JP2011505499A - Anticorrosive material - Google Patents

Abstract

An anticorrosive material comprising colloidal particles and multivalent metal ions is disclosed. The particles are preferably silica. The metal ion may be Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, or Ce. This material can be added to the conversion coating liquid, mixed with a polymer binder, or used as is to form a coating.
[Selection] Figure 1

Description

  The present invention relates to an anticorrosion material including an anticorrosion composition, a composition, a composition, and a method for producing the anticorrosion composition.

  In the metal processing and coating industry, it has good corrosion resistance and does not contain toxic metals while retaining other desirable film properties such as adhesion, strength, anticorrosion properties, thin film thickness etc. There is a need for products and formulations. There is also a need in the art for methods of making and using anticorrosion compositions and formulations.

  The present invention addresses some of the difficulties and problems discussed above by finding new anticorrosive compositions, formulations, and films made therefrom. The composition includes two types of nano-sized metal oxide particles in combination with divalent and trivalent metal ions.

  In one exemplary embodiment, the anticorrosive composition of the present invention is present in an amount of at least about 0.001 wt% to about 10 wt% or less based on the total weight of the solvent; colloidal particles; and the composition. At least one polyvalent metal ion.

  In a further exemplary embodiment, the anticorrosive composition of the invention comprises a solvent; colloidal particles; and at least one polyvalent metal ion; at 60 ° C. for at least 60 minutes, or 25 ° C. for at least 8 hours. Stay stable.

  In a further exemplary embodiment, the anticorrosive composition of the present invention comprises a solvent; colloidal particles; and at least one polyvalent metal ion; wherein the ratio of metal ion to metal oxide is from about 0.001. It is about 0.1 or less. The ratio of polyvalent metal ions to colloidal particles is at least about 0.005, preferably at least about 0.008, more preferably at least about 0.01, even more preferably at least about 0.01 to about 0.1. It may be.

  The invention further relates to a method of forming a representative anticorrosive composition. One exemplary method is to add up to 40% by weight of metal oxide particles (where% by weight is based on the total weight of the dispersion) to water; a polyvalent metal salt in the dispersion. Adding; then mixing the composition; etc. to form a dispersion of colloidal metal oxide particles in water. The resulting dispersion desirably has a stable viscosity for at least 60 minutes at 60 ° C. or at least 8 hours at 25 ° C.

  In another exemplary embodiment, the anticorrosive formulation of the present invention comprises a binder; a solvent; colloidal particles; and at least one polyvalent metal ion; and the ratio of metal ion to metal oxide is about 0. More than 001 and about 0.1 or less. The ratio of polyvalent metal ions to colloidal particles is at least about 0.005, preferably at least about 0.008, more preferably at least about 0.01, even more preferably at least about 0.01 to about 0.1. It may be.

  In a further exemplary method using an anticorrosive formulation, such a method provides a substrate having a first surface; coating the formulation on the first surface of the substrate; and a coated substrate A method of forming a coated substrate comprising the steps of: drying the material; The resulting coating provides a substrate with desirable corrosion resistance that is particularly useful in corrosive environments.

  In one exemplary embodiment, the corrosion resistant material of the present invention comprises a substrate; and colloidal particles and at least one polyvalent metal ion, wherein the ratio of metal ion to metal oxide is about An anticorrosive coating on the substrate that is greater than 0.001 and not greater than about 0.1. The ratio of polyvalent metal ions to colloidal particles is at least about 0.005, preferably at least about 0.008, more preferably at least about 0.01, even more preferably at least about 0.01 to about 0.1. It may be.

  These and other features and advantages of the present invention will become apparent upon review of the following detailed description of the disclosed embodiments and the claims.

FIG. 1 is a cross-sectional view of a representative article of the present invention comprising at least one layer comprising the anticorrosive material of the present invention.

  To facilitate an understanding of the principles of the invention, specific embodiments of the invention are described below, and specific terms are used to describe the specific embodiments. However, it will be understood that the use of specific terms is not intended to limit the scope of the invention. Changes in the principles of the invention that are discussed, further modifications, and such further applications are believed to be normally conceived by one of ordinary skill in the art to which the invention belongs.

  The present invention relates to anticorrosion coatings and formulations and dispersions suitable for forming anticorrosion coatings. The invention further relates to a method for producing an anticorrosion material, as well as a method for using such a material. Descriptions of typical anticorrosive materials, coatings, formulations and dispersions for forming anticorrosive materials, and methods for producing anticorrosive materials, coatings, formulations and dispersions are given below.

  The anticorrosion compositions and formulations of the present invention have good corrosion resistance and are capable of containing toxic metals while still retaining other desirable film properties such as adhesion, strength, thin film thickness, anticorrosion properties, etc. Not included.

  In an exemplary embodiment, the anticorrosive composition of the present invention comprises at least one solvent, colloidal particles, and at least one present in an amount of at least about 0.001 wt% to no more than about 5 wt%, based on the total weight of the composition. A kind of polyvalent metal ion. The polyvalent metal ion is about 0.1% to about 4% by weight, preferably about 0.1% to about 3% by weight, based on the total weight of the composition containing 20-40% solids. More preferably, it can be present in the composition in an amount of from about 0.1% to about 2% by weight, even more preferably from about 0.1% to about 1% by weight. Depending on the solids content, the above-mentioned amounts of polyvalent metal ions in the composition can be increased or decreased, respectively, as the solids content is increased or decreased.

  In a further exemplary embodiment, the anticorrosive composition of the present invention comprises a solvent; colloidal particles; and at least one polyvalent metal ion; and the ratio of metal ions to colloidal particles is from about 0.001. It may be as large as about 0.1 or less. The ratio of polyvalent metal ions to colloidal particles is at least about 0.005, preferably at least about 0.008, more preferably at least about 0.01, even more preferably at least about 0.01 to about 0.1. It may be.

  The particles can be composed of metal oxides, sulfides, hydroxides, carbonates, silicates, phosphates, etc., preferably metal oxides. As used herein, “metal oxide” is defined as a binary oxygen compound in which the metal is a cation and the oxide is an anion. Metals can also include metalloids. Examples of the metal include an element on the left side of a diagonal line drawn from boron to polonium on the periodic table. Metalloids or metalloids include elements on this line. Examples of metal oxides include silica, alumina, titania, zirconia, and the like, and mixtures thereof. The particles may be in a variety of different symmetric, asymmetric, or irregular shapes, such as chain, rod, or piece of wood. The particles may have different structures such as amorphous or crystalline and may be in various forms such as gel, sol, precipitated, fume and the like. The particles can include a mixture of particles that have different compositions, dimensions, shapes, or physical structures, or may be the same except for different surface treatments. Preferably, the metal oxide particles are amorphous, such as colloidal silica.

The term “colloidal particles” or “colloidal sol” means particles derived from a dispersion or sol in which the particles do not settle out of the dispersion for a relatively long time. Such particles are typically less than 1 micron in size. Colloidal sols having an average particle size in the range of about 1 to about 300 nanometers and methods for their production are well known in the art. US Patents 2,244,325; 2,574,902; 2,577,484; 2,577,485; 2,631,134; 2,750,345; 2,892,797; 3,012,972; And 3,440,174 (the contents of which are incorporated herein by reference). A colloidal sol having an average particle size in the range of 5 to 100 nanometers is more preferred for the present invention. The colloidal sol may have a specific surface area (measured by BET nitrogen adsorption) ranging from 9 to about 2700 m ² / g-SiO ₂ .

  Although many types of colloidal sols can be used in the anticorrosive composition of the present invention, representative colloidal silica sols are described below. Most colloidal silica sols contain an alkali that stabilizes the silica particles from agglomeration or gelation. The alkali is usually an alkali metal hydroxide, and the alkali metal is from Group IA of the periodic table (hydroxides such as lithium, sodium and potassium). Most commercially available colloidal silica sols contain sodium derived from sodium silicate that is used to produce colloidal silica at least in part, but sodium hydroxide is added to gel the sol against gelation. It can also be stabilized. Some alkaline colloidal silica sols are stabilized by aqueous ammonia. Such alkaline colloidal silica sols are not suitable for the present invention. Most polyvalent metal ions suitable for the present invention form insoluble metal hydroxides in alkaline solutions, which limits the processing of the anticorrosive formulation. Acidifying an alkaline colloidal silica sol, for example with an inorganic or organic acid, can reduce the stability of the resulting colloidal silica sol and the anticorrosive composition of the present invention and can be detrimental to the anticorrosive properties of the coating It is disadvantageous because of its nature.

Deionized colloidal silica sol is suitable for the present invention. “Deionized” means that all metal ions, such as alkali metal ions such as sodium, have been substantially removed from the colloidal silica solution phase and replaced with hydronium (H ₃ O or H +) or acid ions. Means. Methods for removing alkali metal ions are well known and include ion exchange with suitable ion exchange resins (US Pat. Nos. 2,577,484 and 2,577,485), dialysis (US Pat. No. 2,773,028), and electrodialysis. (US Pat. No. 3,969,266).

  To impart the stability of colloidal silica sols to gelation at acidic pH, the particles are made of aluminum as described in US Pat. No. 2,892,797, the contents of which are incorporated herein by reference. It is also possible to modify the surface with and then deionize the modified silica.

  The term “polyvalent metal ion” as defined herein means a metal ion having a valence of 2 or 3. Examples of polyvalent metal ions include Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, Ba, Mn, Mo, V, etc. For example, but not limited to.

  In an exemplary embodiment of the invention, the solids content (or the amount of colloidal particles) of the anticorrosive composition is about 1 to about 40% by weight, preferably about 1 to about 30, based on the total weight of the composition. % By weight, more preferably about 1 to about 25% by weight, still more preferably about 1 to about 20% by weight.

  In a further exemplary embodiment, the anticorrosive composition of the invention comprises a solvent; colloidal particles; and at least one polyvalent metal ion; at 60 ° C. for at least 60 minutes, or 60 ° C. for at least 120 minutes. Stay stable. The composition typically remains stable at 60 ° C for at least about 3 hours, preferably at 60 ° C for at least about 6 hours, more preferably at 60 ° C for at least about 12 hours, and even more preferably at 60 ° C for at least 24 hours. Can keep. The composition is typically stable at 25 ° C for at least about 24 hours, preferably at 25 ° C for at least about 2 days, more preferably at 25 ° C for at least about 4 days, even more preferably at 25 ° C for at least about 8 days. Can keep. The term “stable” as defined herein means a dispersion of particles that do not gel after a lapse of time.

  The anticorrosive composition of the present invention can be produced by mixing colloidal particles with a solvent and a polyvalent metal ion in the form of a salt. The solvent may be any solvent that is compatible with the colloidal particles and the polyvalent metal ion salt. Water is a preferred solvent, but a mixture of water and a water-miscible organic solvent (eg, methanol, ethanol, propanol, acetone, etc.) can be used. Useful polyvalent metal ion salts are those having a polyvalent metal ion and a polyvalent soluble anion. Preferably, the anion does not promote metal corrosion. Examples of such anions include, but are not limited to, nitrates, nitrites, lactates, phosphates, hydrogen phosphates, sulfates, molybdates, or mixtures thereof.

  Mixing can be done by conventional mixing and blending equipment common to experimental or industrial processes. A high shear mixer can be used but is not required. Since concentrated solutions of polyvalent metal ion salt solutions can cause gelation of colloidal particles upon contact, dilute the polyvalent metal ion salt solution as much as possible to obtain metal for the target colloidal particles. The ratio of ions and the total solids level of the anticorrosion formulation must be achieved. This can typically be achieved by a solution comprising 0.1-1 mol / L of polyvalent metal ions, preferably 0.1-0.5 mol / L of polyvalent metal ions.

  In a further exemplary method using an anticorrosive formulation, the method provides a substrate having a first surface; coating the formulation on the first surface of the substrate; and coated substrate A method of forming a coated substrate comprising the steps of: The resulting coating provides a substrate with desirable anti-corrosion resistance that is particularly useful in corrosive environments. Using dispersions, metal substrates, surface-treated metal substrates, metal substrates with pre-treated layers or other layers thereon, metal composite substrates, or any other that requires corrosion resistance The surface of various substrates, such as but not limited to substrates, as well as combinations thereof, can be coated. The resulting coated substrate can be used in numerous applications such as, but not limited to, chemical conversion applications, direct coating applications, and the like.

  In another exemplary embodiment, the anticorrosion composition of the present invention comprises a binder. In this embodiment, a binder is used to provide desirable film properties by application to a substrate.

  The anticorrosive composition can be included in a conventional coating binder that forms an anticorrosive coating. The binder not only acts to bind the colloidal particles to form a film, but also adheres to the interface between the coating and the substrate, or any intermediate layer between the anticorrosion coating and the substrate. give.

  Water-soluble or water-miscible binders such as latex are particularly suitable in the present invention and may be, for example, epoxy, polyester, polypropylene, polyethylene, acrylic silicone, polyurethane, polyamine, acrylic emulsion, polyvinyl butyral, etc. . Other suitable binders include starch derivatives such as oxidized starch, etherified starch, or phosphate starch; cellulose derivatives such as carboxymethyl cellulose or hydroxymethyl cellulose; casein, gelatin, soy protein, polyvinyl alcohol, or derivatives thereof; Polyacrylate; vinyl alcohol / acrylamide copolymer; cellulose polymer; starch polymer; isobutylene / maleic anhydride copolymer; vinyl alcohol / acrylic acid copolymer; polyethylene oxide modified product; dimethylammonium polydiarylate; and quaternary ammonium polyacrylate; , Maleic anhydride resin, or styrene-butadiene copolymer or methyl methacrylate Conjugated diene type copolymer latex such as diene copolymer; Acrylic polymer latex such as acrylate or methacrylate polymer or copolymer; Vinyl type polymer latex such as ethylene-vinyl acetate copolymer; Functionality such as carboxyl group Functional group modified polymer latices such as various polymers with monomers containing groups; or mixtures thereof. Thermosetting synthetic resin such as melamine resin or urea resin; polymer or copolymer resin of acrylic ester or methacrylic ester such as polymethyl methacrylate; or polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl Synthetic resin type binders such as butyral or alkyd resins; or aqueous adhesives such as mixtures thereof can also be used.

A binder can be mix | blended with an anticorrosion composition using a normal blender and a mixer. Ingredients can be formulated and mixed at ambient conditions.
In an exemplary embodiment of the present invention, the solids content (or the amount of colloidal particles and binder) of the anticorrosive composition is about 1 to about 50% by weight, preferably about 1 to about 50%, based on the total weight of the composition. It is in the range of about 30% by weight, more preferably about 1 to about 25% by weight, still more preferably about 1 to about 20% by weight. The solids content of the colloidal particles and binder may be present in the coating formulation in a ratio of at least 1: 1, more preferably 6: 4 to 4: 1 (by weight). This ratio may be as high as 9.9: 1.

  It may also be desirable to include additional components in the coating composition of the present invention. The coating of the present invention includes the following: dispersant, thickener, fluidity improver, defoamer, foam inhibitor, mold release agent, foaming agent, penetrant, colored dye, colored pigment, fluorescent whitening One or more of an agent, an ultraviolet absorber, an antioxidant, a preservative, a waterproofing agent and the like can be included.

  In one exemplary embodiment, the corrosion resistant material of the present invention comprises a substrate; and colloidal particles and at least one polyvalent metal ion, wherein the weight ratio of metal ion to metal oxide is An anticorrosive coating on the substrate that is greater than about 0.001 and not greater than about 0.1. The ratio of polyvalent metal ions to colloidal particles is at least about 0.005, preferably at least about 0.008, more preferably at least about 0.01, even more preferably at least about 0.01 to about 0.1. It may be. A typical coated substrate is shown in FIG.

  As shown in FIG. 1, a typical coated substrate 1 includes a thin pretreatment layer 2, a primary layer 3, and a top coating layer 4. All layers can contain the anticorrosive composition of the present invention, but typically the top coating layer 4 does not contain this composition. Preferably, the pretreatment layer 2 contains the anticorrosive composition of the present invention. Suitable binder materials for forming the thin pretreatment layer 2 include polyacrylates; vinyl alcohol / acrylamide copolymers; cellulose polymers; starch polymers; isobutylene / maleic anhydride copolymers; vinyl alcohol / acrylic acid copolymers; Water-absorbing materials such as, but not limited to: dimethylammonium polydiarylate; and quaternary ammonium polyacrylates. Suitable materials for forming the optionally used primary layer 3 can include, but are not limited to, polyethylene, polypropylene, polyester, and other polymer materials. The substrate 1 can be composed of various materials that corrode over time, such as any metal or metalloid.

  In a further exemplary embodiment of the present invention, the anticorrosion composition can be used in a method for producing a treated or coated anticorrosion material. In one exemplary method, the method of manufacturing the material provides a substrate having a first surface; and applying an anticorrosive composition on the first surface of the substrate, and further on Forming an anticorrosion coating layer; Next, the coating layer can be dried to form a coated substrate. A pre-treated corrosion resistant substrate can be formed using the coated substrate. In one exemplary method of the present invention, anticorrosion materials can be used in chemical conversion coatings and thin coating surface treatments.

  The invention is further illustrated by the following examples, which should not be construed as limiting the scope in any way. On the contrary, the solution may have various other aspects, modifications, and equivalents, which, after reading the description herein, come from the spirit of the invention and / or the claims. As such, it is suggested to those skilled in the art without departing.

Example 1:
Three types of colloidal silica sols were prepared.
Sol 1: 22 nm particles; ammonia stabilized; pH˜9.

Sol 2: 22 nm particles; alkaline (pH˜9) containing sodium ions.
Sol 3: 22 nm particles; stabilized with aluminate according to the method disclosed in US-2,892,797 and deionized to pH4.

Sol 4: 12 nm particles; stabilized with aluminate according to US-2,892,797 and deionized to pH4.
A mixture of 0.5 M Ca (NO ₃ ) ₂ and water is added to each of these sols with stirring, so that the sample contains 20% SiO ₂ and the weight ratio Ca / SiO ₂ is 0.005 0.01, 0.02, and 0.03. These samples were observed for 8 days at room temperature as follows.

  Samples made from sol 1 and sol 2 gelled almost immediately, indicating that alkaline sols cannot be used. The sample made from sol 3 was stable during the test time at a ratio of 0.005. All other sol 3 samples gelled after 5 days. Samples made from sol 4 were stable during the test time at ratios of 0.005 and 0.01. At a ratio of 0.02, the sample gelled after 8 days and at a ratio of 0.03 the sample gelled after 1 day. This indicates that the size of the colloidal particles plays an important role on the stability of the formulation, and the selection must be made based on the required stability and anticorrosion properties.

Example 2:
A calcium lactate (0.57 M) solution was added to sol 4 of Example 1 to prepare a sample having a Ca / SiO ₂ weight ratio of 0.03 and containing 20 wt% SiO ₂ . This sample gelled after 7 days at room temperature. This shows that this calcium compound can also be used.

Example 3:
This experiment shows that well-selected metal ions work with SiO ₂ to give better corrosion resistance in conversion coatings on galvanized and gallium steels compared to using colloidal silica alone. Indicates. For all samples, the sol 3 of Example 1 was used and all were adjusted to a pH of about 1.5-2 using phosphoric acid (H ₃ PO ₄ ).

Sample 1: Sol 3; 20% SiO ₂ ; adjusted to pH˜2 with phosphoric acid; no polyvalent metal ions.
Sample 2: A mixture of sol 3, calcium hydrogen phosphate (CaHPO ₄ ), and phosphoric acid containing 20% SiO _{2 and} having a Ca / SiO ₂ weight ratio of 0.03 at pH˜2.

Sample 3: Sol 3 containing 20% SiO ₂ and a V / SiO ₂ weight ratio of 0.06 at pH˜1.5, reducing vanadium pentoxide (V ₂ O ₅ ) by conventional means 4+ oxidation state vanadium (V ⁴⁺ ), and a mixture of phosphoric acid.

Sample 4: Sol 20 with 20% SiO ₂ and V / SiO ₂ weight ratio of 0.03 at pH˜1.5, reducing vanadium pentoxide (V ₂ O ₅ ) by conventional means 4+ oxidation state vanadium (V ⁴⁺ ), and a mixture of phosphoric acid.

  These samples were added to a normal chemical conversion solution so that the treatment composition contained 1-5% solids and exhibited a pH of 1-3. Using a 1-3% alkaline solution at 50-80 ° C., the galvanized substrate and the galvalume substrate are cleaned for 30-120 seconds, washed with water, then containing the samples 1-4 described above, Treated with a conversion solution at pH 4.5 for 30-90 seconds. The solids content of the sample was about 1-5%. By this treatment, an anticorrosion layer was deposited on the substrate. The results shown in Table 1 show that the substrate treated with the anticorrosive composition of the present invention (that is, having polyvalent metal ions) functions much better than the substrate treated without using polyvalent metal ions. It shows that.

  It should be noted that the singular forms “a”, “and”, and “the” as used herein and in the claims include plural referents unless the description clearly dictates otherwise. Thus, for example, reference to “an oxide” includes a plurality of such oxides, and reference to “oxide” includes one or more oxides and equivalents known to those skilled in the art, and the like. Includes description.

  For example, modifying the amount, concentration, volume, process temperature, process time, recovery rate or yield, flow rate, and similar values of components in the compositions used in the description of some aspects of the invention, and ranges thereof “About” means, for example, through typical measurement and handling procedures, through accidental errors in these procedures, variations in quantities that may occur through differences in the components used to perform the method; and similar approximation considerations Point to. The term “about” also encompasses amounts that differ by aging of a formulation or mixture having a particular initial concentration, as well as amounts that differ by mixing or processing of a formulation or mixture having a particular initial concentration. The claims encompass equivalent ranges of these quantities, whether modified by the term “about” or not.

Although the invention has been described in terms of a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention otherwise described and claimed herein. It will be apparent to those skilled in the art from consideration of the exemplary embodiments herein that further modifications, equivalents, and changes are possible. All parts and percentages in the examples and the rest of the specification are by weight unless otherwise specified. Further, all numerical ranges set forth in the specification or claims, such as those indicating a particular set of characteristics, units of measure, conditions, physical state, or proportions, are clearly mentioned or otherwise It is intended to literally include all numbers falling within such ranges as indicated by the method, as well as any subset of numbers within any ranges so indicated. For example, whenever a numerical range with a lower limit, R _L and an upper limit, R _U, is disclosed, any number R falling within the range is specifically disclosed. In particular, the number of the following formula within this range: R = R _L + k (R _U −R _L ), where k is a variable in the range of 1% to 100% in 1% increments, for example k is 1%, 2%, 3%, 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98%, 99%, or 100% There is a specific disclosure. Furthermore, any numerical range represented by any two values of R calculated above is also specifically disclosed. In addition to those shown and described herein, any modification of the present invention will become apparent to those skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to fall within the scope of the claims. All publications cited herein are hereby incorporated by reference in their entirety.

Claims (35)

solvent;
Colloidal particles; and at least one polyvalent metal ion;
And a weight ratio of metal ions to colloidal particles is greater than about 0.001 and not greater than about 0.1.   The anticorrosive composition of claim 1, wherein the colloidal particles comprise silica, alumina, titania, zirconia, or a mixture thereof.   The anticorrosion composition according to claim 1, wherein the colloidal particles contain silica.   The polyvalent metal ion comprises Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, or a mixture thereof. The anticorrosive composition as described.   The anticorrosive composition according to claim 1, wherein the polyvalent metal ion comprises Sn, Zn, Ca, or a mixture thereof.   The anticorrosive composition of claim 1, wherein the weight ratio is greater than about 0.005 and not greater than about 0.08.   The anticorrosive composition of claim 1, wherein the weight ratio is greater than about 0.01 and less than or equal to about 0.05. solvent;
Colloidal particles; and at least one polyvalent metal ion present in an amount of at least about 0.001 wt% to about 4 wt% or less based on the total weight of the composition;
An anticorrosion composition comprising:   The anticorrosion composition according to claim 8, wherein the colloidal particles comprise silica, alumina, titania, zirconia, or a mixture thereof.   The anticorrosive composition according to claim 8, wherein the colloidal particles comprise silica.   9. The polyvalent metal ion comprises Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, or a mixture thereof. The anticorrosive composition as described.   The anticorrosive composition according to claim 8, wherein the polyvalent metal ion comprises Sn, Zn, Ca, or a mixture thereof.   The anticorrosion composition of claim 8, wherein the at least one polyvalent metal ion is present in an amount of at least about 0.005 wt% to about 3 wt% or less based on the total weight of the composition.   The anticorrosion composition of claim 8, wherein the at least one polyvalent metal ion is present in an amount of at least about 0.01 wt% to about 2 wt% or less, based on the total weight of the composition. solvent;
Colloidal particles; and at least one polyvalent metal ion;
An anticorrosive composition that remains stable at 25 ° C. for at least 8 hours.   The anticorrosion composition of claim 15, wherein the colloidal particles comprise silica, alumina, titania, zirconia, or a mixture thereof.   The anticorrosive composition according to claim 15, wherein the colloidal particles comprise silica.   The polyvalent metal ion comprises Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, or a mixture thereof. The anticorrosive composition as described.   The anticorrosive composition according to claim 15, wherein the polyvalent metal ion comprises Sn, Zn, Ca, or a mixture thereof.   The anticorrosion composition according to claim 15, which is kept stable at 25 ° C for at least 10 hours.   The anticorrosive composition according to claim 15, which remains stable at 60 ° C for at least 60 minutes. binder;
solvent;
Colloidal particles; and at least one polyvalent metal ion;
And a ratio of metal ions to colloidal particles greater than about 0.001 and not greater than about 0.1.   The anticorrosive composition of claim 22, wherein the colloidal particles comprise silica, alumina, titania, zirconia, or a mixture thereof.   The anticorrosion composition according to claim 22, wherein the colloidal particles comprise silica.   The polyvalent metal ion comprises Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, or mixtures thereof. The anticorrosive composition as described.   The anticorrosion composition according to claim 22, wherein the polyvalent metal ion comprises Sn, Zn, Ca, or a mixture thereof.   23. The anticorrosive composition of claim 22, wherein the weight ratio is greater than about 0.005 and not greater than about 0.08.   23. The anticorrosive composition of claim 22, wherein the weight ratio is greater than about 0.01 and not greater than about 0.05. A substrate; and colloidal particles; and having at least one polyvalent metal ion; the ratio of metal ion to metal oxide is greater than about 0.001 and less than or equal to about 0.1 and less ;
Having corrosion resistant material.   30. The anticorrosion composition of claim 29, wherein the colloidal particles comprise silica, alumina, titania, zirconia, or a mixture thereof.   30. The anticorrosion composition of claim 29, wherein the colloidal particles comprise silica.   30. The multivalent metal ion of claim 29, comprising Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, W, Ce, or mixtures thereof. The anticorrosive composition as described.   30. The anticorrosive composition of claim 29, wherein the polyvalent metal ion comprises Sn, Zn, Ca, or a mixture thereof.   30. The anticorrosive composition of claim 29, wherein the weight ratio is greater than about 0.005 and not greater than about 0.08.   30. The anticorrosion composition of claim 29, wherein the weight ratio is greater than about 0.01 and less than or equal to about 0.05.

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