WO2022072857A1

WO2022072857A1 - Compositions for corrosion inhibition

Info

Publication number: WO2022072857A1
Application number: PCT/US2021/053212
Authority: WO
Inventors: Jun Su An; LoongYi TAN; Frederyk Ngantung; Jason HELANDER; Chris ARCEO
Original assignee: Solugen, Inc.
Priority date: 2020-10-02
Filing date: 2021-10-01
Publication date: 2022-04-07
Also published as: WO2022072857A9

Abstract

A multifunctional additive includes a biochelant; and one or more compounds selected from the group consisting of an acid, a cation, a nickel, a fluoride, a carbonate, a detergent, a solvent, a primer, a sealant, and a combination thereof. A corrosion resistant primer additive includes at least one acid; at least one cation; and a biochelant.

Description

COMPOSITIONS FOR CORROSION INHIBITION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/087,021 filed on October 2, 2020 and entitled, “Compositions for Corrosion Inhibition,” which is incorporated herein by reference in its entirety for all purposes.

TECHNICAL FIELD

[0002] The present disclosure relates generally to multifunctional additives. More specifically, the present disclosure relates chromate substitutes in a variety of applications including corrosion inhibition.

BACKGROUND

[0003] Corrosion inhibitors are chemical substances that, when added in small amounts to the environment in which a metal would otherwise corrode, will reduce, slow down, or prevent corrosion of the metal in such environment. Mechanisms of corrosion inhibition include: (i) the inhibitor may be chemically adsorbed (chemisorption) on the surface of the metal and form a protective thin film; (ii) the inhibitor initiates film formation by oxide protection of the base metal; and/or (iii) the inhibitor reacts with a potential corrosive component present in aqueous media to sequester the component.

[0004] Traditionally, many metallic structures in corrosive environments have been protected by the use of chromates. Chromium corrosion inhibitors (CCC) earliest use was as a protective coating on aluminum alloys. CCCs coatings are formed by contacting the metal surface with solutions containing hexavalent chromium (Cr⁶*) and other components. Before this step, the metal parts may be cleaned to remove contaminants and oxide film from the metal surface. These pretreatment steps can have significant effects on the properties of CCCs but the chromating step is an important factor in producing CCCs with desirable properties.

[0005] Recently, the mechanism of CCC function has been described from a sol-gel perspective. In this model, Cr⁶* is reduced to Cr³⁺. The Cr³⁺ then hydrolyzes and condenses to form Cr³⁺ monomers, dimers, trimers, and tetramers. With the increase in pH near the substrate surface region, these species polymerize and precipitate onto the substrate to form a hydrated oxide film. The precipitated Cr³⁺ oxide forms the “backbone” of CCCs. The Cr⁶* species in solution are then adsorbed onto the chromium oxide backbone. The reduction of chromate to form hydrated chromium oxide is the key reaction in the coating formation. The presence of Cr(VI) provides a self-repair mechanism by reduction to Cr(lll) during oxidative attack.

[0006] Phosphate-based compounds or phosphates are another type of commonly utilized corrosion inhibitor. Phosphates have attracted significant attention as materials for replacing chromium in corrosion inhibition formulations owing to their relatively low cost and high efficiency of corrosion inhibition.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] For a detailed description of various exemplary embodiments, reference will now be made to the accompanying drawing in which:

[0008] The Figure is a photograph of coupons treated as described in Example 1 .

SUMMARY

[0009] A multifunctional additive, comprising a biochelant; and one or more compounds selected from the group consisting of an acid, a cation, a nickel, a fluoride, a carbonate, a detergent, a solvent, a primer, a sealant, and a combination thereof.

[0010] A corrosion resistant primer additive, comprising at least one acid; at least one cation; and a biochelant.

DETAILED DESCRIPTION

[0011] As previously described, CCCs and phosphates are common corrosion inhibitors. While CCCs are effective corrosion inhibitors, recent studies have demonstrated that these materials can be occupational “hot spot” pollutants posing significant risks to workers involved in their production or as by-products of operations such as metal preparation. Consequently, CCCs are generally considered an unacceptable health risk and are progressively being limited or withdrawn from service. In addition, while phosphates can achieve a corrosion-resistant coating that may result in lower corrosion rates, phosphates typically do not perform as well as chromates as corrosion inhibitors. Furthermore, phosphates can cause damage and eutrophication when introduced into the environment. Accordingly, an ongoing need exists for improved materials that function as corrosion inhibitors without the drawbacks of current technologies. [0012] Disclosed herein are compositions for use as multifunctional additives. In an aspect, the compositions disclosed herein may function as corrosion inhibitors, complexing agents that increase the solubility of metals/cations in suspension/solution and corrosion inhibitor synergists. In an aspect, the multifunctional additive functions to replace hexavalent chromium in the area of metal conversion coatings, and metal pretreatment. For simplicity the multifunctional additive that can replace the function of hexavalent chromium is termed a multifunctional inhibitor additive or “MIA”.

[0013] In an aspect, the MIA comprises a biochelant and one or more compounds selected from the group consisting of acids, cations, nickel, fluorides, carbonates, detergents, solvents, primers, sealants, and combinations thereof. The MIA can be applied in a number of forms such as an additive to a fluid in contact with a metal surface, a pre-coating on a metal surface, as a primer on a metal surface, as another coating on a metal surface, or combinations thereof. For example, the MIA can be added to or applied as a primer layer on a metal surface to provide a reservoir of the MIA on the metal surface which functions to prevent corrosion overtime.

[0014] In an aspect, the MIA comprises a chelant. Herein, a chelant, also termed a sequestrant or a chelating agent, refers to a molecule capable of bonding a metal. The chelating agent is a ligand that contains two or more electron-donor groups so that more than one bond forms between a metal ion and the ligand. In an aspect, the chelant is a biochelant. As used herein, the prefix “bio” indicates that the chemical is produced by a biological process such as through the use of an enzyme catalyst.

[0015] In an aspect, the biochelant comprises aldonic acid, uronic acid, aldaric acid, or combinations thereof; and a counter cation. In an aspect, the biochelant comprises a glucose oxidation product, a gluconic acid oxidation product, a gluconate, or a combination thereof. The glucose oxidation product, gluconic acid oxidation product, or combination thereof may be buffered to a suitable pH.

[0016] Alternatively, the biochelant comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucoronolactone, a uronic acid oxidation product, or a combination thereof. In such aspects, the buffered glucose oxidation product, the buffered gluconic acid oxidation product, or the combination thereof is buffered to a suitable pH. In such aspects, the biochelant comprises a mixture of gluconic acid and glucaric acid, and further comprises a minor component species comprising n-keto-acids, C2-C5 diacids, or combinations thereof. In an aspect, the biochelant comprises Biochelate™ metal chelation product commercially available from Solugen, Inc. of Houston, Texas.

[0017] In an aspect, the chelant is present in the MIA in an amount ranging from about 0.1 weight percent (wt.%) to about 70 wt.%, alternatively from about 5 wt.% to about 30 wt.%, alternatively from about 25 wt.% to about 70 wt.%, or alternatively from about 0.1 wt.% to about 10 wt.% based on the total weight of the MIA.

[0018] In an aspect, the MIA comprises an acid. Acids suitable for use in the present disclosure include any material suitable for adjusting the pH of the MIA and compatible with the other components of the MIA. For example, the pH of the MIA may range from about 0 to about 6, alternatively from about 0 to about 3, alternatively from about 0.1 to about 2 or alternatively from about 2 to about 6. Nonlimiting examples of acidic materials suitable for use in the present disclosure include phosphoric, phosphates, nitric, nitrites, nitrates, or a combination thereof. In an aspect, the acid may be included in the MIA in amounts ranging from about 1 wt.% to about 60 wt.%, alternatively from about 5 wt.% to about 60 wt.%, alternatively from about 25 wt.% to about 60 wt.% or alternatively from about 1 wt.% to about 25 wt.%.

[0019] In an aspect, the MIA comprises a cation such as a salt or oxide of zinc, molybdenum, tungsten, vanadium, manganese, potassium, cerium, nickel, zirconium or a combination thereof. For example, the cation may comprise zinc, alternatively a zinc oxide or a zinc salt. Nonlimiting examples of zinc salts suitable for use in the present disclosure include zinc acetate, zinc oxide, zinc nitrate, zinc chlorate, zinc sulfate, zinc phosphate, zinc molybdate, zinc arsenite, zinc arsenate octahydrate, and combinations thereof.

[0020] In an aspect, the cation is present in the MIA in an amount of from about 1 wt.% to about 50 wt.%, alternatively from about 5 wt.% to about 50 wt.%, alternatively from about 15 wt.% to about 35 wt.% or alternatively from about 1 wt.% to about 30 wt.% based on the total weight of the MIA.

[0021] In an aspect, the MIA comprises nickel, alternatively a nickel oxide or a nickel salt. Nonlimiting examples of nickel salts suitable for use in the present disclosure include nickel oxide, nickel sulfate, ammonium nickel (II) sulfate, nickel (II) acetate, nickel (II) bromide, nickel (II) carbonate, nickel (II) chloride, nickel (II) fluoride, nickel (II) hydroxide, nickel (II) iodide, nickel (II) nitrate, and combinations thereof. In an aspect, the nickel, or alternatively the nickel oxide or the nickel salt, is present in the MIA in an amount of from 1 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 25 wt.%, alternatively from about 5 wt.% to about 50 wt.% or alternatively from about 10 wt.% to about 20 wt.% based on the total weight of the MIA.

[0022] In an aspect, the MIA comprises fluoride. Nonlimiting examples of fluorides suitable for use in the present disclosure include ammonium bifluoride, tetramethylammonium fluoride (TMAF), tetrafluoroethylene, 2,2,2-trifluoroethanol (TFE), fluorine (F2), hydrofluoric acid (HF), and combinations thereof. In an aspect, the fluoride is present in the MIA in an amount of from about 0.1 wt.% to about 20 wt.%, alternatively from about 1 wt.% to about 5 wt.% or alternatively from about 2 wt.% to about 10 wt.% based on the total weight of the MIA.

[0023] In an aspect, the MIA comprises a carbonate. Nonlimiting examples of carbonates suitable for use in the present disclosure include ammonium bicarbonate, barium carbonate, calcium carbonate, magnesite, sodium percarbonates, sodium carbonate, sodium bicarbonate, and combinations thereof. In an aspect, the carbonate is present in the MIA in an amount of from about 1 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 20 wt.%, alternatively from about 5 wt.% to about 30 wt.% or alternatively from about 10 wt.% to about 50 wt.% based on the total weight of the MIA.

[0024] In a further aspect, the MIA comprises a detergent or surfactant. Non-limiting examples of surfactants suitable for use in the present disclosure include nonionic surfactants, ionic surfactants, amphoteric surfactants, and combinations thereof. In an aspect, the surfactant may be a nonionic surfactant. In a further aspect, the surfactant comprises one or more functional groups including, but not limited to, alkoxylates, polyalkoxylates, ethoxylates, polyethoxylates, glucosides, sulfates, sulfonates, disulfonates, phosphate esters, sulfosuccinates, quaternary ammonium salts, betaines, or combinations thereof. In aspects, the surfactant comprises one or more or alkyl, aryl, or alkylaryl sulfates, sulfonates or phosphates of alkali metals, or the corresponding ammonium salts. Suitable surfactants can also comprise alkylsulfonic acids, sulfosuccinate salts, fatty acid salts, ethoxylated alcohols, amphiphilic copolymers, or combinations thereof.

[0025] In a still further aspect, the surfactant may comprise one or more of the following: 1-Oleoyl-rac-glycerol, Brij® 58, Brij® L23, Brij® L4, Brij® 010, CYMAL-2®, CYMAL-5®, CYMAL-6®, Decaethylene glycol monododecyl ether, Decyl -D- glucopyranoside, Decyl p-D-maltopyranoside, Deoxy-BigCHAP, Digitonin, ECOSURF™ EH-9, ECOSURF™ SA-9, Genapol® X-100, Igepal® CA-630, Igepal® CA-720, Kolliphor® P 188, Kolliphor® P 407, Kolliphor® EL, MEGA-8, MEGA-9, MEGA- 10, Methoxypolyethylene glycol, N,N-Dimethyldodecylamine N-oxide, n-Dodecyl p-D- maltoside, n-Heptyl p-D-thioglucopyranoside, n-Hexadecyl p-D-maltoside, n-Nonyl-p- D-Glucopyranoside, n-Nonyl-p-D-maltoside, n-Octyl-p-D-maltoside, n-Octyl-p-D- thioglucopyranoside, n-Octyl-b-D-Glucopyranoside, Nonaethylene glycol monododecyl ether, Nonidet™ P40 Substitute, Nonylphenyl-polyethyleneglycol acetate, Octaethylene glycol monododecyl ether, PLURONIC® 25 R-2, PLURONIC® 10 R-5, PLURONIC® F-127, PLURONIC® F-68, Poloxamer 407, Polyethylene glycol), Polyoxyethylene (10) tridecyl ether, Polyoxyethylene (40) stearate, Polysorbate 20, Polysorbate 60, Polysorbate 80, Saponin, Span® 20, Span® 40, Span® 60, Span® 80, Span® 85, Sucrose monolaurate, Synperonic® PE/P84, SURFYNOL® 61 , SURFYNOL® 465, SURFYNOL® 2502, TERGITOL™, TERGITOL™ NP-7, TERGITOL™ NP-9, TERGITOL™ NP-10, TERGITOL™ NP-40, TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-30, TERGITOL™ 15-S-40, TERGITOL™ TMN 6, TERGITOL™ TMN 10, TERGITOL™ TMN-100X, Tetraethylene glycol monododecyl ether, Tetramethylammonium hydroxide pentahydrate, Thesit®, TRITON™ X-100, TRITON™ X-114, TRITON™ X-165, TRITON™ X-305, TRITON™ X-405, TRITON™ X-405, TRITON™ X-705, TRITON™-CG-110, TWEEN® 20, TWEEN® 40, TWEEN® 60, TWEEN® 65, TWEEN® 80, TWEEN® 85, Tyloxapol, and Undecyl-p-D-maltoside, all of which are available commercially from MilliporeSigma, and AQUA-CLEEN® available commercially from Chemical Products Industries, Inc. In an aspect, the surfactant is present in the MIA in an amount of from about 0.01 wt.% to about 10 wt.%, alternatively from about 0.01 wt.% to about 1 wt.%, alternatively from about 0.5 wt.% to about 5 wt.% or alternatively from about 1 wt.% to about 10 wt.% based on the total weight of the MIA.

[0026] In an aspect, the MIA comprises a primer and/or can form a part of a primer. Alternatively, the MIA comprises a sealant and/or can form a part of a sealant. Herein, a sealant refers to a substance used to block the passage of fluids through a surface, a joint, or an opening in a material while a primer refers to a base protectant used on an outer surface of a substrate. The primer or sealant may be selected from the group consisting of water-borne polymers, solvent-borne polymers, hybrids, and combinations thereof. Nonlimiting examples of polymers or sealants suitable for use in the MIA include amines, resins, epoxies, acrylic copolymers, silicone, polysiloxane, urethanes, fluoropolymers, polyvinyl compounds siloxanes, polyurethane, polyester, latex, alkyd, polyurethane, and combinations thereof. In an aspect, the primer, the sealant, or both is/are present in the MIA in an amount of from about 0.1 wt.% to about 30 wt.%, alternatively from about 0.1 wt.% to about 5 wt.%, alternatively from about 5 wt.% to about 30 wt.% or alternatively from about 1 wt.% to about 10 wt.% based on the total weight of the MIA.

[0027] In a further aspect, the MIA comprises a solvent. Solvents suitable for use in the present disclosure include without limitation water, hydrocarbons, halogenated hydrocarbons, ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles, and combinations thereof. In an aspect, the solvent is present in the MIA in an amount of from about 1 wt.% to about 50 wt.%, alternatively from about 10 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 20 wt.% or alternatively from about 5 wt.% to about 30 wt.% based on the total weight of the MIA. In an alternative aspect, solvent constitutes the remainder of the MIA when all other components are accounted for.

[0028] In an aspect, the MIA excludes a trivalent chromium-containing compound, a hexavalent chromium-containing compound, or both. In one or more aspects, the MIA comprises less than about 1 wt.% of a trivalent chromium-containing compound, alternatively less than about 0.5 wt.%, alternatively less than about 0.25 wt.%, or alternatively less than about 0.1 wt.% of based on the total weight of the MIA. In one or more aspects, the MIA comprises less than about 1 wt.% of a hexavalent chromium-containing compound, alternatively less than about 0.5 wt.%, alternatively less than about 0.25 wt.%, or alternatively less than about 0.1 wt.% of based on the total weight of the MIA. In an aspect, the MIA excludes a phosphate. In one or more aspects, the MIA comprises less than about 1 wt.% of a phosphate compound, alternatively less than about 0.5 wt.%, alternatively less than about 0.25 wt.%, or alternatively less than about 0.1 wt.% of based on the total weight of the MIA.

[0029] In an aspect, the MIA functions as a corrosion resistant primer additive. In another aspect, the MIA functions as a corrosion resistant epoxy additive. In an aspect, the MIA functions as a corrosion resistant paint additive. [0030] In an aspect, the MIA of the present disclosure functions to replace hexavalent chromium in areas such as aircraft coatings, chrome plating, avionics electronics, rinses (for aluminum or steel), sealants, and aluminum. In an aspect, the MIA advantageously is characterized as both phosphate free and chromate free having less than about 1 wt.% of phosphate and/or chromate based on the total weight of the MIA.

[0031] The following are non-limiting, specific embodiments in accordance with the present disclosure:

[0032] A first aspect is a composition for chromate-free corrosion inhibitor, pretreatment additive, and corrosion inhibitor synergist. The composition comprising: a chelant comprising an aldonic, uronic, or aldaric acid, or a salt or derivative thereof, or a combination thereof; metals and metal salts; polyamines, polyphosphates, phosphates; nitrates; nitrites; primers; solvents; epoxies; urethane; surfactants and dispersants or a combination thereof.

[0033] A second aspect is the composition of the first aspect wherein the chelant comprises of citric acid, tartaric acid, glucaric acid and gluconic acid liquid oxidation product comprising predominantly gluconic acid, glucaric acid, gluconate, citrate, tartarate and glucarate anions with minor component species of n-keto-acids and C2- C5 diacids.

[0034] A third aspect is the composition of any of the first through second aspects wherein the cation comprises of zinc, molybdenum, tungsten, vanadium, manganese, potassium, cerium, nickel, zirconiumand mixtures thereof

[0035] A fourth aspect is the composition of any of the first through third aspects wherein the epoxies and primers comprise of amines, resins, epoxies, urethanes, fluoropolymers, urethanes, polyvinyl compounds, siloxanes.

[0036] A fifth aspect which is a multifunctional additive, comprising a biochelant; and one or more compounds selected from the group consisting of an acid, a cation, a nickel, a fluoride, a carbonate, a detergent, a solvent, a primer, a sealant, and a combination thereof.

[0037] A sixth aspect which is the multifunctional additive of the fifth aspect, wherein the biochelant comprises an aldonic acid, uronic acid, aldaric acid, or a combination thereof. [0038] A seventh aspect which is the multifunctional additive of any of the fifth through sixth aspects wherein the biochelant comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucoronolactone, a uronic acid oxidation product, or a combination thereof.

[0039] An eighth aspect which is the multifunctional additive of the seventh aspect wherein the buffered glucose oxidation product, the buffered gluconic acid oxidation product, or the combination thereof further comprises n-keto-acids, C2-C5 diacids, or a combination thereof.

[0040] A ninth aspect which is the multifunctional additive of any of the fifth through eighth aspects wherein the acid comprises phosphoric, phosphate, nitric, nitrite, nitrates, or a combination thereof.

[0041] A tenth aspect which is the multifunctional additive of any of the fifth through ninth aspects wherein the cation comprises zinc, molybdenum, tungsten, vanadium, manganese, salts, oxides, or a combination thereof.

[0042] An eleventh aspect which is the multifunctional additive of any of the fifth through tenth aspects wherein the cation comprises zinc acetate, zinc oxide, zinc nitrate, zinc chlorate, zinc sulfate, zinc phosphate, zinc molybdate, zinc arsenite, zinc arsenate octahydrate, or a combination thereof.

[0043] A twelfth aspect which is the multifunctional additive of any of the fifth through eleventh aspects wherein the nickel comprises nickel oxide, nickel sulfate, ammonium nickel(ll) sulfate, nickel (II) acetate, nickel (II) bromide, nickel(ll) carbonate, nickel(ll) chloride, nickel(ll) fluoride, nickel(ll) hydroxide, nickel(ll) iodide, nickel(ll) nitrate, or a combination thereof.

[0044] A thirteenth aspect which is the multifunctional additive of any of the fifth through twelfth aspects wherein the fluoride comprises ammonium bifluoride, tetramethylammonium fluoride (TMAF), ammonium fluoride (NH4F or AF), tetrafluoroethylene, 2,2,2-trifluoroethanol (TFE), fluorine (F2), hydrofluoric acid (HF), or a combination thereof.

[0045] A fourteenth aspect which is the multifunctional additive of any of the fifth through thirteenth aspects wherein the carbonate comprises ammonium bicarbonate, barium carbonate, calcium carbonate, magnesite, sodium percarbonates, sodium carbonate, sodium bicarbonate or a combination thereof. [0046] A fifteenth aspect which is the multifunctional additive of any of the fifth through fourteenth aspects wherein the solvent comprises water, hydrocarbons, halogenated hydrocarbons, ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles, or a combination thereof.

[0047] A sixteenth aspect which is the multifunctional additive of any of the fifth through fifteenth aspects wherein the primer comprises water-borne polymers, solvent-borne polymers, hybrids, or a combination thereof.

[0048] A seventeenth aspect which is the multifunctional additive of any of the fifth through sixteenth aspects wherein the primer comprises amines, resins, epoxies, acrylic copolymers, silicone, polysiloxane, urethanes, fluoropolymers, polyvinyl compounds siloxanes, polyurethane, polyester, latex, alkyd, polyurethane, or a combination thereof.

[0049] An eighteenth aspect which is the multifunctional additive of any of the fifth through seventeenth aspects wherein the surfactant comprises alkylsulfonic acids, sulfosuccinate salts, fatty acid salts, ethoxylated alcohols, amphiphilic copolymers, or a combination thereof.

[0050] A nineteenth aspect which is the multifunctional additive of any of the fifth through eighteenth aspects excluding hexavalent chromium, phosphate, or both.

[0051] A twentieth aspect which is a corrosion resistant primer additive, comprising at least oneacid; at least one cation; and a biochelant.

[0052] A twenty-first aspect which is the additive of the twentieth aspect wherein the biochelant comprises an aldonic acid, uronic acid, aldaric acid, or a combination thereof.

[0053] A twenty-second aspect which is the additive of any of the twentieth through twenty-first aspects wherein the biochelant comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucoronolactone, a uronic acid oxidation product, or a combination thereof.

[0054] A twenty-third aspect which is the additive of any of the twentieth through twenty-second aspects wherein the acid comprises phosphoric, phosphate, nitric, nitrite, nitrates, or a combination thereof.

[0055] A twenty-fourth aspect which is the additive of any of the twentieth through twenty-third aspects wherein the cation comprises zinc, molybdenum, tungsten, vanadium, manganese, potassium, cerium, nickel, zirconium salts, oxides, or a combination thereof

EXAMPLES

[0056] The subject matter having been generally described, the following examples are given as particular aspects of the disclosure and are included to demonstrate the practice and advantages thereof, as well as aspects and features of the disclosed subject matter. It should be appreciated by those of skill in the art that the techniques disclosed in the examples that follow represent techniques discovered by the inventors to function well in the practice of the presently disclosed subject matter. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific aspects which are disclosed and still obtain a like or similar result without departing from the scope of the subject matter of the instant disclosure. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims to follow in any manner.

EXAMPLE 1

[0057] The effectiveness of a MIA, of the type disclosed herein, was investigated. Specifically, two galvanized coupons were exposed to an MIA of the type disclosed herein. Coupon 1 was incubated in a solution having 10 ml of a commercially available zinc phosphate and 90 ml of water while Coupon 2 was incubated in a solution having 10 ml of a MIA of the type disclosed herein comprising a biochelant, zinc and phosphate and 90 ml of water. The results are presented in Table 1.

Table 1

[0058] The results demonstrate that Sample 1 which was immersed in a MIA of the type disclosed herein yielded a coating that did not brush off and also gained mass as shown in the Figure.

[0059] While aspects of the disclosure have been shown and described, modifications thereof can be made without departing from the spirit and teachings of the presently disclosed subject matter. The aspects and examples described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the present disclosure.

[0060] At least one aspect is disclosed and variations, combinations, and/or modifications of the aspect(s) and/or features of the aspect(s) made by a person having ordinary skill in the art are within the scope of the disclosure. Alternative aspects that result from combining, integrating, and/or omitting features of the aspect(s) are also within the scope of the disclosure. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, 5, 6, . . . ; greater than 0.10 includes 0.11 , 0.12, 0.13, 0.14, 0.15, . . .). For example, whenever a numerical range with a lower limit, Rl, and an upper limit, Ru, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=RI +k* (Ru-RI), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, 50 percent, 51 percent, 52 percent... 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed. Use of the term “optionally” with respect to any element of a claim means that the element is required, or alternatively, the element is not required, both alternatives being within the scope of the claim. In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to... .” Use of broader terms such as comprises, includes, and having should be understood to provide support for narrower terms such as consisting of, consisting essentially of, and comprised substantially of.

[0061] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are an addition to the detailed description of the presently disclosed subject matter.

Claims

CLAIMS What is claimed is:

1 . A multifunctional additive, comprising: a biochelant; and one or more compounds selected from the group consisting of an acid, a cation, a nickel, a fluoride, a carbonate, a detergent, a solvent, a primer, a sealant, and a combination thereof.

2. The additive of claim 1 , wherein the biochelant comprises an aldonic acid, uronic acid, aldaric acid, or a combination thereof.

3. The additive of claim 1 , wherein the biochelant comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucoronolactone, a uronic acid oxidation product, or a combination thereof.

4. The additive of claim 3, wherein the buffered glucose oxidation product, the buffered gluconic acid oxidation product, or the combination thereof further comprises n-keto-acids, C2-C5 diacids, or a combination thereof.

5. The additive of claim 1 , wherein the acid comprises phosphoric, phosphate, nitric, nitrit, nitrates, or a combination thereof.

6. The additive of claim 1 , wherein the cation comprises zinc, molybdenum, tungsten, vanadium, manganese, salts, oxides, or a combination thereof

7. The additive of claim 1 , wherein the cation comprises zinc acetate, zinc oxide, zinc nitrate, zinc chlorate, zinc sulfate, zinc phosphate, zinc molybdate, zinc arsenite, zinc arsenate octahydrate, or a combination thereof.

8. The additive of claim 1 , wherein the nickel comprises nickel oxide, nickel sulfate, ammonium nickel(ll) sulfate, nickel (II) acetate, nickel (II) bromide, nickel(ll) carbonate, nickel(ll) chloride, nickel(ll) fluoride, nickel(ll) hydroxide, nickel(ll) iodide, nickel(ll) nitrate, or a combination thereof. The additive of claim 1 , wherein the fluoride comprises ammonium bifluoride, tetramethylammonium fluoride (TMAF), ammonium fluoride (NH4F or AF), tetrafluoroethylene, 2,2,2-trifluoroethanol (TFE), fluorine (F2), hydrofluoric acid (HF), or a combination thereof. The additive of claim 1 , wherein the carbonate comprises ammonium bicarbonate, barium carbonate, calcium carbonate, magnesite, sodium percarbonates, sodium carbonate, sodium bicarbonate or a combination thereof. The additive of claim 1 , wherein the solvent comprises water, hydrocarbons, halogenated hydrocarbons, ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles, or a combination thereof. The additive of claim 1 , wherein the primer comprises water-borne polymers, solvent-borne polymers, hybrids, or a combination thereof. The additive of claim 1 wherein the primer comprises amines, resins, epoxies, acrylic copolymers, silicone, polysiloxane, urethanes, fluoropolymers, polyvinyl compounds siloxanes, polyurethane, polyester, latex, alkyd, polyurethane, or a combination thereof. The additive of claim 1 , wherein the surfactant comprises alkylsulfonic acids, sulfosuccinate salts, fatty acid salts, ethoxylated alcohols, amphiphilic copolymers, or a combination thereof. The additive of claim 1 , excluding hexavalent chromium, phosphate, or both. A corrosion resistant primer additive, comprising: at least one acid; at least one cation; and a biochelant. The additive of claim 16, wherein the biochelant comprises an aldonic acid, uronic acid, aldaric acid, or a combination thereof. The additive of claim 16, wherein the biochelant comprises a buffered glucose oxidation product, a buffered gluconic acid oxidation product, an oxidized glucoronolactone, a uronic acid oxidation product, or a combination thereof. The additive of claim 16, wherein the acid comprises phosphoric, phosphate, nitric, nitrite, nitrates, or a combination thereof. The additive of claim 16, wherein the cation comprises zinc, molybdenum, tungsten, vanadium, manganese, potassium, cerium, nickel, zirconium salts, oxides, or a combination thereof

16