprises dispersing the composition in the substrate such that the composition is substantially evenly distributed throughout the substrate. For example, if the substrate is cement, the composition or components of the composition may be mixed with dry cement or prepared (wet) cement. As another example, the melted material forming the glass can be mixed with the composition prior to cooling so that the components of the composition are dispersed in the glass.

Polymer molecular hybrid nanocrystal (PMHNC) compositions are transition metal salts, organofunctional silanes, organometallic compounds, wetting agents (including non-reactive silanes), other reactive and / or non-reactive (or substantially non-reactive) compositions. Inactive) Additives such as organic and / or inorganic compounds and any combination thereof can be included. These aqueous compositions contain at least about 90%, at least about 95%, or at least about 98% water. The temperature, pressure, and pH of the aqueous reaction mixture are selectively controlled throughout the preparation of the PMHNC composition.

The components of the aqueous inorganic PMHNC described herein are catalytic, photocatalytic, antibacterial, antiviral, antifungal, corrosion resistant, antifouling, semi-conducting, conductive, insulating, electromagnetic, It can be selected to form coatings with transparency, optics, radioactivity, flame retardancy, piezoelectricity, and other properties of choice. Coatings formed from the compositions described herein can be used in air / water purification, biomedical applications, thermocurability-thermoplastic enhancement, pigment dispersion, hydrogen storage, dye sensitized solar cells, and supercapacitor thin films. Useful and may be useful in applications in electrical applications, surface studies, optics, high refractive index coatings, electro-optics, acoustic optics, laser optics.

With reference to FIG. 1, procedure 100 represents the preparation of an aqueous PMHNC composition. First, an amorphous metal hydroxide mixture is prepared. In step 102, one or more metal salts (eg, metal M)^１An acidic aqueous mixture of) is formed. The metal salt may be a transition metal chloride or a halide salt of one or more metals such as silicon, titanium, vanadium, gallium, germanium, zirconium, tin, tellurium, hafnium, rhenium, iridium, and platinum. In some embodiments, the metal salt is a metal tetrachloride.

The pH of the mixture is less than about 1. The acid used to acidify the mixture may be, for example, a strong acid such as hydrochloric acid, hydrofluoric acid, nitric acid, and sulfuric acid, or any combination thereof. Other acids that can be used include acetic acid, arginine, azelaic acid, behenic acid, benzenesulfonic acid, boric acid, butyric acid, capric acid, castor oil, chromic acid, docosanoic acid, dodecylbenesulfonic acid. acid), hydrofluoric acid, fluosilicaten, formic acid, fumaric acid, glutamine, glycine, hydrochanic acid, hydroxyproline, hydroxystearic acid, isophthalic acid, lauric acid, linolenic acid, lysine, malonic acid, metaphthalic acid , Methionine, myristic acid, oleic acid, orthophthalic acid, ortholic acid, oxalic acid, palmitic acid, paraphthalic acid, paratoluenesulfonic acid, phenylalanine, phosphoric acid, phosphorus-containing acid, phthalic acid, pimeric acid, polyphosphoric acid, propionic acid, Licinolic acid, sodium formate, stearic acid, succinic acid, sulfanic acid, sulfamic acid, tartrate acid, terephthalic acid, toluenesulfonic acid, as well as other amino acids, carboxylic acids, carboxylates, chloride acids, dicarboxylic acids, fatty acids, halides. There are, but are not limited to, acids, organic acids, organic diacids, polycarboxylic acids, and any combinations thereof.

Step 104 is one or more additional metal salts (eg, metal M, which may be a transition metal) to the mixture formed in step 102.^２Includes), organometallic compounds (eg, transition metals may be M)^３Includes), organic functional silanes, or any combination thereof. M^１, M^２, And M^３Both may be the same or different.

The metal salt is selected to impart the desired properties to the PMHNC composition. For example, ZnCl₂Corrosion resistance can be imparted by adding zinc salts such as. In some cases, the metal is selected for the desired solubility at a certain pH in the method shown in FIG. Alternatively, the pH of the composition in the method can be adjusted to obtain the desired solubility of the selected metal salt.

In some embodiments, the second metal salt is a metal chloride. Metal chlorides are, for example, SiCl₄, TiCl₄, GeCl₄, VCl₄, GaCl₄, ZrCl₄, SnCl₄, TeCl₄, HfCl₄, ReCl₄, IrCl₄, PtCl₄Tetra chloride salt, such as, or other chloride salt, such as Na₂PtCl₆, CCl₃CO₂Na, Na₂PdCl₄, NaAuCl₄, NaAlCl₄, ClNaO₃, MgCl₂, AlCl₃, POCl₃, PCl₅, PCl₃, KCl, MgKCl₃, LiClEKCl, CaCl₂, FeCl₂, MnCl₂, Co (ClO₄)₂, NiCl₂, Cl₂Cu, ZnCl₂, GaCl₃, SrCl₂, YCl₃, MoCl₃, MoCl₅, RuCl₃, RhCl₃, PdCl₂, AsCl₃, AgClO₄, CdCl₂, SbCl₅, SbCl₃, BaCl₂, CsCl, LaCl₃, CeCl₃, PrCl₃, SmCl₃, GdCl₃, TbCl₃, HoCl₃, ErCl₃, TmCl₃, YbCl₃, LuCl₃, WCl₆, ReCl₅, ReCl₃, OsCl₃, IrCl₃, PtCl₂, AuCl, AuCl₃, Hg₂Cl₂, HgCl₂, HgClO₄, Hg (ClO₄)₂, TlCl₃, PbCl₂, BiCl₃, GeCl₃, HfCl₂O, Al₂Cl₆, BiOCl, [Cr (H)₂O)₄Cl₂] Cl₂E2H₂O, CoCl₂, DyCl₃E6H₂O, EuCl₂, EuCl₃E6H₂O, NH₄AuCl₄ExH₂O, HAuCl₄ExH₂O, KAuCl₄, NaAuCl₄81ExH₂O, InCl₃, (NH₄)₃IrCl₆, K₂IrCl₆, MgCl₂E6H₂O, NdCl₃, (NH₄)₂OsCl₆, (NH₄)₂PdCl₆, Pd (NH₃)₂Cl₂, [Pd (NH (NH)₃)]₄Cl₂EH₂O, (NH₄)₂PtCl₆, Pt (NH₃)₂Cl₂, Pt (NH₃)₂Cl₂, [Pt (NH)₃)₄] Cl₂ExH₂O, [Pt (NH)₃)₄] [PtCl₄], K₂PtCl₄, KClO₄, K₂ReCl₆, (NH₄)₃RhCl₆, [RhCl (CO) ((C₆H₅)₃P)₂], [RhCl (C)₆H₅)₃P)₃], [Rh (NH (NH)₃)₅Cl] Cl₂, K₃RhCl₆, RbCl, RbClO₄, (NH₄)₂RuCl₆, [RuCl₂((C₆H₅)₃P)₃], {Ru (NH)₃)₆} Cl₂, K₂RuCl₆, ScCl₃ExH₂O, AgCl, NaCl, TlCl, SnCl₂And the additional water adduct may be.

In some cases, PMHNC compositions are used to chemically bond other organometallic compounds (eg, in monomer / oligomer / polymer networks or matrices) to allow inclusion of organometallic compounds in inorganic vehicle systems. Can be provided. Desirable properties of the film or coating are enhanced by the addition of selected organometallic compounds, imparting or enhancing properties such as mechanical strength, electrical conductivity, corrosion resistance, antifouling properties.

The organometallic compound added in any step 104 can be selected such that one or more organic substituents are hydrolyzed in the acidic mixture of step 102 as shown in FIG. The organic metal compounds added in any step 104 include, for example, metal alkoxides such as methoxydo, ethoxydo, methoxyethoxydo, butoxide, isopropoxide, pentoxide and zinc, tungsten, titanium, tantalum, tin, molybdenum, magnesium and lithium. , Lantern, indium, hafnium, gallium, iron, copper, boron, bismuth, antimony, barium, zirconium, zinc, ittrium, vanadium, tin, silver, platinum, palladium, samarium, placeodim, nickel, neodymium, manganese, magnesium, lithium , Lantern, indium, formium, hafnium, gallium, gallium, iron, europium, erbium, dysprosium, copper, cobalt, chromium, cesium, cerium, aluminum, barium, berylium, cadmium, calcium, iridium, arsenic, germanium, gold, lutetium , Niob, potassium, renium, rhodium, rubidium, ruthenium, scandium, selenium, silicon, strontium, tellurium, terbium, turium, thorium, itterbium, ittrium and other metal pentadiates, propionates, acetates, hydroxides. , Hydrate, stearate, oxalate, sulfate, carbonate and / or acetyl alkoxide.

The organic functional silane added in step 104 promotes adhesion between the organic polymer and the inorganic substrate and acts as a binder-based cross-linking agent and curing agent. The bond strength and hardness (or abrasion resistance) of the film or coating formed on the substrate was determined by adding organic functional silanes in step 104 during the preparation of the composition to add peroxymetal hydroxysilane (PMHS) monomers. It forms and increases, which polymerizes to form the inorganic polymer PMHNC composition. As used herein, the "PMHS monomer" generally comprises a metal peroxide species covalently attached to a metal silanol species and is a silicate matrix (-Si (OH))._y-OM¹(OOH)_x-O-Si (OH)_yIt means a monomer that forms a structure such as-). As used herein, an "organic functional silane" is generally a silicon-containing compound having one or more hydrolyzable substituents. Organic functional silanes are typically bifunctional molecules with a hydrolyzable alkoxy group R, Y-Si (OR).₃It may be written as. In the presence of water, the alkoxy group R is hydrolyzed to form a reactive silanol (Si-OH) group without the alcohol (R-OH), as shown in FIG. The choice of alkoxy group affects the rate and extent of the hydrolysis reaction.

The reaction of silanol groups and the nature of Y determine how silanes function in the composition. Y may be organic or inorganic, hydrophobic or hydrophilic, ionic or cationic, zwitterionic or nonionic. In some cases, Y is halogenated (eg, chlorinated or fluorinated). Y can act as a surface modifier in the coating of substrates such as particles (eg pigments), colloids (eg latex).

When Y is a non-reactive group such as an alkyl group, the organic functional silane is generally referred to as a non-reactive silane. When Y is a reactive organic group such as an alkoxy group, the organic functional silane is generally referred to as a reactive silane. In some cases, Y is a reactive organic group attached to the reactive group of the polymer, and the organic functional silane behaves as a comonomer in the polymerization reaction.

Organic functional silanes suitable for PMHNC compositions that cause the formation of inorganic polymer vehicles include alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, dipodal silanes such as bis (trimethoxysilylpropyl) -amine, and bis. (Triethoxysilyl) methane, silsesquioxane, siloxane, disiloxane, polydimethylsiloxane, disilylmethylene, disilylethylene, silphenylene, metal silanolate, silazane, X, -Cl, CN, -NH₂, -SH, Hybrid Acetate-Alkene, Epoxide (RO)₃Si-CH₂CH₂CH₂There are, but are not limited to, X, or any combination thereof. Other suitable silanes have special functional groups including allyl, alkynyl, phenyl, hydroxyl, phenoxy, and substituents such as acetoxy groups, cyclic trimmers, tetramers, and pentamers, halogens, ketones, azides, and isocyanates. be able to. Some organically functional silanes, such as aminofunctional silanes, are autocatalytic, while other organically functional silanes require a small amount of acid to initiate hydrolysis. Organic functional silanes can be selected based on properties such as the desired reaction rate. For example, methoxysilane is known to hydrolyze faster than ethoxysilane.

The bis (trimethoxysilylpropyl) amine shown below is an example of an organic functional silane (amine bifunctional dipodal silane) having a non-polar alkyl segment. Condensation of bis (trimethoxysilylpropyl) amine with a colloidal suspension of polar metal hydroxides in step 110 can improve the dispersion of additives such as pigments in the aqueous composition, forming a film with non-polar segments. A hybrid molecular hybrid inorganic vehicle system is produced.<chemistry id="" num="1"><img id="000002" he="22" wi="159" file="0005651477.tif" img-format="tif" img-content="drawing" /></chemistry>

The 1,2-bis (trimethoxysilyl) decane shown below is another example of a reactive organic functional silane with non-polar segments. Condensing 1,2-bis (trimethoxysilyl) decane with a polar metal hydroxide colloidal suspension in step 110 also improves the dispersion of additives such as pigments in the aqueous composition, which is non-polar. A film-forming molecular hybrid inorganic vehicle system with segments is produced.<chemistry id="" num="2"><img id="000003" he="30" wi="159" file="0005651477.tif" img-format="tif" img-content="drawing" /></chemistry>

In some practices, non-reactive organic functional silanes that impart dispersibility in various resins and solvents are used to provide the PMHNC composition with steric stability and wettability. Polar, nonionic, water-soluble wetting agents (neutral pH) to which ethylene glycol functional groups are chemically bonded are particularly suitable. These ethylene glycol functional silanes can regulate the surface energy of the substrate surface within a wide pH range. Since these ethylene glycol functional silanes are hydrophilic but non-reactive, their addition facilitates uniform application of the composition and at the same time the particles such as nanoparticle composites into the aqueous composition. It also promotes substantially homogeneous dispersion. The hydrophilic surface of most mineral fillers and pigments can be made hydrophobic to increase their affinity for hydrophobic organic resins. The hydrophobization that occurs when the PMHNC composite alkylsilane binds to the surface of the filler particles makes it possible to improve the dispersion of the filler particles in the resin and the mechanical strength of the composition. Ethylene glycol functional silanes and / or other non-reactive organic functional silanes are added to the PMHNC composition along with the organic functional silanes while boiling and / or under pressure above atmospheric pressure to improve particle dispersibility. , The mechanical performance of the composition can be improved.

Organic functional silanes are effective adhesion promoters when the substrate has chemically active sites such as hydroxyl or oxide groups on its surface. PMHNC vehicle systems can be formulated to further promote adhesion to substrates (including particle substrates) with chemically active sites including, but not limited to, glass, metals, and metal alloys.

Metal substrates include aluminum, antimony, arsenic, beryllium, bismuth, cadmium, calcium, cerium, chromium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, germanium, gold, holmium, indium, iridium, iron, Lantern, lithium, lutetium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, palladium, platinum, praseodymium, renium, rhodium, ruthenium, samarium, scandium, selenium, silicon, tantalum, tellurium, terbium, thulium, thulium, tin, There are titanium, tungsten, itterbium, ittium, and zinc.

Metal alloy substrates include metals containing scandium-aluminum, ittrium-aluminum, beryllium-copper, calcium-magnesium, calcium-aluminum, calcium-silicon, chromium-silicon, samarium-cobalt, scandium-aluminum, and titanium-nickel. Any combination, alloys of aluminum (including one or more of lithium, copper, silicon, magnesium, palladium, manganese, etc.), alloys of bismuth (including one or more of lead, tin, cadmium, etc.), alloys of cobalt (including one or more of lead, tin, cadmium, etc.) Contains one or more of chromium, tungsten, carbon, etc.), alloys of copper (including one or more of beryllium, silver, zinc, tin, aluminum, nickel, gold, silver, iron, zinc, tin, manganese, lead, etc.) ), Gold alloys (including one or more of copper, silver, etc.), gallium alloys including gallinstan, indium alloys (including one or more of bismuth, tin, etc.), iron alloys (steel, carbon steel, etc.) Stainless steel, surgical stainless steel, etc. and / or carbon, chromium, nickel, Molybdenum, silicon, tungsten, manganese, cobalt, nickel, cobalt, ferroborone, ferrochrome, ferromanganese, ferromolybdenum, ferronickel, ferrophosphol, ferrotitanium, ferrovanadium, ferrosilicon, ferrotungene, etc.), lead , Copper, tin, and (optionally) antimony alloys, magnesium, aluminum, and (optionally) zinc-containing alloys, mercury-amalgam alloys, nickel alloys (copper, zinc, chromium, molybdenum, iron, nickel) , Manganese, silicon, magnesium, silicon, bronze, copper, etc.), titanium-shape memory alloy, silver alloy (including copper, gold, etc.), tin alloy (copper, antimony) , Including one or more such as lead), alloys of zirconium such as zircaloy, and alloys of uranium or deteriorated uranium with other metals such as titanium or molybdenum.

Polymer substrates include thermoplastic resins such as acrylonitrile-butadiene-styrene (ABS), acetal or polyoxymethylene (POM, DELRIN®), acrylate-styrene-acrylonitrile (ASA), cellulose polymers, cyclic olefins. Copolymer (COC), acrylic, (poly) acrylic, polymethyl-methacrylate (PMMA), polylactic acid (PLA), butyl rubber or polyisobutylene (polybutene), ethylene copolymer (polyethylene acrylate acid (EAA), polyethylene methylacrylate ( EMAC), Polyethylene Ethylacrylate (EEA), Polyethylene Vinyl Acetate (EVA), Polyethylenebutylacrylate (EBAC), Polyethylene Vinyl Acetate (EVA or EVAC), Polyethylene Vinyl Alcohol (EVAL or EVOH), Polyethylene Propropylene Tarpolymer (EPM), Polyethylene, (PE), Functionalized PE, High Density PE (HDPE), Low Density PE (LDPE), Linear Low Density PE (LLDPE), Medium Density (MDPE), Polytetrafluoroethylene (PTFE) Or fluoropolymers such as polyvinylidene fluoride (PVDF), ionomers, liquid crystal polymers (LCP), ketones, polyaryl ether ketones, or polyether ether ketones (PEEK), polyketones, polyurethanes (PURs), polyethylene sulfones (PES). , Polyethylene, Polyethylene (PA, PAII, P12, PA4,6, PA6, PA6,6, PA6-10, semi-aromatic PA), polyamideimide (PAI), polycarbonate, thermoplastic polyester or terephthalate (PET, PBT, PETG), polyethylene (PEN, PTT), thermoplastic elastomer (TPE, TPE-E) , TPE-S), methacrylate butadiene styrene copolymer (MBS), polyether blockamide (PEBA), copolyester elastomer (COPE), thermoplastic olefin (TPE-O), styrene-butadiene-styrene (SBS), styrene- Ethylene-butadiene-styrene (SEBS), thermoplastic urethane (TPE-U), thermoplastic hard rubber (TPV), polyetherimide (PEI), polyimide, polyolefin, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polysulfone, polyphthalamide (aramid), polyvinylidene chloride (PVDC), styrene or polystyrene, foamed styrene (EPS), general purpose crystal (GPPS), impact resistant polystyrene (HIPS), styrene acrylonitrile copolymer (SAN, ASA) , AES), styrene butadiene rubber (SBR), styrene maleic anhydride (SMA), vinyl or polyvinyl chloride (PVC), polysulfone (PSU), polylactic acid (PLA), and ethylene-viryl acetate.(PLA), and ethylene-bilyl acetate.(PLA), and ethylene-bilyl acetate.

Other substrates include thermosetting resins such as diallyl phthalate (DAP), epoxies, fluoropolymers, furans, melamines, phenolic resins, polybutadienes, polyesters, alkyds, vinyl esters, polyimides, polyureas, polyisosianates, etc. Polyurethane, silicone, thermosetting elastomer (isoprene), resorsinol or resorcin, vulture fibers, and specialty resins such as thermosetting resins, epoxy resins (EP), melamine formaldehyde resins (MF), phenol / phenolformaldehyde resins ( There are P / PF), urea formaldehyde resin (UF), unsaturated polyester (UPR), and (UV) cured (meth) crylate.

Other substrates include fabrics, building materials such as concrete, ceramics, pigments (organic and inorganic), fillers, fiber materials, electronic devices, carbon, graphite, inorganic materials, organic materials, wood, paper, waste. ), Skin, hair, and especially substrates and surfaces such as surgical steel, stainless steel, untreated steel, medical equipment, fiberglass, cement, and optical fibers.

The addition of the organic functional silane in step 104, prior to the neutralization in step 106, allowed the molecular level mixing of syroxy groups into the vehicle system, allowing the syroxy-peroxy hybrid (mixed metal oxide) film-forming product. Produces. "Syroxy" as used herein means a compound containing -Si-R-, where R is an aliphatic or aromatic group which may contain heteroatoms such as oxygen, nitrogen and sulfur. In some cases, the acidic sol formed in steps 102 and 104 is heated or boiled (eg refluxed) in step 105 prior to neutralization in step 106. The pH of the mixture is less than 1 or substantially less than 1. This additional heating step increases the solubility of the components in the mixture (eg, organometallics, metal chlorides, silanes) and produces a more homogeneous solution with smaller particles, thereby making it more effective and homogeneous. Promote harmony. The obtained hybrid siloxy-peroxy hybrid metal oxide film-forming body and PMHNC exhibit desirable properties such as increased photocatalytic efficiency, increased hydrophobicity, and stronger corrosion resistance.

In step 106 of FIG. 1, NH₄Strong bases such as OH or NaOH are added to the mixture to form a metal hydroxide colloidal suspension. The base substantially neutralizes the aqueous mixture. By slowly adding the base and stirring the mixture, the components of the mixture can remain suspended during and after the neutralization process. The pH after neutralization is at least 7 or at least 8. The supernatant can be discarded.

In step 108, the amorphous metal hydroxide mixture is washed (eg, by various forms of decantation or filtration) and ions such as chlorides or other ions are removed from the mixture. Washing may include adding distilled or deionized water (DIW) to the mixture, stirring the mixture, allowing the mixture to stand, and decanting. Washing is repeated until no ions are substantially detected in the supernatant. For example, the chloride ion test can be carried out by measuring the concentration of chloride ion in the supernatant using silver nitrate or by using a chloride ion probe. In some practices, washing is repeated until the concentration of unwanted ions in the supernatant is less than about 50 million percent (ppm). In some cases, the mixture may be centrifuged. After sufficient ion removal, the amorphous metal hydroxide can be recovered by filtration or other suitable means. The final supernatant is slightly or moderately basic (eg, pH about 8-10).

In step 110, the amorphous metal hydroxide is dispersed in water to form a colloidal suspension. The water may be deionized or distilled. Amorphous metal hydroxide colloidal suspensions may be slightly basic to moderately basic (eg, pH about 8-10). In step 110 or one or more subsequent steps, the water added is added in the amount required to form the composition of the desired density. The density of the composition can be adjusted depending on the surface or substrate to which the solution is applied. For example, for porous or absorbent surfaces or substrates such as concrete, the density of the mixture may be relatively high, but for non-porous or non-absorbable surfaces or substrates such as glass, the density of the mixture. May be relatively low. The thickness of the film applied increases with the density of the mixture.

In any step 112, one or more organometallic silanes, organometallics, wetting agents, and / or other reactive or inert components can be added to the aqueous metal hydroxide colloidal suspension. .. Suitable organic functional silanes and organometallics have been previously described as optional additives in step 104.

One or more wetting agents can be added in any step 112 to improve the hydrophobicity or wettability of the composition on the substrate so that a thinner film of the composition can be applied onto the substrate. Advantageously, the thinner the film, the less yellowish the appearance, the less moire patterns, and the shorter the cure time. Suitable wetting agents include polyethylene oxide silane, isopropyl alcohol, polar (hydrophilic) nonionic ethylene glycol functional silane, condensation of the above 1,2-bis (trimethoxysilyl) decane with polar metal hydroxide. Non-polar (hydrophobic) PMHNC compositions formed from, but are not limited to these.

The amount of wetting agent added to the mixture can be adjusted depending on the other additives in the composition, the type of substrate or surface to which the composition is applied, and the like. In some embodiments, it is not necessary to add a wetting agent to the composition for substrates or surfaces with very high water absorbency, such as concrete. In other embodiments, as much as 0.03% by volume of wetting agent may be added to a low surface tension or high water repellent substrate or surface composition such as glass, polished metal, or certain silicon wafers.

Other components added in any step 112 that can impart selected physical and chemical properties to the composition include reactive and / or inert (substantially non-reactive) organic and / or inorganic. There are compounds. Inorganic compounds added in any step 112 include, for example, zirconium, zinc, ittium, tungsten, titanium, terbium, tantalum, tin, silver, silicon, scandium, samarium, placeodim, niobium, nickel, neodymium, molybdenum, iron, etc. Manganese, magnesium, lutetium, lithium, lantern, indium, formium, hafnium, germanium, gallium, gadolinium, europium, terbium, dysprosium, copper, cobalt, chromium, cesium, cerium, boron, aluminum, bismuth, antimony, ruthenium, beryllium, There are metal oxides such as oxides such as cadmium, calcium and indium, and titanates such as titanates such as strontium, lead and barium.

Organic compounds added in any step 112 include methylmethacrylate, pentaerythritol, TMP, TME, dibasic acid, carboxylic acid, olefin, diene, acetylene, styrene, acrylic acid, cyclic monomer (cyclic ether, lactone, lactam). , Cyclic amines, cyclic sulfides, cyclic carbonates, cyclic acid anhydrides, cyclic imino ethers, amino acids N-carboxyl anhydrides, cyclic imides, phosphorus-containing cyclic compounds, silicon-containing compounds, cyclic olefins, etc.), and any combination thereof, etc. There is a monomer of. Like organometallic compounds, the additive can combine with PMHS species (monomers, oligomers, etc.) to form oligomers dispersed in the composition. Composite PMHNC nanoparticles designed to exhibit partially non-reactive, non-polar functional groups and partially reactive silanes, and organometallic functional groups can be mixed into hydrophobic monomers. As an example, condensation of reactive silanes such as 1,2-bis (trimethoxysilyl) decane added in step 124 can result in increased non-polar functionality in PMHS species. Increasing the amount of 1,2-bis (trimethoxysilyl) decane added to PMHS will eventually run out of metal peroxide and optimize hydrophobicity throughout PMHNC. The PMHNC nanocomposite can be dehydrated and mixed with non-polar monomers as described herein.

Other substantially non-reactive or inert additives added in any step 112 include, for example, fillers, pigments, metals, carbon nanotubes (single-walled and / or multi-walled), nanographite platelets, silica airgels. , Carbon airgel, glass flakes, quantum dots, nanoparticles, etc. Nanoparticles include, for example, aluminum, aluminum nitride, aluminum oxide, antimony, antimony oxide, antimonthine oxide, barium titanate, beryllium, bismuth oxide, boron carbide, boron nitride, calcium carbonate, calcium chloride, calcium oxide, calcium phosphate, Cobalt, Cobalt Oxide, Copper, Disprosium, Disprosium Oxide, Elbium, Elbium Oxide, Europium, Europium Oxide, Gadrinium, Gadrinium Oxide, Gold, Hafnium Oxide, Holmium, Indium, Indium Oxide, Iridium, Cobalt Iron, Iron, Nickel Iron, Oxide Iron, lantern, lanthanum oxide, lead oxide, lithium manganese oxide, lithium, lithium titanate, lithium vanadate, lutetium, magnesium, magnesium oxide, molybdenum, molybdenum oxide, neodymium, neodymium oxide, nickel, nickel oxide, nickel titanium, niobium , Niobium Oxide, Palladium, Platinum, Placeodym, Placeozim Oxide, Renium, Luthenium, Samalium, Samalium Oxide, Silicon Carbide, Silicon Nanoparticles, Silicon Nanoparticles, Silicon Nitide, Silicon Oxide, Silver, Strontium Carbonate, Strontium Titanium, Tantal, Oxide Tantal, terbium, terbium oxide, turium, tin, tin oxide, titanium carbide, titanium, titanium nitride, titanium oxide, tungsten carbide, tungsten, tungsten oxide, vanadium oxide, itterbium, ittria stabilized zirconia, ittium, zinc oxide, zirconium, There are nanoparticles such as zirconium oxide, and any combination thereof.

Other particles of nanometer to micron size, such as polycrystalline, single crystal, or shaped charge microparticles and / or nanoparticles, can be added to them in any step 112 with the PMHNC composition. It may be applied. These particles include antimony selenium, antimony tellurium, bismuth serene, bismuth tellurium, boron carbide, silicon carbide, tungsten carbide, gallium antimony, gallium arsenide, gallium antimony indium, gallium phosphide, phosphorus. Gallium phosphide, gallium tellurate (II), gallium tellurate (III), germanium tellurate, indium antimony, indium arsenide, indium phosphide, indium phosphide, indium selenium, indium sulfide, indium tellurate, There are silicon arsenide, silicon phosphide, tin arsenide, tin selenium, tin tellurate, zinc tellurate, etc.

In some practices, the amorphous metal hydroxide colloidal suspension composition formed in step 110 is applied directly to the surface to form a coating on the surface, as indicated by step 114. In other practices, the amorphous metal hydroxide colloidal suspension composition formed in step 110 is dehydrated (eg, spray dried) and recovered as a powder for use in the form of nanopowder or nanocomposite powder. ..

In step 116, a peroxide solution is added to the amorphous metal hydroxide colloidal suspension to reduce the pH of the composition to about 1 or less. Peroxide-based solutions include, for example, hydrogen peroxide, benzoyl peroxide, tert-butyl hydroperoxide, 3-chloroperoxybenzoic peroxide, di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone. There are peroxides, [dioxybis (1-methylpropylidene)] bishydroperoxides, (1-methylpropyridene) bishydroperoxides, peroxides, and combinations thereof. The mixture is cooled and reacted for some time to form a stable amorphous metal peroxide colloidal suspension. The stable amorphous metal peroxide colloidal suspension has M as M depending on the components in the composition.¹, M², Or M³Any combination of M (OOH)_x, M (OOH)_yOM, M (OOH)_yOM, M (OOH)_yMetal peroxides such as OSi and various condensation products of these with other species can be included, but x and y depend on the oxidation state of M and the number of other substituents.

In some practices, cooling is achieved in a sealed reaction vessel by depressurizing the vessel below atmospheric pressure. The pressure inside the vessel can be adjusted to obtain the desired temperature. In some cases, the mixture is optionally cooled by thermal cooling from the outside of the system with decompression of the system. The formulation of the mixture can determine the degree of vacuum required to reduce the temperature of the system by the desired amount or to the desired threshold.

The composition may be agitated during cooling. The level of agitation is chosen to achieve ionization so that the amorphous metal peroxide colloidal suspension is formed without particle agglomeration. For example, the level of agitation may be from about 500 to about 10,000 revolutions per minute (rpm), depending on the volume of the mixture. In some practices, the level of agitation is from about 2500 to about 7000 rpm. If the wetting agent is added, for example in step 112, the need for shaking or stirring is reduced or eliminated. Due to the presence of the wetting agent, the thickness of the coating or the film can be reduced and the film forming property can be improved.

When the reaction in step 116 is substantially complete, the resulting amorphous metal peroxide colloidal suspension is equilibrated at room temperature and room pressure, as shown in step 118. Suspension is amorphous metal hydroxide M¹(OH)₄And metal peroxide M¹(OOH)₄And M¹Includes other species such as (Si-OH) and condensation products of these with other species, but is stable, can be stored at room temperature for later use, can be dried to form a powder and evaporated. Can form vapor and can be applied to the surface as shown in step 120.

The coating formed in step 120 can later be processed as desired to alter the chemistry or functionality of the coating. For example, the coating formed in step 120 is post-treated and is catalytic, photocatalytic, antibacterial, antiviral, antifungal, corrosion resistant, antifouling, semi-conducting, conductive, insulating, electromagnetic, Transparency, optics, radioactivity, flame retardancy, piezoelectricity, etc., or any combination thereof can be improved or imparted to the coating. Treatments include, for example, mixing additives (such as nanoparticles) into the PMHNC composition, applying an additional PMHNC composite coating, depositing additional layers by chemical vapor deposition (CVD) or atomic layer deposition (ALD), soft lithography. There is the use of technology.

In step 122, the amorphous metal peroxide colloidal suspension is heated to a boil at a pressure above atmospheric pressure for a suitable period of time. The composition may be agitated during heating. The temperature at which the suspension is heated can be determined by several factors, including the components present in the mixture, the pressure inside the reaction vessel, and manufacturing constraints. In one example, a colloidal suspension of amorphous metal peroxide with a volume of about 2 liters, from about 45 ° C to about 250 ° C, for about 1.5 to 2 hours, 10 to 100 pounds per square inch (psi). It can be heated at (about 68.9 to 689 kPa). For larger volumes of mixtures, the pressure can be suitably increased, for example, up to 2500 psi (about 17.2 MPa), as used in the production. During the heating and applying pressure steps, the properties of the mixture (eg, temperature, pH, etc.) can be monitored to ensure that a substantially homogeneous solution is being formed.

The amorphous metal peroxide / metal oxide composition formed in step 122 can have a pH of about 7. The light transmittance of the solution is about 92-98%, which makes it appear transparent to the human eye. In addition, the density of the solution (ie, the amount of solids dispersed in the solution) can range from about 0.125% to about 2.0% or more, depending on the intended use of the composition.

Reactive or inert additives containing nanoparticles, composite PMHNC powders and vapors, such as organic functional silanes, organometallic compounds, wetting agents, and / or those described in any of step 112 above, in step 122. It can be added as desired in any step 124 before or during heating of the suspension. Organic functional silanes, organometallic compounds, wetting agents, and / or reactive or inert additives present from any step 104, 112, and / or 124 are the metals present in the hydrolysis and composition. Following subsequent condensation with hydroxide, a covalent structure, eg M (OOH)_xOM and M (OOH)_xOM (M is M in the previous formula¹, M², M³, Or any combination of these), along with M (Si-OH) and M¹, M², And M³Oxide can be formed, and at the same time, the metal hydroxide existing before the reaction with the peroxide solution is substantially consumed. In some cases, similar covalent structures are metal M.¹, M², And / or M³Includes reactive additives with or instead. These covalent structures serve as inorganic binders for the formation of non-porous coatings. In particular, when the composition is heated, the metal peroxide reacts with the silane to improve the cross-linking, hardness and wear resistance of the binder.

Substrates (or fillers) that cannot be covalently bonded to silane alone (polyolefins, polyethers, etc.) or that exhibit only weak interactions with silane (CaSO)₄, BaSO₄, Inorganic pigments, carbon black, calcium carbonate, graphite, etc.) can be bound by a silane-containing PMHNC vehicle system. For example, the PMHNC hybrid vehicle system of step 122 has exposed, unreacted peroxy groups capable of reacting with additives capable of undergoing hydrolysis and condensation. Addition of metharoxysilane (N- (3-acrylicoxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, etc.) in step 124 is M (OOH).₂(OR)₂(In the previous equation, R is a methacrylosilane that condenses with the PMHS monomer after hydrolysis), forming a peroxide metal methacrylate composite vehicle system with two functionalities, thus producing a colloidal oligomer dispersed in water. Form. Since the hybrid colloidal oligomer is dispersed in a high percentage of water, such as about 98%, the free peroxy group of the oligomer maintains steric stabilization.

When the composite vehicle system is applied to the surface and the water evaporates, the peroxy group acts as a catalyst to promote polymerization. For PMHS oligomerization, peroxides are essential inorganic substituents on PMHS. As described above, the peroxide is also involved in the final polymerization by hydrolysis and condensation as shown in FIG. During the polymerization, one leg of the methacryl functional group double bond splits and begins to connect with the central carbon atom of the other methylmethacrylate molecule to form a chain until the final hybrid polymer is formed. repeat. This type of coating increases the number of coupling sites on the substrate that interact weakly with silane, resulting in up to 50% improvement in tensile and bending properties over silane treatment alone. Similarly, PMHNC vehicles are surprisingly free of other additives with weak (or virtually no) silane interactions, such as carbon nanotubes, carbon black, graphite, calcium carbonate, calcium sulphate, barium sulphate, and inorganic pigments. With a high weight ratio, it can be bonded and stably dispersed.

When the organic functional silane is added in any step 112 and / or step 124, the silanol group undergoes a condensation reaction with the metal peroxide in the aqueous solution to form a PMHS monomer, where the silicon is metallic. Bonds directly or indirectly (with one or more intervening atoms such as oxygen) to metal atoms in the oxide.

For organometallic compounds such as those containing zinc, for example, Ti (OOH) in titanium peroxide mixtures.₄+ Zn (OOH)₄Reacts with the formation of anatase titanium oxide crystals in the PMHNC composition, as well as the formation of complexes such as the -Ti-O-Zn-O-Ti-O-Ti-O-Ti-O-Zn-O matrix. .. In some cases, due to the nature of the organometallic compound and the organofunctional silane, the silane enhances the dispersion of the organometallic compound in the PMHS composition and increases the steric stabilization of the dispersion, such as the composite nanoparticle dispersion. ..

In some practices, metal alkoxides as well as organic functional silanes are partially hydrolyzed to form reactive monomers, which undergo polycondensation to form colloid-like oligomers. Addition of one or more organic functional silanes in step 104 of FIG. 1 yields a siloxy-peroxy hybrid film-forming product. The hydrolysis and condensation of the siloxy-peroxy hybrid membrane-forming body is shown in FIG.¹, M², And M³Is a transition metal and R is an aliphatic or aromatic group. In some embodiments, R comprises a heteroatom such as oxygen, nitrogen, sulfur. The polymerization and cross-linking shown in FIG. 3 yields a hybrid three-dimensional matrix, where drying promotes additional cross-linking during film formation to form a siroxy-peroxy hybrid film.

The composition of step 122 can be applied to the surface as shown in step 126 to form a protective coating on the surface and also to seal the surface. During film formation, the reactive silanol groups in the PMHS monomer condense with the hydroxyl groups on the surface of the substrate and directly or indirectly (along with one or more intervening atoms such as oxygen) with the atoms on the surface of the substrate. Join. In some cases, the metal atoms in the organometallic compound mixed in the composition bond directly or indirectly to the PMHS monomer and further directly or indirectly to the surface of the substrate, coating the substrate. Strengthen the adhesion of. As such, the compositions described herein contain a random monomer / oligomer network that binds to each other and to the substrate, with one or more intervening atoms between the metal and the substrate (directly or indirectly). ), By covalent bond between silicon and substrate (directly or indirectly with one or more intervening atoms) and between metal and silicon (directly or indirectly with one or more intervening atoms). Form an inorganic polymer coating, layer, or film that adheres to the substrate.

The inorganic vehicle system formed in step 122 can include PMHNCs formulated for a variety of applications, including sealants for substrates including metals, wood, plastics, glass, fabrics and the like. The coating applied in step 126 can be used alone as a sealant to protect the substrate from the environment, but in some cases due to the chemistry of the second coating applied over the sealant. It can also protect the substrate. The coating applied in step 126 can be post-processed (eg, by electromagnetic radiation, heating, pressure, etc.) to alter the chemical and / or physical properties of the coating.

Step 128 shows continuous boiling under pressure of the composition formed in step 122. This continuous heating under pressure above atmospheric pressure decomposes the metal peroxide and promotes the crystal growth of the metal oxide particles, as well as the formation of additional oligomers and cross-linking as shown in FIG. Thus, the ratio of metal oxides to metal peroxides in solution increases. Due to the metal oxides present and other components in the composition, certain desirable properties of the composition formed in step 128 are enhanced compared to the same properties of the composition formed in step 122.

Boiling at a pressure higher than atmospheric pressure in steps 122 and 128 forms metal oxide crystals from the suspension formed in step 116 and the metal peroxide / metal oxide composition formed in step 122. Effectively shortens the time required for the process compared to the time required for atmospheric pressure. In addition, the resulting PMHNC composition has a narrower particle size distribution than the PMHNC composition formed by boiling at atmospheric pressure and exhibits a more transparent coating.

The temperature and pressure inside the reaction vessel in step 128 can be adjusted according to the amount of solution and the components in the solution. In one example, 1-5 liters of amorphous titanium peroxide / titanium oxide composition from about 45 ° C to about 250 ° C, under a pressure of 10-100psi (about 68.9-689kPa), peroxide for about 3 hours. May be heated until is substantially exhausted and the metal oxide nanoparticles become the predominant metal species. Transparent metal oxide compositions include, for example, coating, spraying, drying, ALD, soft lithography (microcontact printing (μCP), replica molding (REM), microtransfer molding (μTM), capillary micromolding (micromolding capillaries)). It can be applied to any suitable surface by MIMIC), solvent assisted micromolding (SAMIM), self-assembled monolayer (SAM), or other methods.

At a density of about 1.2-1.5 wt% metal oxide, the composition formed in step 128 has a light transmittance of about 87-93%, so that the solution appears transparent to the human eye. In some practices, the density of the metal oxide solution (ie, the amount of solids dispersed in the solution) will be any point from about 0.5% to about 2.0% by weight, depending on the desired use of the composition. sell. The composition is a homogeneous dispersion of stabilized metal oxide nanoparticles with a diameter of less than about 10 nm or less than about 5 nm (eg, about 0.3 nm to about 7 nm in diameter, or about 2 nm to about 5 nm in diameter). It has improved film forming and / or surface treatment capabilities determined by the silanes, organometallic compounds, and other components added at 104, 112, and / or 124.

One or more organic functional silanes may be added in step 112 and / or step 124 during the method shown in FIG. In some practices, the first organic functional silane is mixed with the aqueous amorphous metal hydroxide in step 112. After stabilization of the resulting colloidal metal peroxide suspension, a second organic functional silane is added in step 124 before or during boiling of the amorphous metal peroxide mixture under high pressure. The second organic functional silane may be the same as or different from the first organic functional silane.

The zeta potentials of the compositions shown in FIG. 1 are indicators of the stability of these compositions. Particles with high zeta potentials with the same charge sign, both negative and positive, repel each other. Traditionally, high zeta potentials are considered to be -30 mV or less or + 30 mV or more. For molecules and particles that are small enough and dense enough to remain suspended, high zeta potentials are stable, i.e. the solution or dispersion does not tend to aggregate. The average zeta potential of the compositions described herein ranges from about -25 mV to about -50 mV, for example about -30 mV or about -40 mV.

The compositions formed in steps 122 and 128 can be applied to any suitable surface as described above, dried under ambient conditions or in the presence of heat and coated on the surface as shown in steps 126 and 130. To form. The coating can have a monolayer thickness of, for example, on the order of a few nanometers. In some practices, the coating thickness is about 2-10 nm, about 3-8 nm, or 4-6 nm. In other applications, the coating can have a thickness of about 10 nm to about 1 μm. For example, the coating can be from about 10 nm to about 800 nm, from about 100 nm to about 600 nm, or from about 200 nm to about 500 nm. These coatings are continuous, covalent, cross-linked, cured polymer films in which agglomerated discontinuous particles are apparently absent. In some practices, the viscosities of the compositions formed in steps 122 and 128 are adjusted to form thicker layers or coatings, eg, on the order of a few microns or more. Repeated application of one or more compositions can result in a coating having the desired thickness and the desired number of layers with the same or different functionality.

The composition can be vaporized in steps 126 and / or 130 to allow deposition of ALD, CVD, etc. to form a coating or thin film of the desired thickness. Continuous deposition of precursors of the same or different PMHNC formulations or treatment of the membrane in ALD allowed atomic layer control of membrane growth and was chemically bonded to a substrate, optionally with a thickness of about 1 nm to about 500 nm. It produces a monolayer without symformity defects. ALDs are suitable for forming various thin films, including conductors, insulators, etc., on a porous or non-porous substrate that is patterned or unpatterned. The composition and thickness of the coating can be selected to obtain values suitable for properties such as dielectric constant, conductivity, refractive index, transparency, reactivity and the like. In particular, a pure, high dielectric constant coating, essentially free of carbon (organic) or silicon dioxide contamination, is obtained with the compositions described herein. The small particle size in the compositions prepared in step 128 makes these compositions particularly suitable for the vapor deposition process.

In some practices, PMHNC compositions with 0.005% to 10% stabilized solids dispersed in water can be used to form nanocomposite powder particles less than about 100 nm in diameter. These nanopowder or nanocomposite powders are added to PMHNC compositions (eg, in steps 112 and / or 124) or other dispersions and machines such as thermosetting resins, thermoplastic extrusions, organic pigment dispersions, etc. Physical, physical and / or chemical properties can be improved. The PMHNC composite powder can be bonded to a particle substrate that is not easily dispersed in the PMHNC vehicle system or, for example, particles that are not easily dispersed in the thermosetting resin or thermoplastic resin system.

In some practices, two or more coatings are applied to the substrate, as shown in FIG. The first composition is applied to the substrate 400 and dried to form the first coating 402 on the substrate. The second composition is then applied to the first coating 402 and dried to form a second coating 404 that is adhered to the first coating 402. The second composition may be the same as or different from the first composition. The thickness of the first coating 402 may be approximately the same as or different from the thickness of the second coating 404.

Similarly, as shown in FIG. 5, the first composition can be applied to the particles 500 or a plurality of particles and dried to form a first coating 502 on the particles. The particles may be, for example, microparticles. The second composition is then applied to the first coating 502 and dried to form a second coating 504 adhered to the first coating 502. The second composition may be the same as or different from the first composition. The thickness of the first coating 502 may be approximately the same as or different from the thickness of the second coating 504.

In some embodiments, the coated substrate can be further treated to alter the properties of the coating. Treating the coated substrate to change the properties of the substrate is shown in step 132 of FIG. In some practices, the coating formed in steps 114, 120, and / or 126 is added to or independently of the treatment of the coated substrate formed in step 132 after the formation of the coating. Can be processed.

The organometallic added in steps 104, 112, and / or 124 imparts certain desirable properties to the PMHNC composition. Some non-limiting examples are given below.

Zirconium 2,4-pentandionate is useful for the formation of high dielectric constant layers (eg, by ALD) of metal oxides containing Group 4 metals such as hafnium oxide. Zirconium oxide resulting from the mixing of zirconium 2,4-pentanedionate into the PMHNC composition imparts hardness and scratch resistance to the PMHNC coating.

2,4-Zinc pentandionate hydrate and zinc methoxyoxide are TiO₂When mixed with the PMHNC composition, it forms a Ti / Zn composite film having improved photocatalytic properties compared to the photocatalytic properties of the Ti film. These compounds are transparent and conductive ZnO-In₂O₃It can be used for film formation, sol-gel production of lead zirconate titanate film, sol-gel coating of alumina powder in composites, and preparation of transparent monolithic poly (tetramethylene oxide) ceramics. These compounds can also be used as catalysts for co-polymerization and esterification and as components of high refractive index, wear and corrosion resistant coatings. The resulting zinc oxide is a heat resistant material.

Yttrium 2,4-pentandionate can be added to the PMHNC vehicle system to facilitate the preparation of nanocomposite thin films in which yttrium oxide and other oxide components are mixed. In some cases, the yttrium oxide imparts superconductor-like properties to the coating formed from the composition containing yttrium.

Tungsten (V) ethoxide and / or tungsten (VI) ethoxide can be added to the PMHNC composition to form tungsten nanoparticles and composites useful for electronic and luminescent applications. Tungsten nanoparticles and composites can help to obtain a coefficient of thermal expansion similar to compositions containing silicon and other metals used in microelectronics. Nanomaterial inks and pastes containing tungsten may be useful in the preparation of improved DRAM chips, other silicon devices, and liquid crystal display products.

Titanium ethoxydo is mixed with PMHNC composition to enhance photocatalyticity and SiO₂Can act as a high-k dielectric gate material as an alternative to. When added in step 112 of the method shown in FIG. 1, the titanium ethoxydo is TiO in the crystal lattice during film formation.₂Increase the concentration of.

Titanium dioxide plays a complex role in durability in various coating compositions such as paints. TiO₂Is a photocatalyst that absorbs UV light, thereby protecting other components in the coating composition that decompose upon exposure to UV light. The desired coating composition enhances binder protection and reduces photocatalytic activity. The PMHNC composition containing titanium is an organic pigment such as phthalocyanine blue in an aqueous dispersion, and the pigment dispersion amount can be increased. Copper phthalocyanines are non-polar like other organic pigments that exhibit a resonant structure with amine functional groups (eg, perylene, quinacridone, etc.). By stabilizing the expensive organic pigment dispersion, a lower blending amount can be achieved while improving the chromaticity (color depth or intensity) at a significantly lower cost.

Tantalum (V) ethoxydo may be added as a gate material to the PMHNC composition for use in the ALD formation of high-k dielectric layers of metal oxides containing Group 4 metals such as hafnium oxide.

Tin (II) methoxide is useful in the preparation of nanoparticle tin-containing PMHNC compositions. The tin oxide in the resulting coating imparts flame retardancy and catalytic properties and is also useful for ion exchange systems as well as conductive powders and membranes.

Silver 2,4-pentandionate (I), added in steps 112 and / or 124 of the method shown in FIG. 1, imparts antiseptic properties and enhances the photocatalytic properties of the coating formed by the PMHNC vehicle system. The film formed with the silver (I) component of 2,4-pentanedionate is transparent and, in some cases, conductive. Similarly, gold, platinum, and palladium organic compounds can be mixed to impart conductivity as needed, for example in the case of thin film electrodes and catalyst carriers. Platinum 2-4 pentanedionate can be mixed with, for example, a composition for a transparent electrode for use in dye-sensitized solar cells. Platinum 2,4-pentandionate can also be added to form composite Ti / Si with bissilane as a mesoporous nanocoating for catalytic converters.

Samarium 2,4-pentanedionate can be used in the PMHNC composition to form a thin film containing samarium oxide. Samarium oxide promotes dehydration and dehydrogenation of ethanol. A nanolayer PMHNC coating containing samarium oxide, mixed onto a microporous glass filter, provides an increased surface area for the reaction as ethanol passes through the filter.

Metal-insulator-metal or metal-insulator-metal or used as a memory cell in a storage device such as DRAM (Dynamic Random Access Memory) or as a passive element for high frequency applications by mixing placeozium 2,4-pentandionate with a PMHNC composition. With a series of metal-insulator-semiconductor layers, a titanate nanofilm composite for electronic devices can be formed.

Nickel 2,4-pentandionate (II) can be added to the PMHNC composition to provide properties such as corrosion protection and catalytic activity. The resulting membrane can serve as a catalyst for conjugate addition of alkynyl aluminum to enones, formation of biaryls by Grignard reagent coupling, formation of alkenes by Grignard addition to silyl enol ethers, and coupling of dialkylzinc and alkyl iodide. Can work. The resulting film can exert a thermal discoloration effect in a non-coordinating solvent and act as a UV stabilizer for polyphenylene sulfide.

When neodymium 2,4-pentandionate (III) is added to the PMHNC composition, ferroelectric titanate is formed in the PMHNC film. When added to PMHNC compositions, molybdenum (V) ethoxydos produce molybdenum oxides in the resulting membrane, which is useful in electrochemical devices and displays.

The structure of the ordered porous manganese-based octahedral molecular sieve (OMS) is MnO.₆It is determined by the type of octahedral aggregation (eg, vertex sharing, edge sharing, or face sharing). Manganese's ability to undergo multiple oxidation states and MnO₆The ability of octahedrons to aggregate in different arrangements allows the formation of a wide variety of OMS structures. Addition of 2.4-manganese pentandioate (II) to the PMHNC composition under ambient conditions causes manganese oxide and MnO to the membrane that binds to the substrate.₆It can promote the mixing of octahedrons. In some cases, PMHNC membranes containing manganese oxide can be used as ion insertion hosts for lithium ion batteries.

Addition of magnesium 2,4-pentanedionate to the PMHNC composition results in a catalytic membrane. The PMHNC membrane containing magnesium oxide can be used as a polymerization catalyst for olefins and / or as a catalyst for thickening reactions of polyesters.

When magnesium ethoxydo is mixed with steps 104, 112, and / or 124 of the method shown in FIG. 1, TiO₂To produce a spinel that can be used for highly heat-resistant thin-film crucible linings and gas-permeable inorganic membranes.

When magnesium methoxydo is added to the PMHNC composition, a film containing magnesium oxide (magnesia) is formed. Due to the high coefficient of thermal expansion of magnesia, this oxide is particularly suitable for porous structures for use as a carrier for inorganic membranes with comparable coefficients of thermal expansion. Magnesia is a heat-resistant ceramic with a high coefficient of thermal expansion and a substantially pure phase, thus imparting unique properties to PMHNC coatings. PMHNC coatings containing magnesium oxide are used, for example, in core windings for other applications, including the production of fluorophlogopite, where the dielectric constant of magnesium oxide and the optical properties of the sol-gel derived from it are desirable. it can. In some cases, PMHNC coatings containing magnesium oxide can be used to deoxidize paper.

Addition of lithium 2,4-pentandionate to the method shown in FIG. 1 results in a nanolithium composite film and powder. The small particle size and narrow diameter distribution obtained are convenient for use as electrodes for lithium-ion batteries and allow the battery to maintain its charge capacity at high charge / discharge rates.

When the method shown in FIG. 1 contains lanthanum 2,4-pentanedionate, the resulting PMHNC film contains lanthanum oxide and is suitable as a high-k dielectric gate material. These membranes can be intermediates for ferroelectrics and sol-gel-derived superconductors.

In the presence of the selected yttrium compound, lanthanum methoxyethoxydo is added to the LaYO in the PMHNC membrane.₃To form. LaYO₃Can be used as an exhaust gas catalyst or in combination with other components to form an oxidation resistant film.

Addition of lanthanum isopropoxide to the PMHNC composition results in a low leak dielectric film. Coatings containing lanthanum oxide as the dielectric layer have a relatively high dielectric constant, a relatively high conduction band offset, and a high crystallization temperature.

Addition of indium 2,4-pentandionate and / or indium methoxyethoxydo to the process shown in FIG. 1 forms a transparent, conductive film that can be used in field effect transistors.

PMHNC compositions containing hafnium 2,4-pentandionate and / or hafnium ethoxydo produce a thermostable coating or film with a high-k dielectric layer containing hafnium oxide.

When added to the PMHNC composition, gallium 2,4-pentandionate (III) and gallium (III) ethoxide produce a film containing gallium oxide nanocrystals. Membranes containing gallium oxide nanocrystals are useful for optoelectronic devices and gas detection and catalytic applications. The co-hydrolysis of gallium (III) ethoxide and tellurium alkoxide in the PMHNC vehicle system produces a film useful for heat mode erasable optical memory.

The PMHNC composition made of gadolinium trihydrate 2,4-pentandionate produces a film useful for controlling or containing radioactive contamination by providing a neutron absorbing material at the site of radioactive contamination.

Iron (III) pentandionate and iron (III) ethoxide, when added to the method shown in FIG. 1, act as intermediates for the formation of ferrite sol-gel. The resulting iron oxide-containing coating produces a catalytic coating and a magnetic coating. Iron (III) ethoxide reacts with other components to form iron oxide and other products. For example, iron (III) ethoxide reacts with platinum to produce FePt nanoparticles. In some cases, iron oxide-containing membranes are useful as insertion hosts for lithium-ion batteries.

In some embodiments, addition of europium 2,4-pentanedionate to the PMHNC composition results in a fluorescent coating. Erbium oxide gives a pink color to films made from vehicle systems made by the addition of erbium 2,4-pentandionate.

PMHNC compositions containing dysprosium oxide derived from 2,4-pentanedionate dysprosium are suitable for ALD. The addition of copper (II) and copper (II) ethoxydo 2,4-pentandionate to the PMHNC composition results in a film useful for electrochemical and superconducting applications.

When mixed with the PMHNC composition, cobalt 2,4-pentanedionate (III) acts as a catalyst in certain types of polymerization reactions that promote film formation. This organometallic compound is also used in the preparation of photosensitive photographic materials.

The nanoparticles derived by adding chromium 2,4-pentanedionate (III) to the PMHNC composition are incorporated into the crystal matrix during film formation. In some cases, the chromium oxide-containing membrane is catalytic.

Cesium 2,4-pentanedionate can be used in the preparation of PMHNC compositions to produce films useful for field emission displays. The resulting film containing cesium oxide is useful as a conductive layer in the formation of electrodes for electronic devices.

When added to the PMHNC composition, cerium 2,4-pentandionate produces a coating containing cerium oxide. The coating containing cerium oxide absorbs ultraviolet radiation and can also be used as a high-k dielectric gate material.

Boron ethoxide is useful in the formation of boron oxide nanocomposites for nanofilms and nanopowder. PMHNC compositions containing boron, boron-modified SiO in microelectronics₂Can be used as a CVD precursor of.

Addition of bismuth (III) t-pentoxide to the PMHNC composition results in a film containing bismuth oxide. Membranes containing bismuth oxide are characterized by X-ray opacity and radio frequency opacity. Membranes containing bismuth oxide can be used in the production of varistor and can also be used in the coating of microparticulate plastics for extrusion.

Aluminum 2,4-pentandionate (III) can be used to form high-k dielectrics with ALD. In some embodiments, PMHNC membranes containing barium oxide derived from barium 2,4-pentandionate are useful as intermediates for sol-gel-derived superconductors.

The addition of beryllium 2,4-pentanedionate to the PMHNC composition results in a highly thermally conductive ceramic coating in some cases. PMHNC films containing cadmium oxide derived from the addition of cadmium 2,4-pentandionate are transparent to infrared radiation and exhibit luminescence and conductivity.

The addition of calcium 2,4-pentanedionate to the PMHNC composition facilitates the coating of the glass microparticles with a thin film, resulting in the desired melting effect. Mixing iridium oxide with the PMHNC coating by the addition of iridium 2,4-pentandionate (III) results in a catalytic and / or photoreducing film.

Other suitable organometallic compounds for addition to the PMHNC composition include lithium ethoxydo, vanadium pentanandionate (III), tin 2,4-pentanedionate (II), palladium 2,4-pentanedionate, There are, but are not limited to, formium 2,4-pentanedionate, antimony (III) ethoxydo, and barium (II) methoxypropoxide.

In addition to the metal oxides formed by the method shown in FIG. 1, various metal oxides, sulfides, phosphides, arsenides, etc. are added in steps 104, 112, and / or 124 to select the PMHNC composition. It is possible to enhance the properties that have been made. Metals suitable for inclusion as oxides, sulfides, phosphates, hafniums, etc. include, for example, titanium, zirconium, zinc, strontium, cadmium, calcium, indium, barium, potassium, iron, tantalum, tungsten, samarium, etc. Bismus, nickel, copper, silicon, molybdenum, ruthenium, cerium, ittrium, barium, tellurium, tantalum, tin, silver, scandium, placeozim, niobium, neodymium, manganese, magnesium, leutium, lithium, lantern, formium, hafnium. , Germanium, gallium, gadolinium, europium, erbium, dysprosium, cobalt, chromium, cesium, boron, aluminum, antimony, lead, barium, beryllium, iridium, etc., or any combination thereof.

The above compounds may be added to the PMHNC composition in the process of FIG. 1, but may be formed during the methods shown in FIG. The advantages, properties, and uses of various oxides and other compounds in coatings and nanopowder formed from PMHNC compositions are described below. The macroscopic properties of these compounds exhibit the properties they exhibit at the molecular level when bound to PMHNC coatings or nanopowder.

Zirconium Oxide and Yttrium Stabilized Zirconium Oxide is a hard, white amorphous powder useful for pigments, heat resistant materials, and ceramics. Zinc oxide is also useful as a heat resistant material and exhibits lower thermal expansion than alumina, magnesia, and zirconia. These oxides impart wear and corrosion resistance to the PMHNC coating.

In PMHNC films, yttrium oxide is useful as a catalyst, colorant, flux, and dye and has flame retardancy. Tungsten oxide can be added to the PMHNC composition as a pigment, opacity agent, and / or catalyst. It is desirable in optical coatings, welding rod fluxes, ceramic finishes, plastics, elastomers, coated fabrics, printing inks, roof granules, glass, and glazes.

In PMHNC films, titanium oxide, titanium dioxide, and tantalum pentoxide provide a high refractive index, low absorption material that can be used for coatings in the near-ultraviolet to infrared region. High density layers or layers can be used. Titanium oxide / titanium dioxide and tantalum pentoxide can be used with silicon dioxide to form a hard, scratch resistant, adhesive coating. A film containing titanium oxide / titanium dioxide can be used as a dielectric in a film capacitor and as a gate insulator in an LSI circuit that requires low leakage voltage characteristics. Tantalum pentoxide also exhibits ferroelectricity. Tantalum oxides are useful in PMHNC compositions as emulsions and pigments and are useful in applications including ceramics, capacitors, and conductive coatings.

When added to the PMHNC composition, the silicon monoxide powder can provide antireflection and / or coherence. In some cases, silicon monoxide powder is used with ZnS and other materials to form a reflective coating. Membranes containing SiO can be used in electronic applications such as thin film capacitors, hybrid circuits, and semiconductor components, but various insulating properties and dielectric properties are determined by the film thickness. Mixed with PMHNC membrane, SiO adds corrosion resistance and wear resistance and can be used as a filler in various applications. Silicon dioxide, synthetic silicon dioxide, silicate powder, silica sand, quartz sand and powder, amorphous silica, and silica airgel are also added to the PMHNC composition (eg ZrSiO).₂/ TiO₂(Composition containing), a high-k film can be formed, and heat resistance and thermal shock resistance can be enhanced. These films are also useful for electronic ceramics.

Scandium oxide can be added to the PMHNC composition to give it a yellow tint and enhance its magnetism. In PMHNC compositions, nickel oxide can act as a corrosion inhibitor and / or oxygen donor and react with molybdenum compounds to form nickel molybdate. Films containing nickel oxide are useful for thermistors, varistor, cermets, resistance heating devices, ceramic glazes, enamel, and pigments.

When added to PMHNC compositions, niobium oxide enhances its use-related properties in ceramic capacitors, glazes, and tinted glass. Addition of mica-like iron oxide to the PMHNC composition results in a durable, corrosion-resistant coating that reflects ultraviolet light. PMHNC nanopowder containing mica-like iron oxide can be dispersed in paints, primers, or other coating compositions to add improved corrosion and weather resistance. The horizontal stacking and superposition of lamellar (mica) particles strengthens the coating composition and acts as a barrier to corrosive elements and the ingress of UV light.

In some practices, manganese oxide powder (MnO)₂) Is added to the PMHNC composition as a colorant or decolorant. MnO imparts ferromagnetism and catalytic properties to PMHNC coatings. Magnetic / black iron oxide powder is a natural iron oxide magnet. When added to the PMHNC composition, the resulting coating is useful as a heat resistant material, an absorbent coating, a catalytic coating, and a catalytic carrier. PMHNC nanopowder containing iron oxide can also be used for cement, fertilizer, gas cleaning applications, etc.

When added to the PMHNC composition, hematite (Fe)₂O₃) Helps resistance to corrosion, including rust and oxidation, thus allowing the composition to flow through the regulating valve without contamination or clogging. In addition, Fe₂O₃Adds non-hygroscopicity to PMHNC films and is useful in steel production or as a colorant and / or coating for rubber, adhesives, plastics, concrete, and iron.

PMHNC compositions containing lutetium oxide powder and / or lanthanum oxide powder exhibit desirable optical properties. Applications include X-ray image intensifying screens, phosphors, dielectric ceramics, conductive ceramics, and barium titanate capacitors.

Indium tin oxide powder is a transparent and conductive material and has various uses in display devices, photovoltaic devices, and thermal reflectors. PMHNC compositions containing indium tin oxide can be used in flat panel display applications, glass manufacturing techniques, electroluminescence display applications, plasma display panel applications, electrochromic display applications, electroemission display applications, and transparent coatings. PMHNC compositions containing indium oxide enhance the performance of resistors, sputtering targets, and conductive inks in integrated circuits.

In PMHNC compositions, hafnium oxide powder adds desirable properties to heat resistant materials and gate oxides. In some embodiments, the addition of germanium oxide powder to the PMHNC composition results in a coating for optical glass.

Gallium oxide powder can be used in PMHNC coatings as a chemical intermediate or as a composition or coating performance enhancer used in semiconductor electronics such as piezoelectric resonators and transducers.

Gadrinium oxide powder is used as a raw material for various fluorescent compounds, atomic reaction absorbers, bubble memory materials, screen sensitizers, and in many other applications in the chemical, glass, and electronics industries. There is. Similar benefits are apparent with PMHNC coating of gadolinium oxide powder and mixing with nanopowder.

Addition of copper oxide powder to the PMHNC composition imparts a red pigment to the PMHNC film and nanopowder, imparting antifouling properties. PMHNC containing chromium dioxide powder can be used as an additive to bricks, pigments, and mortars to extend the life of these materials. When present in PMHNC coatings and nanopowder, boron oxide powder acts as a flame retardant and corrosion inhibitor. Boron oxide powder acts as an acid catalyst or chemical intermediate in the production of various boron compounds.

Bemite Alumina Powder (AlO (OH)) and Alumina Powder (Al₂O₃) Is used in heat resistant materials, abrasives, cement, slag adjusters, ceramics, aluminum chemicals, flame retardants, fillers, welding fluxes, adsorbents, adhesives, coatings, and zeolite detergents. Addition of boehmite alumina powder to the PMHNC composition imparts desired properties on a nanoscale to PMHNC coatings and nanopowder for similar applications.

Similarly, bismuth oxide powder is used in optical glass, flux, varistor formulations, ceramic capacitor formulations, and as a substitute for lead oxide in white porcelain (bone china, etc.). The addition of bismuth oxide powder to the PMHNC composition imparts desired properties on a nanoscale to PMHNC coatings and nanopowder for similar applications.

When added to PMHNC compositions, antimony oxide adds antistatic properties, infrared absorption, transparency, and conductivity that make it advantageous for use in optics and electronic components, especially in display panels. ..

Antimony oxide powder imparts flame retardancy to the PMHNC composition. Coatings made from PMHNC compositions containing molten aluminum oxide powder exhibit improved wear resistance. These compositions are also useful as heat resistant coatings.

Other oxides useful in PMHNC compositions include ruthenium oxide, beryllium oxide, cadmium oxide, calcium oxide, vanadium oxide, samarium oxide, neodymium oxide, molybdenum oxide, placeodium oxide, ferric hydroxide, lithium oxide, oxidation. There are, but are not limited to, formium, europium oxide, cerium oxide, and aluminum oxide.

Various titanium stones can be added to the PMHNC composition to impart the desired properties to the coatings and nanopowder formed from the composition. For example, crystalline strontium titanate is SiO₂It is a high dielectric constant material that can be mixed with PMHNC films used as a dielectric gate material as an alternative to. PMHNC compositions containing lead zirconate titanate may be useful in the field of both loudspeaker and microphone transducers. When added to the PMHNC composition, barium titanate enhances the quality of coatings for use in ferroelectric ceramics, single crystals, storage devices, and dielectric amplifiers.

The following non-limiting examples describe the various steps in the preparation of PMHNC compositions.

Hybrid metal oxides, including silicon, can be formed with one or more additional metal salts in other embodiments. For example, when silicon halide and one or more additional metal salts are added in step 102 or steps 102 and 104, the resulting vehicle system is silicon and M.¹, M²Includes hybrid metal oxides of any or any combination thereof. An exemplary hybrid metal oxide includes [SiO_x : TiO_y], [TiO_y : SiO_x], [SiO_x : ZrO_z], [SiO_x : ZrO_z : TiO_y], [SiO_x : ZrO_z : TiO_y], And [TiO_y : ZrO_z : SiO_x] There is. As used herein, hybrid metal oxides are expressed in descending order by weight%, with 100% by weight representing the total weight of the metal oxides in the composition applied to the substrate. Therefore, vehicle systems containing 19% by weight zirconium oxide, 1% by weight titanium oxide, and 80% by weight silicon oxide are [SiO]_x : ZrO_z : TiO_y] Represented as a hybrid, systems containing 98% by weight titanium oxide and 2% by weight silicon oxide are [TiO_y : SiO_x] Represented as a hybrid. SiO_x, TiO_y, And ZrO_zIs referred to herein as a "metal oxide" and can represent various molar ratios of a metal to oxygen. In some embodiments, the oxide can be dioxide.

Due to these vehicle-based properties, the hybrid metal oxide coating can be applied to a wide range of substrates at room temperature and an inorganic polymer thin film can be formed on the substrate. Due to the vehicle-based composition, the hybrid metal oxide coating can be either hydrophilic or hydrophobic without further treatment after film formation. That is, once the coating has dried, no additional treatment, such as irradiation with UV light, is required to obtain the desired hydrophobicity / hydrophilicity. As used herein, a "hydrophilic" surface has a contact angle with water of less than about 20 °, less than about 10 °, or less than about 5 °. As used herein, a "hydrophobic" surface has a contact angle with water of at least about 90 °.

In one example, it contains more than 50% by weight titanium oxide (as used herein, [TiO]._y : SiO_x], [TiO_y : SiO_x : MO_z], [TiO_y : MO_z: SiO_x] Etc.) The aqueous hybrid metal oxide composition forms a hydrophilic coating that absorbs water and repels non-polar solvents such as toluene. Contains more than 50% by weight silicon oxide (as used herein, [SiO]_x : TiO_y], [SiO_x : TiO_y : MO_z], [SiO_x : TiO_y : MO_z] Etc.) In an aqueous hybrid metal oxide composition, the vehicle system forms a hydrophobic coating that repels hydrophilic polar solvents such as water.

Hydrophobic coatings impart corrosion resistance to the substrate, repel water and make water droplets more like balls on the surface of the coating than to absorb water. Thus, hydrophobic coatings can form corrosion resistant coatings for metal substrates, while hydrophilic coatings cause water to come into contact with the substrate and contribute to electrochemical corrosion.

Hydrophobic coatings formed from silicon-titanium hybrid metal oxide vehicle systems can include, for example, more than 50% by weight silicon oxide and less than 50% by weight titanium oxide. Examples are about 80:20, about 95: 5, about 98: 2, about 99: 1, and about 99.99: 0.01 SiO_x : TiO_yThere is. Hydrophobic coatings formed from hybrid metal oxide vehicle systems containing silicon, titanium, and zirconium may contain more than 50% by weight silicon oxide, and the sum of titanium and zirconium oxides may be less than 50% by weight. it can. As an example, for non-photocatalytic coatings, [SiO_x : ZrO_z : TiO_y] May be about 80:19: 1. In some cases, there is no titanium and [SiO_x : ZrO_z] It becomes a vehicle system.

The hydrophilic coating formed from the titanium-silicon hybrid metal oxide vehicle system can include, for example, more than 50% by weight titanium oxide and less than 50% by weight silicon oxide. Examples are about 80:20, about 95: 5, about 98: 2, about 99: 1, and about 99.99: 0.01 TiO._{y: y:}SiO_x There is. Hydrophilic coatings formed from hybrid metal oxide vehicle systems containing titanium, silicon, and zirconium contain more than 50% by weight titanium oxide, and the sum of silicon oxide and zirconium oxide can be less than 50% by weight. .. In some cases, there is no silicon, [TiO_y: ZrO_z] It becomes a vehicle system.

Optimal solid content and vehicle-based film-forming, binding, and stability are determined by the chloride and ammonium ion concentrations, amount of peroxide added, and various steps described above in connection with FIG. It is obtained by paying attention to factors such as pH, pressurization during heating, heating and cooling temperatures. The resulting vehicle system functions as a binder and a film-forming body of the hybrid metal oxide nanoparticles that are stabilized in a solution state. It is advantageous for the nanoparticles to have a very small particle size and be formed to exhibit a high zeta potential.

In particular, the ammonium ion concentration is related to the pH of the mixture formed during the process. Chloride ion removal to less than about 2 ppm or less than about 1 ppm and effective ammonium ion concentration promote the formation of a stable vehicle system. The weight ratio of the peroxide added to the solid of the colloidal suspension after chloride ion removal may be about 30 ± 20%, for example about 28-33%. The pH value increased from less than 1 in step 102 in FIG. 1 to a maximum of 9 or 11.5 before the chloride ion removal in step 108 and to 4 or less after the addition of peroxide in step 116, throughout the method. It fluctuates over. In step 118, the mixture is slightly acidic and has a pH of about 5-7. The vehicle system resulting from step 128 is mostly neutral and is about 7.0 to about 7.5, or about 7.0 to about 10, depending on the pH of the neutralization in step 106. In FIG. 1, the weight ratio of titanium oxide is higher than the sum of the weight ratios of silicon oxide and other metal oxides, [TiO_y : SiO_x : MO_z] The vehicle system is described in detail below. MO_z(For example, ZrO_z) May or may not exist. MO for simplicity_zIs not present in this exemplary description. [TiO_y : SiO_x] Measured indicators such as pH in the vehicle system, heat generated, etc. are based on reactions that occur during similar treatment steps [SiO]_x:TiO_y] It is different from the vehicle index.

An acidic aqueous mixture of titanium tetrachloride and silicon tetrachloride is formed in step 102. The pH of the mixture starts below 1 and steadily rises to about 11.5 towards a neutral pH of about 7.5, depending on the molar ratio of titanium to silicon present in the solution. During neutralization with ammonium hydroxide in step 106, hydroxides of titanium and silicon float from the colloidal suspension and redisperse in suspension with gentle agitation. Flakes are rarely visible throughout the neutralization process. The heat released in the neutralization reaction is steadily generated as the reaction progresses. After neutralization, the metal hydroxide mixture is a white opaque body with a seaglass greenish tint, like pebbles on the beach.

Once neutralized, the mixture stabilizes in about 24 hours or less (eg, about 12 hours or less, about 8 hours or less, or about 4 hours or less). Suspended particles form light, fluffy aggregates that appear to be held together by van der Waals forces. The agglomerated particles settle quickly, forming a loosely sticky mass. At this point in the process, the colloidal suspension can be packaged and transported in containers. The particles may settle during transport but can be resuspended with light agitation.

As described above, steps 108-116 may be followed. After the final filtration / decantation in step 108, one or more different ion exchange resins can be added to the suspension to easily remove chloride ions. Chloride ions are effectively replaced by ammonium ions (including those derived from ion exchange resins) to increase the pH and the colloidal suspension in step 110 is the addition of peroxide in step 116. Prepare for. Prior to peroxide addition, the suspension is cooled to a temperature below about 10 ° C. During the addition of the peroxide, cooling is performed to control and stabilize the rate of exothermic reaction between the metal hydroxide forming the metal peroxide and the peroxide. Addition of about 30 ± 20% by weight of peroxide, such as about 25-35% by weight, or about 30-33% by weight of peroxide with respect to the colloidal solids reduces the pH of the mixture to about 2 or less. To do. Three-dimensionally stabilized according to steps 118-128 [TiO_y : SiO_x] Vehicle system can be formed.

Three-dimensionally stabilized [TiO_y : SiO_x] The vehicle system can be applied to the substrate and dried under ambient conditions. Hydrolysis and condensation reactions occur during drying to form a hybrid metal oxide coating or film on the substrate. Condensation reactions include, for example, bonding of a peroxide to a surface hydroxyl group with elimination of water, binding of one peroxide to another peroxide, and the like. The hybrid metal oxide coating is polymeric and hydrophilic and may be photocatalytic in the presence of photocatalytic species such as anatase titanium dioxide.

FIG. 1 shows silicon oxide (SiO) in the composition applied to the substrate._x) Weight percentage is TiO_yExceeds the weight percentage of, [SiO_x : TiO_y : MO_z] The vehicle system is described in detail below. MO_z(For example, ZrO_z) May or may not exist. MO for simplicity_zDoes not exist in this example.

An acidic aqueous mixture of titanium tetrachloride and silicon tetrachloride is formed in step 102. The pH of the mixture is less than about 1. The amount of base required for neutralization and the shape of the titration curve are the amount ratio of silicon oxide to titanium oxide (that is, [SiO]._x : TiO_y]) Depends on. [SiO_x : TiO_y] Vehicles produce hydrophobic coatings, but produce hydrophilic coatings [TiO_x : SiO_y] Compared to vehicle type, it requires less base for neutralization (for example, about 1/3 less) and produces higher pH. During neutralization with ammonium hydroxide in step 106, hydroxides of titanium and silicon float from the colloidal suspension and redisperse in suspension with gentle agitation. The flakes are barely visible throughout the neutralization process. Heat is released non-linearly during neutralization, and as the pH approaches 7, [TiO_x : SiO_y] More heat is released than was observed in the vehicle system. The base is added until the pH of the mixture is from about 7.0 to 8.0 (eg, about 7.5 or about 7.65), or from about 7.0 to 11.5. Silicon hydroxide becomes highly soluble at high pH. Therefore, higher pH may be desirable for systems with a higher percentage of silicon. After neutralization, the metal hydroxide suspension, which has a higher silicon molar ratio than the titanium molar ratio, is opaque, white, and has a translucent aqua green tint, which is that of titanium. It shows that the colloid average particle size distribution is smaller than that of the greenish metal hydroxide mixture having a molar ratio higher than that of silicon.

When left at room temperature for about 12 hours, the pH of the mixture will be about 7.0 to 8.5 (eg, about 7.6 to about 8.2), or about 7.0 to 11.5, which may vary from the bottom to the top of the container containing the mixture. is there. After forming a homogeneous suspension with sufficient stirring, a single pH value is obtained. The suspended particles form light, fluffy aggregates that appear to be held together by van der Waals forces. The agglomerated particles settle quickly, forming a loosely sticky mass. The particles can be resuspended with light agitation.

Effective chloride ion removal is achieved during filtration or decantation, followed by reconstruction or resuspension in step 108. Filtration, such as with a Nutnel filter, allows quantitative separation and at the same time is gelatinous by mixing additives such as silanes, organic metals, monomers and nanoparticles in the solid phase, liquid phase or gas phase. While allowing it to react with the clay, the decantation is advantageously rapid. The advantages of decantation may not be apparent in the filtration of hydrophobic metal hydroxide clays over the filtration of hydrophilic metal hydroxide clays, because hydrophobic clays absorb less water and filter faster. Is possible.

With continuous reconstruction, as the amorphous hydroxide clay becomes denser and denser, more agitation may be required for sufficient removal of chloride ions. The ammonium ions present in the mixture have a strong affinity for chloride ions, promote the removal of chlorides from the metal chlorides and allow the formation of metal hydroxides. For example, chloride ions may not be sufficiently removed unless the size of the suspended particles is sufficiently reduced by wetting and stirring. In some cases, aqueous ammonium ions, as well as one or more of the additives, fillers, etc. described herein, are added during the reconstitution (eg, in reconstituted water) as part of the process of introduction into the suspension. Is added. Ammonium ions from the ion exchange resin may also enter the suspension.

After the first filtration, most of the amorphous metal hydroxide remains in the clay separated from the filter (eg, multi-layer filter). The clay is a translucent, glassy milky white gel with a slight green tint, but the filtrate contains chloride and ammonium ions and is transparent. The filter may be, for example, a 0.75 micron (GF / F) or 1 micron or 20 micron Whatman grade GF / B glass microfiber filter (Whatman plc, UK). The silicon hydroxide remains in the gelatinous clay.

After the third filtration or decantation, the chloride ion concentration is about 100-200 ppm and the pH is above about 8.0-8.5, about 8.0-11.5, or 11.5. Gelatinous clays and filtrates can be visually tested to evaluate chloride ion removal. The clear filtrate shows the presence of an undesirably large amount of chloride ions, but the turbidity indicates that the chloride ions have been properly removed.

After the fourth filtration or decantation, which may be the last filtration or decantation, the chloride ion concentration after reconstruction drops from about 10 to about 100 ppm, or from about 10 to about 20 ppm, and the solution. The pH of is about 8.5 to about 9.5 (eg, about 8.8), or about 8.5 to about 11.5. In some cases, one or more additional filtrations or decantations may be required to reduce the chloride ion concentration to acceptable levels. Based on the solid content of the reconstituted clay obtained from the last filtration, over about 30-40 minutes to 2.5 hours, one or more different ion exchange resins are added in increasing amounts to about 2 ppm or less of chloride ions. Concentrations and pHs of about 7.0 to about 8.0, or about 7.0 to about 11.5 can be obtained. As chloride ions are removed, ammonium ions are prevented from entering the colloidal suspension, in contrast to hydrophilic vehicle systems. Sulfonic acids from ion exchange resins can enter the suspension, lowering the pH. Factors such as chloride ion concentration can be used to determine the required amount of ion exchange resin and the time required to perform substantially complete removal of chloride ions. The steric stabilization required to obtain a stable vehicle system cannot be achieved if chloride ions remain after the filtration and ion exchange process, for example due to inadequate filtration and / or molecular interference from pollution sources. Desirable chemical and physical properties such as hydrophobicity, film formation, binder capacity, flexibility, stability, and durability are such that the chloride ion concentration is reduced to about 2 ppm or less, more preferably about 1 ppm or less. This can be achieved when the pH of the turbid liquid is in the range of about 8.3 to about 9.3 (eg, about 8.8 to about 9.2), or about 8.3 to about 11.5.

The removal of chloride ions must be substantial while obtaining the desired pH prior to the addition of peroxide to the metal hydroxide reconstituted colloidal suspension. Peroxide is added with cooling of the colloidal mixture below 10 ° C. Based on the colloidal solids, about 30 ± 20% (eg, about 25-35% by weight or about 30-33% by weight) of peroxide is added to the cooled colloidal clay suspension and the mixture is added. Reduce the pH to about 4 or less or about 2 or less. This metal hydroxide reacts with the peroxide at low temperatures, which effectively controls the rate of the exothermic reaction. If the suspension is not cooled sufficiently, the particles may not be in a dissolved state. In some cases, uniform cleavage of the peroxide occurs. Excess peroxide can give the film an overly yellow appearance. Instability will increase the tendency for precipitation and separation from the solution. Insufficient peroxides leave unreacted hydroxyl groups on metals in clays (eg, silicon, titanium, zirconium) and remain redispersed in colloidal suspensions, resulting in membrane and binding capabilities. Will reduce and contribute to instability. Instability can also be caused by adverse variations in composition that lead to precipitation of colloidal suspensions.

The reaction between metal hydroxides and peroxides can be shown as follows: M (OH)₄ + 3H₂O₂+ 4NH₄⁺ (aq) M (OO)₄⁺ + 5H₂ + 3O₂ + 4NH₄⁺FIG. 6 represents a model of silicon peroxide formed by this reaction and stabilized in solution, with ammonium ions in the immediate vicinity of the peroxide group. Hydrogen bonds with water in the aqueous solution are thought to stabilize the arrangement of silicon peroxide and ammonium ions. After addition and cooling of the peroxide (eg, for about 24 hours), the mixture has a pH of about 5 to about 6 (eg, about 5.6) and is brought to room temperature. The pH rises and stabilizes at about 6.5 to about 7.5 (eg, about 7.0 to about 7.3) or about 6.5 to about 11.5. The mixture may be filtered through a GF / B (1 micron filter) and placed in a flask. After about 50-80% of the mixture has been filtered, silica-containing mesoporous nanogelatinized membranes form on the filter. When the peroxo group is stabilized by ammonium ions on the metal, a secondary reaction occurs in the filtrate, which is evidenced by the generation of bubbles from the filtrate (eg, hydrogen and oxygen gas).

Mesoporous gelatinous membranes allow sub-nanometer to nanometer-sized particles throughout the gel, with stable suspensions of sub-nanometer and nanometer-sized particles of about 7.3 to about 7.6, or about 7.3 to about 11.5. Formed at pH ranges. These nanoparticles are sterically stabilized and can be thought of as a type of ionic salt in a nearly neutral aqueous phase solution. These ions are further stabilized by hydrogen bond interactions. Metal peroxides are characterized by high zeta potentials. Silica-containing nanogelatinous membranes formed as a side reaction in the filtration residue have a mesoporous attribute (about 2 nm to about 50 nm, or about 2 nm to about 300 nm) that stabilizes metal peroxide nanoparticles in the aqueous phase. Hole diameter) is shown. When these stabilized nanoparticles are applied to the substrate, hydrolysis and condensation reactions cause polymer film formation. Gels are nanocomplexes of hybrid metal oxides that can be reconstituted and refiltered to produce additional vehicle-based or heterogeneous catalyst carriers for use in a variety of other applications. it can.

The metal peroxide agglomerates of nanoparticles in a clear metal peroxide solution (with a maximum light transmittance of about 99.9%) appear to have a size distribution of agglomerates from about 10 nm or less to about 15 nm. The solid content of the solution is about 0.1% to 1%. FIG. 7 (scale is not constant) depicts metal peroxide aggregates in solution and submesoporous interactions that may be present. Ammonium-stabilized metal peroxide 700 seems to be about two to three nanometers tenths. These stabilized metal peroxides aggregate to form particles on the order of nanometers. The particles can aggregate side by side in row 702 and can interact with other rows of particles in solution. The rows will be on the order of tens of nanometers. When the solution is applied to the substrate, hydrolysis and condensation reactions occur on the glassy polymer film bonded to the surface of the substrate. These membranes range in thickness from less than 1 nm to about 5 nm, and in some cases from about 1 nm to about 10 nm, indicating loosely bonded metal peroxide aggregates.

The metal salts added in step 102 or 104 can be selected to improve the method of forming the vehicle system, improve the properties of the resulting vehicle system, or both. For example, [SiO_x : ZrO_z: TiO_y] Vehicle type is about 80% by weight SiO_x, About 15% by weight ZrO_z, And about 5% by weight TiO_yCan be included. ZrCl during step 102₄Reacts with concentrated HCl, ZrOCl₄To form. This exothermic reaction is [SiO_x : TiO_y] SiO in the formulation₂Compared to the solubility of [SiO_x : ZrO_z: TiO_y] SiO in the formulation₂Increases the solubility of. In addition, [SiO_x : ZrO_z: TiO_y] Zirconium oxide in the polymer film formed by the vehicle system produces a harder, more crack resistant film.

[SiO_x : ZrO_z : TiO_y] The formulation is a scratch-resistant, transparent optical coating that can be used in a variety of applications, such as catalytic carriers, where strength, adhesion, chemical and physical (eg, thermal) durability are desired. As a catalyst carrier, the vehicle system is photocatalytic [TiO_y : SiO_x] Can be applied as a protective layer to organic substrates that will be damaged by the composition. In some embodiments, the photocatalytic coating protects [SiO]_x : ZrO_z : TiO_y] It is applied on the coating. [SiO_x : ZrO_z : TiO_y] The coating can also increase the adhesive strength of the photocatalytic coating. In some cases, [TiO_y : SiO_x] The formulation is [SiO]_x : ZrO_z : TiO_y] Dispersed in the formulation to give the desired distribution of metal oxides. In other cases, protection [SiO_x : ZrO_z : TiO_y] Coating is photocatalyst [TiO_y : SiO_x] Is applied on top.

In some embodiments, [SiO_x : TiO_y] Or [SiO]_x : ZrO_z : TiO_y], The silica-containing nanogelatinized membrane can be reconstituted to form a vehicle system having a solid content of about 0.1 to 0.25% by weight or about 0.1 to 1% by weight of the whole system. The vehicle system can be spray-dried as a heterogeneous mesoporous silica pigment. The surface area of the dispersed nanoparticles is considered to be several hundred square meters per gram. The applied composition is [SiO_x : TiO_y] Form a thin and durable film of "glass". Using a foam brush, application of a 25 micron undried film of a composition with a solid content of about 0.25% after filtration results in a film coating thickness of about 63 ± 6 nm. Similarly, application of a 25 micron undried film of a composition with a solid content of about 0.1% after filtration using a foam brush results in a film coating thickness of about 25 nm.

[SiO_x : ZrO_z : TiO_y] Vehicle systems can be used to form high-κ dielectrics for use in semiconductor chips. In some embodiments, [SiO_x : ZrO_z : TiO_y] Weight ratios are formulated to achieve the desired dielectric constant while achieving the industry's target film thickness of about 4-6 nm, and even less than 1 nm for future progress. The vehicle-based percentage composition can be a selected amount of silicon (silicon dioxide dielectric constant = 2 to 3.8), zirconium (zirconium oxide dielectric constant = 12.5), titanium (titanium oxide dielectric constant = 110), or these. It can be adjusted to obtain a high κ dielectric by adding any combination. As such, the hybrid metal oxides described herein can easily provide a reasonably thin film with a tunably higher dielectric constant than pure silicon dioxide. In addition, these layers can be formed by a simple (eg, spray or brush) application of a purely inorganic aqueous film-forming body, which can occur by drying at ambient temperature, thus organic metals and volatile harmful air. Eliminates the need for contaminating solvents. In addition, problems associated with carbon soot and charged gate leakage are avoided.

Due to the high water content (at least about 98%) and low solid content (less than about 2%, or about 0.1% to 1%) of the vehicle system described herein, the vehicle system is suitable for coating transparent substrates. Is. With a valid percentage of anatase titanium oxide, [SiO_x : TiO_y] The photocatalytic property of the system can be enhanced. These systems can be attached to transparent substrates such as glass and other substrates with hydroxydo groups on the surface. Since silicon oxide has a lower refractive index than titanium oxide, a high percentage of silicon oxide allows light to remain in the film for a longer period of time, leading to improved photocatalytic efficiency of the coating. Therefore, [SiO_x : TiO_y] Systems can form catalytic carrier matrices for various catalytic reactions that benefit from large surface areas. In some embodiments, [SiO_x : TiO_y] The formulation is applied to an elastic, thermosetting, or thermoplastic substrate and a photocatalytic coating is applied to protect the organic polymer substrate from photocatalytic degradation.

In order for the corrosion-resistant film to be applied on the metal substrate, [SiO_x : TiO_y] The composition is SiO_x : TiO_yMay be included in a weight ratio of about 9: 1 to about 9.99: 0.01. In some cases, the vehicle system is 100% weight SiO._xincluding. Hybrid [SiO_x : ZrO_z : TiO_y] Formulations are also suitable for corrosion resistant coatings and can protect the substrate with a hard, substantially impervious, scratch resistant film. Free radical degradation by outdoor exposure is inhibited at the interface between the coating and the metal. These inorganic polymer coatings can protect various metal substrates from anode and cathode electrochemical transport, galvanic corrosion, tint cell corrosion, oxygen tint cell corrosion, filamentous corrosion, metal ion tint cell corrosion, active / passive corrosive batteries ( It inhibits the electrochemical circuits required for corrosion such as active / passive corrosion cells), intergranular corrosion, exfoliation corrosion, and metallic mercury corrosion.

The small particles in the vehicle system described herein give rise to a thin flexible glass coating that can be used to seal exposed surfaces at nanometer to mesoporous and macro film thickness levels and thus base. Covers virtually all exposed areas on the material. In some cases, the organic monomer can be polymerized by hydrolysis and condensation reactions to form the polymer upon subsequent application of the thin film. For example, mixing urethane or polyester functional groups with silane can provide flexibility. Two or more coatings of the same or different composition and thickness can be applied to the surface to obtain the desired result.

In some embodiments, a low percentage of photocatalytic anatase particles are [SiO]._x : TiO_y] It is basically fixed in an inorganic glass film or matrix formed by a vehicle system. These vehicle systems are, for example, at least about 90% by weight or at least about 99.9% by weight SiO._xincluding. In one embodiment, about 98% by weight SiO_xAnd about 2% by weight TiO_yVehicle systems containing, produce glass films with a thickness of about 1 nm to about 5 nm. In these hydrophobic embodiments, low concentrations of anatase particles can effectively function as UV absorbers without degrading the coating.

In certain embodiments, [SiO_x : ZrO_z: TiO_y] Vehicle systems include, for example, the addition of dipodal silanes such as, but not limited to, bis (trimethoxysilyl) methane or bis (triethoxysilylethanesilane). Silane affinities are largely TiO._yMost of them are SiO_xIt is higher than the vehicle system. Therefore, bis (trimethoxysilyl) methane or (triethoxysilylethane) [SiO]_x : ZrO_z: TiO_y] Contains the same additives when mixed with vehicle [TiO_y : SiO_x] A coating with better hardness, adhesiveness, and scratch resistance than a coating formed from a vehicle system is produced.

<p>(Example 1) SiCl₄Was mixed with an aqueous mixture of titanium-based solutions containing acids and other metal chlorides. The organic metal was miscible with the vehicle by the method shown in FIG. 1, including neutralization of the acidic mixture with an ammonia-based solution. The solution then had the appearance of water glass or liquid silica. After filtration, reconstruction of the metal hydroxide, and addition of the peroxide solution, bis (triethoxysilyl) ethane was added to the amorphous metal peroxide solution. Bis (triethoxysilyl) ethane is a dipodal silane capable of forming six bonds with the substrate. Once these bonds are formed, the resistance to hydrolysis is about 100,000 times that of conventional coupling agents capable of forming only three bonds with the substrate, or silanes capable of forming four bonds with the substrate ( It is estimated to be about 75,000 times that of (tetraethoxysilane, etc.).</p><p> The solution was boiled under pressure above atmospheric pressure. Continued boiling under pressure to increase the proportion of nanocrystalline metal oxides resulted in an adhesive, transparent photocatalytic film that would provide corrosion protection when bonded to the untreated steel substrate. The resulting PMHNC coating is believed to be a hybrid crystal of silicon, anatase, and zinc oxide and contains linear species such as Si-O-Ti-O-Ti-O-Ti-O-Zn-O. it is conceivable that.</p><p>(Example 2) In composition A prepared as described herein for the method of FIG. 1, the relative percentage of Si: Ti: Zr: Sn oxide in the hybrid metal oxide is 0.63: 90.68: 3.31: 4.48. , Non-porous ceramic tile coated.</p><p> Two tiles were coated with Composition A and the two tiles coated with a competing product were cured at ambient temperature for 24 hours. With a 3 mL pipette, 5 drops of deionized water: methylene blue solution (water: methylene blue ratio, 1000: 1) were deposited on one tile with composition A coating and one tile with competing product coating. .. The water droplets spread in a circle with a diameter of 2 cm. Tile without methyln blue (one with a coating formed from Composition A and one with a coating formed from a competing product) was stored in the dark (dark contrast tile).</p><p> Tiles with methylon blue water droplets were exposed to sunlight in South Florida for one day. Overnight, the tiles were placed 33 cm from a UV lamp (F15 T8BL 15W T8 18 "BLACK LIGHT LITE F15W / BL, emitting 365 nm light, manufactured by General Electric). , X-Rite 918 Tristimulus Reflection Colorimeter measured every 8 hours using 0 ° / 45 °. Delta E of methylene blue spots on dark control tiles and exposed tiles was recorded. Stain cleansing on two exposed tiles. As it was done, the stained area became lighter in overall color, approaching the color of the dark contrast tile.</p><p> FIG. 8 shows a dark control (no stain) and% cleansing of stains on exposed tiles coated with Composition A and competing products. Exposure tiles coated with Composition A (Plot 800) showed a dramatic and surprising increase in photocatalytic efficiency compared to exposure tiles coated with competing products (Plot 802). Dark controls are indistinguishable (plot 806). After approximately 100 hours of exposure, tiles coated with Composition A purified methylene blue with a photocatalytic efficiency 48% more effective than tiles coated with competing products.</p><p> Some embodiments of the present invention have been described. Nevertheless, it will be appreciated that various improvements are possible without departing from the spirit and scope of the invention. Therefore, other embodiments are also within the scope of the following claims.</p>