WO2012085830A2 - Inhibition de la corrosion par des solutions d'hypochlorite contenant un polyacrylate et ca, zn et ca, des acides de sucres et ca - Google Patents

Inhibition de la corrosion par des solutions d'hypochlorite contenant un polyacrylate et ca, zn et ca, des acides de sucres et ca Download PDF

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Publication number
WO2012085830A2
WO2012085830A2 PCT/IB2011/055798 IB2011055798W WO2012085830A2 WO 2012085830 A2 WO2012085830 A2 WO 2012085830A2 IB 2011055798 W IB2011055798 W IB 2011055798W WO 2012085830 A2 WO2012085830 A2 WO 2012085830A2
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WO
WIPO (PCT)
Prior art keywords
corrosion inhibitor
hypochlorite
corrosion
composition
hypochlorite source
Prior art date
Application number
PCT/IB2011/055798
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English (en)
Other versions
WO2012085830A3 (fr
Inventor
Kim R. Smith
Erik C. Olson
Steven E. Lentsch
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Ecolab Usa Inc.
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Filing date
Publication date
Priority claimed from US12/974,520 external-priority patent/US8114344B1/en
Priority claimed from US12/974,468 external-priority patent/US8114343B1/en
Priority claimed from US12/974,560 external-priority patent/US8105531B1/en
Application filed by Ecolab Usa Inc. filed Critical Ecolab Usa Inc.
Publication of WO2012085830A2 publication Critical patent/WO2012085830A2/fr
Publication of WO2012085830A3 publication Critical patent/WO2012085830A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors

Definitions

  • the invention relates to corrosion inhibitor compositions and methods of using the same.
  • polyacrylate and calcium compounds, sugar acids and calcium compounds and/or zinc and calcium compounds are used with hypochlorite sources and have the beneficial effect of corrosion inhibition of metal in contact with hypochlorite sources.
  • the present compositions and methods employing the compositions reduce and/or eliminate the corrosive effects of hypochlorite on metal surfaces.
  • Sodium hypochlorite solutions are commonly used and highly effective as bleaches and sanitizers for cleaning a variety of surfaces.
  • sodium hypochlorite solutions are extremely corrosive to many treated surfaces, in particular, metal surfaces become highly corroded.
  • Hypochlorite solutions corrode surfaces as a result of its composition of sodium hypochlorite, sodium chloride and often sodium hydroxide, each having distinct mechanisms of corrosion.
  • Sodium hypochlorite is a strong oxidant causing metal corrosion through a redox attack.
  • a further object of the claimed invention is a corrosion inhibitor composition capable of preventing metal corrosion caused by sodium hypochlorite solutions without adversely impacting the stability of the hypochlorite solution.
  • a further object of the invention is to provide methods for hypochlorite corrosion inhibition.
  • the present invention provides compositions and methods of use that synergistically reduce corrosion of metal surfaces treated with hypochlorite bleach solutions.
  • An advantage of the invention is a corrosion inhibitor composition that simultaneously prevents the corrosive mechanisms of hypochlorite solutions on treated surfaces. It is an advantage of the present invention that the claimed methods and compositions prevent substrate corrosion caused by hypochlorite solutions without adversely impacting the stability of the hypochlorite solution.
  • Corrosion inhibitor compositions according to the invention may comprise a hypochlorite source and a corrosion inhibitor comprising a water soluble polyacrylate compound and a water soluble calcium compound, wherein the pH of said composition is at least about 7 and wherein the molecular weight of said polyacrylate is less than about 10,000.
  • the corrosion inhibitor according to the invention may be a water soluble polyacrylate compound and a water soluble calcium salt.
  • the corrosion inhibitor according to the invention may further be a water soluble polyacrylate compound and a water soluble calcium salt having a chloride or non-halide anion.
  • the ratio of hypochlorite source to corrosion inhibitor is from about 10: 1 to about 600:1.
  • the ratio of said polyacrylate compound to said calcium salt is from about 6:1 to about 1 :6.
  • a further embodiment of the corrosion inhibitor compositions according to the invention may comprise a hypochlorite source and a corrosion inhibitor comprising a sugar acid compound and a water soluble calcium compound, wherein the pH of said composition is at least about 7.
  • the corrosion inhibitor according to the invention may be a sugar acid compound and a water soluble calcium salt.
  • the corrosion inhibitor according to the invention may further be a sugar acid and/or its oxidation product or products and a water soluble calcium salt having a chloride or non-halide anion.
  • the ratio of hypochlorite source to corrosion inhibitor is from about 10: 1 to about 600:1.
  • the ratio of said sugar acid to said calcium salt is from about 6:1 to about 1 :6.
  • the corrosion inhibitor compositions according to the invention may comprise a hypochlorite source and a corrosion inhibitor comprising a water soluble zinc compound and a water soluble calcium compound, wherein the pH of said composition is at least about 7.
  • the corrosion inhibitor according to the invention may be a water soluble zinc salt and a water soluble calcium salt.
  • the corrosion inhibitor according to the invention may further be a water soluble zinc salt and a water soluble calcium salt having a chloride or non-halide anion.
  • the ratio of hypochlorite source to corrosion inhibitor is from about 10: 1 to about 600:1.
  • the ratio of said zinc salt to said calcium salt is from about 6: 1 to about 1 :6.
  • the hypochlorite source is a solution of sodium hypochlorite, sodium chloride and optionally sodium hydroxide.
  • the hypochlorite solution is free of carbonate or bicarbonate anions.
  • the corrosion inhibitor composition has a neutral or alkaline pH.
  • the corrosion inhibitors according to the invention are preferably EPA approved inert material for antimicrobial formulations.
  • the corrosion inhibitor according to the invention does not adversely impact the stability of the hypochlorite source.
  • the corrosion inhibitor compositions may comprise a hypochlorite source comprising sodium hypochlorite, sodium chloride and sodium hydroxide and about 0.01 to about 2 wt- % corrosion inhibitor, wherein the pH of said composition is at least about 7, wherein the ratio of said hypochlorite source to corrosion inhibitor is from about 50:1 to about 200:1.
  • the corrosion inhibitor composition according to the invention may further have a ratio of corrosion inhibitor to calcium salt from about 4: 1 to about 1 :4.
  • the corrosion inhibitor is preferably an EPA approved inert material for antimicrobial formulations and does not adversely impact the stability of the hypochlorite source.
  • the combined hypochlorite and corrosion inhibitor composition has a pH of at least 9.
  • a method for inhibiting corrosion of a surface contacted by a hypochlorite source comprises adding a corrosion inhibitor to a hypochlorite source to form a corrosion inhibitor composition, and contacting a surface with said corrosion inhibitor composition.
  • the methods according to the invention simultaneously control corrosive mechanisms of sodium hypochlorite, sodium chloride, and sodium hydroxide of said hypochlorite source.
  • the methods for inhibiting corrosion of a surface are suitable for metal surfaces.
  • a corrosion inhibitor is added to a hypochlorite source to provide a corrosion inhibitor concentration in the hypochlorite use solution from about 25 ppm to about 2000 ppm.
  • the methods according to the invention result in a surface loss of at least less than about 0.1 % of its weight in the presence of said corrosion inhibitor composition.
  • the methods according to the invention may further comprise the formation of a corrosion-inhibiting layer on a treated surface.
  • FIG. 1 shows data from Example 3 in the form of a graph illustrating the effect of zinc / calcium corrosion inhibitor concentration ratio on the corrosiveness of a bleach concentrate.
  • FIG. 2 shows data demonstrating the effect of pH on corrosion of stainless steel with ready-to-use corrosion inhibitor.
  • the term "about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like.
  • the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities refers to variation in the numerical quantity that can occur.
  • the term "disinfectant” refers to an agent that kills all vegetative cells including most recognized pathogenic microorganisms, using the procedure described in A. OA. C. Use Dilution Methods, Official Methods of
  • the term “high level disinfection” or “high level disinfectant” refers to a compound or composition that kills substantially all organisms, except high levels of bacterial spores, and is effected with a chemical germicide cleared for marketing as a sterilant by the Food and Drug Administration.
  • the term “intermediate-level disinfection” or “intermediate level disinfectant” refers to a compound or composition that kills mycobacteria, most viruses, and bacteria with a chemical germicide registered as a tuberculocide by the Environmental Protection Agency (EPA).
  • the term “low-level disinfection” or “low level disinfectant” refers to a compound or composition that kills some viruses and bacteria with a chemical germicide registered as a hospital disinfectant by the EPA.
  • hard surface includes surfaces including, for example, showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors, and the like.
  • health care surface refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity.
  • health care surfaces include surfaces of medical or dental instruments, of medical or dental devices, of electronic apparatus employed for monitoring patient health, and of floors, walls, or fixtures of structures in which health care occurs.
  • Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms. These surfaces can be those typified as "hard surfaces” (such as walls, floors, bed-pans, etc.), or fabric surfaces, e.g.
  • knit, woven, and non-woven surfaces such as surgical garments, draperies, bed linens, bandages, etc.
  • patient-care equipment such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.
  • Health care surfaces include articles and surfaces employed in animal health care.
  • hypochlorite refers to a mixture of sodium hypochlorite, sodium chloride, and optionally sodium hydroxide.
  • instrument refers to the various medical or dental instruments or devices that can benefit from cleaning with a stabilized composition according to the present invention.
  • the phrases “medical instrument”, “dental instrument”, “medical device”, “dental device”, “medical equipment”, or “dental equipment” refer to instruments, devices, tools, appliances, apparatus, and equipment used in medicine or dentistry. These various instruments, devices and equipment include, but are not limited to: diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws ⁇ e.g.
  • hemostats knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straightener, punches, extractors, scoops, keratomes, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g. , endoscopes, stethoscopes, and arthoscopes) and related equipment, and the like, or combinations thereof.
  • scopes e.g. , endoscopes, stethoscopes, and arthoscopes
  • ware includes items such as eating and cooking utensils.
  • ware washing refers to washing, cleaning, or rinsing ware.
  • water soluble refers to a compound that can be dissolved in water at a concentration of more than about 1 wt-%.
  • the terms “sparingly soluble” or “sparingly water soluble” refer to a compound that can be dissolved in water only to a concentration of about 0.1 to about 1.0 wt-%.
  • water insoluble refers to a compound that can be dissolved in water only to a concentration of less than about 0.1 wt-%.
  • weight percent refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent,” “%,” and the like are intended to be synonymous with “weight percent,” “wt-%,” etc.
  • etch and corrosion inhibition systems are disclosed in U.S. Patent Nos. 7,709,434 and 7,759,299 and U.S. Patent Application Serial Nos. 12/114,364, 12/114,342 and 12/726,179, the disclosures of which are herein incorporated in its entirety.
  • Such corrosion inhibitor compositions have been found to provide suitable etch protection to glass and soft metal surfaces, such as aluminum, against corrosive attack by alkalinity in warewash detergents.
  • additional corrosion, salt deposit and scale-inhibitor systems known in the art include for example U.S. Patent No. 3,965,027 the disclosure of which is herein incorporated in its entirety.
  • compositions according to the present invention provide the benefit of anticorrosive effects traditionally observed when metal surfaces are contacted with hypochlorite solutions at concentrations often as low as about 100 ppm.
  • the corrosion inhibitor compositions according to the invention are suitable for use in any application where it is desirable to reduce surface corrosion caused by such hypochlorite solutions.
  • the anticorrosive effects are obtained at a rate of corrosion of a treated surfaces that is less than the rate of corrosion for an otherwise identical use solution of hypochlorite except for the absence of the corrosion inhibitor according to the invention.
  • a corrosion inhibitor e.g. water soluble, non- thickening polyacrylate compound, water soluble zinc, sugar acid
  • water soluble calcium salt provides a mechanism of synergistic corrosion inhibition.
  • the calcium compound forms a microscopic protective film on the surface of articles exposed to the present corrosion inhibitor composition.
  • the protective film can be transparent or not visible to the unaided eye and functions as a protective layer to slow or prevent the corrosive hypochlorite solutions components, namely sodium hypochlorite, sodium chloride and often sodium hydroxide, from attacking and corroding the surface of the article via the different corrosive mechanisms.
  • the film may function to allow the corrosive hypochlorite solution to attack and remove portions of the film, rather than attack the surface of the article.
  • the combined use of the corrosion inhibitor provides further mechanism of corrosion inhibition that acts in synergy with the calcium compound.
  • a corrosion inhibitor composition comprises, consists of and/or consists essentially of a hypochlorite source and a corrosion inhibitor comprising both a polyacrylate compound and a calcium compound.
  • the corrosion inhibitor package of a polyacrylate and calcium compound exhibits excellent corrosion inhibition for metal surfaces in the presences of a hypochlorite source.
  • the corrosion inhibitor package according to the invention may therefore be added to compositions, wherein hypochlorite sources are employed, to inhibit the corrosion of metal surfaces.
  • the combination of the polyacrylate compound and calcium compound generate synergistic increases in corrosion inhibition caused by hypochlorite sources, compared to corrosion inhibition obtained with the use of either a polyacrylate compound or calcium compound alone.
  • the calcium compound according to the corrosion inhibitor compositions provides a source of calcium ions.
  • Any water soluble calcium compounds that provide calcium ions may be used according to the invention.
  • the sources of calcium ions can be provided as elemental metals, organic salts, inorganic salts, organic oxides, inorganic oxides or mixtures thereof.
  • the sources of calcium ions can further be provided as an anhydrous compound or as a hydrated component.
  • the polyacrylate is a non- thickening polyacrylate.
  • the polyacrylate compound may further be a polyacrylate derivative.
  • Suitable polyacrylate compounds according to the invention are not effective as thickening agents, oxidizing agents and/or reducing agents.
  • suitable polyacrylate compounds do not contain an anion that acts as a bleach catalyst.
  • the polyacrylate and calcium corrosion inhibitor package is preferably comprised of a water soluble polyacrylate salt (also referred to as a polymeric salt according to the invention) and a water soluble calcium salt.
  • copolymers and homopolymers of the water soluble polyacrylate salts may be used for the corrosion inhibitor package.
  • the water soluble polymeric salt and water soluble calcium salt are sufficiently water- soluble so that when the composition is combined with a diluent, such as water, the compounds dissolve.
  • sufficiently water-soluble means that the salts dissolve at a relatively quick rate in water.
  • the solubility of the water soluble zinc and calcium salts is at least about 0.5 wt-% in water at about 20°C and atmospheric pressure.
  • the water soluble calcium and polymeric salts remain soluble in solution.
  • the water soluble calcium and polymeric salts remain dispersed in solution.
  • the polymeric and calcium salts of the corrosion inhibitor composition have a chloride or non-halide anion.
  • the polymeric and calcium salts do not contain bromide or iodide anions.
  • a corrosion inhibitor composition with non- halide anions particularly not containing bromide or iodide anions, avoids conversion of the ions into hypobromite and/or hypoiodite oxidants through the in situ reaction of the bromide and iodide with the hypochlorite.
  • the polymeric and calcium salts of the corrosion inhibiter are free of aluminum and magnesium ions.
  • Suitable water soluble polymeric salts according to the invention are not effective as thickening agents, oxidizing agents and/or reducing agents.
  • suitable water soluble polymeric salts do not contain an anion or cation that acts as a bleach catalyst.
  • oxidizing halogens and/or their hypohalous acids are not desirable for use according to the invention.
  • suitable polymeric salts for the corrosion inhibitor composition include sodium polyacrylate, sodium methacrylate, a hydrate thereof, and a mixtures thereof or the like.
  • the salts can be provided as hydrated salts or anhydrous salts.
  • the polyacrylates and polymeric salts for the corrosion inhibitor composition according to the invention have a molecular weight of less than about 10,000, preferably less than about 7,000, and more preferably less than about 4,000.
  • the molecular weight ranges of the preferred polyacrylates and polymeric salts for the corrosion inhibitor composition according to the invention correlate with the non-thickening properties of the polyacrylate corrosion inhibitors.
  • a corrosion inhibitor composition comprises, consists of and/or consists essentially of a hypochlorite source and a corrosion inhibitor comprising both a zinc compound and a calcium compound.
  • the corrosion inhibitor package of a zinc and calcium compound exhibits excellent corrosion inhibition for metal surfaces in the presences of a hypochlorite source.
  • the corrosion inhibitor package according to the invention may therefore be added to compositions, wherein hypochlorite sources are employed, to inhibit the corrosion of metal surfaces.
  • the combination of the zinc compound and calcium compound generate synergistic increases in corrosion inhibition caused by hypochlorite sources, compared to corrosion inhibition obtained with the use of either a zinc compound or calcium compound alone.
  • the zinc compound and calcium compound according to the corrosion inhibitor compositions provide a source of zinc and calcium ions.
  • Any water soluble zinc and calcium compounds that provide zinc and calcium ions may be used according to the invention.
  • the sources of each ion can be provided as elemental metals, organic salts, inorganic salts, organic oxides, inorganic oxides or mixtures thereof.
  • the sources of each ion can further be provided as an anhydrous compound or as a hydrated component.
  • the zinc and calcium corrosion inhibitor package is preferably comprised of a water soluble zinc salt and a water soluble calcium salt.
  • the water soluble zinc salt and water soluble calcium salt are sufficiently water-soluble so that when the composition is combined with a diluent, such as water, the compounds dissolve.
  • sufficiently water-soluble means that the salts dissolve at a relatively quick rate in water.
  • the solubility of the water soluble zinc and calcium salts is at least about 0.5 wt-% in water at about 20°C and atmospheric pressure.
  • the water soluble calcium and zinc salts remain soluble in solution.
  • the water soluble calcium and zinc salts remain dispersed in solution.
  • the zinc and calcium salts of the corrosion inhibitor composition have a chloride or non-halide anion.
  • the zinc and calcium salts do not contain bromide or iodide anions.
  • a corrosion inhibitor composition with non-halide anions particularly not containing bromide or iodide anions, avoids conversion of the ions into hypobromite and/or hypoiodite oxidants through the in situ reaction of the bromide and iodide with the hypochlorite.
  • the zinc and calcium salts of the corrosion inhibiter are free of aluminum and magnesium ions.
  • Suitable water soluble zinc salts according to the invention are not effective as oxidizing agents or reducing agents.
  • suitable water soluble zinc salts do not contain an anion that acts as a bleach catalyst.
  • oxidizing halogens and/or their hypohalous acids are not desirable for use according to the invention.
  • Zinc salts may include, for example, zinc acetate, zinc benzoate, zinc chlorate, zinc chloride, zinc dihydrogen phosphate, zinc formate, zinc gluconate, zinc glycerophosphate, zinc lactate, zinc metasilicate, zinc nitrate, zinc pantothenate, zinc phosphate, zinc salicylate, zinc succinate, zinc sulfate, a hydrate thereof, and a mixtures thereof or the like.
  • the salts can be provided as hydrated salts or anhydrous salts.
  • suitable zinc salts for the corrosion inhibitor composition include zinc chloride and zinc sulfate.
  • a corrosion inhibitor composition comprises, consists of and/or consists essentially of a hypochlorite source and a corrosion inhibitor comprising both a sugar acid and a calcium compound.
  • the corrosion inhibitor package of a sugar acid and calcium compound exhibits excellent corrosion inhibition for metal surfaces in the presences of a hypochlorite source.
  • the corrosion inhibitor package according to the invention may therefore be added to compositions, wherein hypochlorite sources are employed, to inhibit the corrosion of metal surfaces.
  • the combination of the sugar acid and calcium compound generate synergistic increases in corrosion inhibition caused by hypochlorite sources, compared to corrosion inhibition obtained with the use of either a sugar acid or calcium compound alone.
  • the sugar acid and calcium compound according to the corrosion inhibitor compositions provide a source of calcium ions.
  • Any water soluble calcium compound that provides calcium ions may be used according to the invention.
  • the sources of calcium ions can be provided as elemental metals, organic salts, inorganic salts, organic oxides, inorganic oxides or mixtures thereof.
  • the sources of calcium ions can further be provided as an anhydrous compound or as a hydrated component.
  • any sugar acid may be utilized and/or any oxidation product of a sugar acid.
  • Sugar acids include monosaccharides with an -OH group oxidized to a carboxyl group.
  • Exemplary sugar acids include aldonic acids, ulosonic acids, uronic acids and aldaric acids.
  • aldonic acids are those sugar acids where the aldehyde functional group of an aldose is oxidized.
  • Ulosonic acids are those sugar acids in which a keto- acid is formed via oxidation of the first hydroxyl of a 2-ketose is oxidized.
  • Uronic acids are those sugar acids where an aldose's or ketose's first hydroxyl group is oxidized.
  • aldaric acids are those sugar acids with both ends of an aldose oxidized.
  • Suitable sugar acids according to the invention include the following nonlimiting examples, including ascorbic acid, gluconic acid, galaturonic acid, mucic acid, and glucaric acid. Both ascorbic acid and gluconic acid are particularly suitable sugar acids for use in the corrosion inhibitor package.
  • ascorbic acid may be considered a "vinyl"carboxylic acid with the double bond's electrons shared between the hydroxyl and the carbonyl moieties.
  • There are two resonance structures for the deprotonated form differing in the position of the double bond.
  • Ascorbic acid might also be considered an enol.
  • the deprotonated form would then be a strongly basic enolate with the adjacent double bond stabilizing the deprotonated form.
  • the sugar acid and calcium corrosion inhibitor package is preferably comprised of a sugar acid selected from the group consisting of ascorbic acid, gluconic acid, galaturonic acid, mucic acid, and glucaric acid and a water soluble calcium salt.
  • the sugar acid and water soluble calcium salt are sufficiently water-soluble so that when the composition is combined with a diluent, such as water, the compounds dissolve.
  • sufficiently water-soluble means that the salts dissolve at a relatively quick rate in water.
  • the solubility of the water soluble zinc and calcium salts is at least about 0.5 wt-% in water at about 20°C and atmospheric pressure.
  • the water soluble calcium and sugar acid remain soluble in solution.
  • the water soluble calcium and sugar acid remain dispersed in solution.
  • the calcium salt of the corrosion inhibitor composition has a chloride or non-halide anion.
  • the calcium salt does not contain bromide or iodide anions.
  • a corrosion inhibitor composition with non-halide anions particularly not containing bromide or iodide anions, avoids conversion of the ions into hypobromite and/or hypoiodite oxidants through the in situ reaction of the bromide and iodide with the hypochlorite.
  • the zinc and calcium salts of the corrosion inhibiter are free of aluminum and magnesium ions.
  • suitable water soluble calcium salts according to the invention are not effective as oxidizing agents or reducing agents.
  • suitable water soluble calcium salts do not contain an anion that acts as a bleach catalyst.
  • oxidizing halogens and/or their hypohalous acids are not desirable for use according to the invention.
  • Calcium salts may include, for example, calcium acetate, calcium benzoate, calcium chlorate, calcium chloride, calcium dihydrogen phosphate, calcium formate, calcium gluconate, calcium glycerophosphate, calcium lactate, calcium metasilicate, calcium nitrate, calcium pantothenate, calcium phosphate, calcium salicylate, calcium succinate, calcium sulfate, a hydrate thereof, and a mixtures thereof or the like.
  • the salts can be provided as hydrated salts or anhydrous salts.
  • Exceptionally suitable calcium salts for the corrosion inhibitor composition include calcium chloride and calcium sulfate.
  • the corrosion inhibitor compositions comprise low levels of corrosion-inhibiting additives.
  • the corrosion inhibitor compositions comprise ingredients on the U.S. Environmental Protection Agency (EPA) Inert Ingredient List for antimicrobial formulations.
  • hypochlorite sources may be utilized.
  • the corrosion inhibitor is preferably a bleach hypochlorite solution.
  • the hypochlorite source according to the invention includes sodium hypochlorite and sodium chloride.
  • the hypochlorite source may further optionally include sodium hydroxide.
  • a commercially- available hypochlorite source is XY-12, available from Ecolab, Inc. and provides a concentrated bleach hypochlorite suitable for use according to the invention.
  • the hypochlorite solution is free of carbonate or bicarbonate anions.
  • the corrosion inhibitor compositions according to the invention have a suitable ratio of a hypochlorite source to corrosion inhibitor from about 10:1 to about 600:1.
  • the level of corrosion inhibitor in a hypochlorite solution varies with the particular ratio of the corrosion inhibitor agent to calcium utilized for the corrosion inhibitor package.
  • Particularly suitable ratios of hypochlorite source to corrosion inhibitor are from about 50: 1 to about 200:1, from about 40:1 to about 150: 1, from about 30: 1 to about 100: 1, from about 20:1 to about 50:1, and from about 10:1 to about 1: 1.
  • the corrosion inhibitor composition can include a corrosion inhibitor package, comprising a corrosion inhibitor and calcium compound, in an amount from about 0.01 wt-% to about 50 wt-%, preferably about 0.01 wt-% to about 20 wt- %, more preferably from about 0.1 wt-% to about 10 wt-% and most preferably from about 0.1 wt-% to about 2 wt-%.
  • the corrosion inhibitor composition includes an effective amount of the corrosion inhibitor package in order to provide a use solution inhibiting corrosion of metal surfaces contacted with hypochlorite sources.
  • the phrase "effective amount" in reference to the corrosion inhibitors refers to an amount sufficient to provide a use corrosion inhibitor composition that inhibits surface corrosion compared with a composition that is identical except that it does not contain a sufficient amount of the corrosion inhibitor to reduce surface corrosion after contact with a hypochlorite source. According to a preferred embodiment, the sufficient amount of corrosion inhibitor does not adversely impact the stability of the hypochlorite source.
  • the corrosion inhibitor composition according to the invention further has a suitable ratio of the particular corrosion inhibitor to calcium compound.
  • a suitable ratio of the particular corrosion inhibitor to a calcium salt for the corrosion inhibitor package is from about 6: 1 to about 1 :6.
  • Particularly suitable ratios of said corrosion inhibitor to the calcium salt are from about 4: 1 to about 1:4.
  • the ratio of the corrosion inhibitor to calcium salt for the corrosion inhibitor package may be controlled to provide reduced corrosion of treated metal surfaces compared with the use of either component alone.
  • the combined use of a corrosion inhibitor and calcium compound, namely water soluble calcium and polymeric salts can provide a synergy in the reduction of metal corrosion caused by a hypochlorite source.
  • the corrosion inhibitor composition generally includes a use solution that has a non-acidic pH.
  • the pH suitable for use with the corrosion inhibitor composition may be either neutral or alkaline.
  • basic or alkaline pH refers to pH greater than 7, greater than or equal to 8, about 8 to about 9.5, about 8 to about 11, greater than about 9, or about 9 to about 10.5.
  • a preferred use solution pH to provide a corrosion-inhibited hypochlorite bleach source is from about pH 7 to about pH 9, more preferably from about pH 7 to about pH 8.
  • the present corrosion inhibitor composition or a composition containing the corrosion inhibitors can be provided in the form of a concentrate or a use solution.
  • a concentrate refers to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired corrosion inhibition according to the invention.
  • a use solution may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having desired corrosion inhibition properties.
  • the corrosion inhibitor composition that contacts the articles to be protected from hypochlorite corrosion can be referred to as a use composition.
  • a concentrate composition may be diluted at a weight ratio of diluent to concentrate of at least about 1 : 1 or about 1 : 1 to about 2000: 1.
  • the use solution of a corrosion inhibitor composition will include at least about 25 parts per million (ppm) of the corrosion inhibitor to provide desired corrosion inhibition properties. Larger amounts of corrosion inhibitor can be used in the use solution without deleterious effects.
  • Embodiments of the use solution of a corrosion inhibitor composition according to the invention can include from about 25 ppm to about 3000 ppm of the corrosion inhibitor, or about 50 to about 2000 ppm of the corrosion inhibitor. The amount of corrosion inhibitor is calculated based upon the combined amount of polyacrylate and calcium compounds used according to the invention.
  • the concentrate may be diluted with water at the location of use to provide the use solution.
  • the corrosion inhibitor composition When the corrosion inhibitor composition is used in an automatic warewashing or other machine, it is expected that the location of use will be inside the automatic machine.
  • the hypochlorite source ⁇ i.e. bleach or sanitizer
  • the corrosion inhibitor composition may be provided in a unit dose form or in a multi-use form.
  • a large quantity of corrosion inhibitor composition may be provided in a compartment that allows for the release of a single dose amount of the composition for each cycle. Such a compartment may be provided as part of the warewashing machine or as a separate structure connected to the warewashing machine.
  • the use solution of a corrosion inhibitor composition according to the invention may also be used in the form of a wipe, including a pre-saturated wipe.
  • a use solution according to the invention is provided on a wipe for direct application to a surface.
  • the use solution of the corrosion inhibitor composition includes at least about 25 parts per million (ppm) of the corrosion inhibitor to provide desired corrosion inhibition properties. In particular embodiments at least about 50 ppm corrosion inhibitor are included, at least about 100 ppm, at least about 150 ppm, and more preferably at least about 200 ppm of the corrosion inhibitor are contained in the use solution of the composition saturated into a wipe.
  • the ratio of corrosion inhibitor to a calcium salt for the corrosion inhibitor package is from about 6: 1 to about 1 :6, preferably about 4: 1 to about 1 :4. According to a particular embodiment the ratio of hypochlorite source to corrosion inhibitor are from about 10:1 to about 600: 1.
  • a wipe housing the corrosion inhibitor composition according to the invention such as a pre-saturated wipe has between about 500 ppm to about 30,000 ppm disinfectant hypochlorite, preferably between about 1 ,000 ppm to about 20,000 ppm and more preferably from about 4,000 ppm to about 7,000 ppm disinfectant hypochlorite.
  • the corrosion inhibitor composition has a ratio of corrosion inhibitor to a calcium salt from about 4: 1 to about 1:4.
  • Corrosion inhibitor compositions made according to the invention may further include additional functional agents or additives that provide a beneficial property.
  • additional agents or additives may be selected from the group consisting of pH adjusters or other neutralizing agents, surfactants, emulsifiers, sequestrants, solubilizers, other lubricants, buffers, detergents, cleaning agent, rinse aid composition, secondary anti-corrosion agent, preservatives, binders, thickeners or other viscosity modifiers, processing aids, carriers, water-conditioning agents, foam inhibitors or foam generators, threshold agent or system, aesthetic enhancing agent (i.e. , dye, odorant, perfume), other agents or additives suitable for formulation with a corrosion inhibitor composition and the like, and mixtures thereof. Additional agents or additives will vary according to the particular corrosion inhibitor composition being manufactured and its intend use as one skilled in the art will appreciate based on the enabling disclosure of the present invention.
  • the corrosion inhibitor compositions do not contain any of the additional agents.
  • a corrosion inhibitor composition according to the invention only contains hypochlorite-compatible additional agents, for example, surfactants, viscosity modifiers and fragrances.
  • the corrosion inhibitor composition does not contain the additional agents commercially- available in common detergent compositions.
  • the corrosion inhibitor compositions according to the present invention can be dispensed in any suitable method generally known by one skilled in the art.
  • spray-type dispenser such as that disclosed in U.S. Pat. Nos. 4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re 32,763 and 32,818, the disclosures of which are incorporated by reference herein.
  • a spray-type dispenser functions by impinging a water spray upon an exposed surface of the solid composition to dissolve a portion of the composition, and then immediately directing the concentrate solution including the composition out of the dispenser to a storage reservoir or directly to a point of use.
  • the present corrosion inhibitor composition can be dispensed by immersing either intermittently or continuously in water.
  • the composition can then dissolve, for example, at a controlled or predetermined rate.
  • the rate can be effective to maintain a concentration of dissolved cleaning agent that is effective for use according to the methods of the claimed invention.
  • the present corrosion inhibitor composition can be dispensed by scraping solid from the solid composition and contacting the scrapings with water.
  • the scrapings can be added to water to provide a concentration of dissolved corrosion inhibitor that is effective for use according to the methods of the claimed invention.
  • the methods for corrosion inhibition according to the invention protect surfaces in contact with hypochlorite sources from corrosion caused by hypochlorite bleach used for a variety of surfaces and antimicrobial treatments.
  • Methods for corrosion inhibition according to the invention may comprise, consist of and/or consist essentially of contacting a surface with a corrosion inhibitor composition, wherein said corrosion inhibitor composition comprises a hypochlorite source and a water soluble polyacrylate and calcium compound.
  • the corrosion inhibitor composition may comprise a hypochlorite source and a sugar acid and calcium compound.
  • the corrosion inhibitor composition may comprise a hypochlorite source and a zinc compound and calcium compound.
  • the corrosion inhibitor compositions provide an inhibited hypochlorite solution that can be used as a bleach or surface antimicrobial agent in a variety of applications.
  • One skilled in the art will appreciate and know various application methods.
  • the methods of the invention relate to a method employing the corrosion inhibitor composition.
  • the method can include providing the corrosion inhibitor composition to a surface treated with a hypochlorite solution in order to inhibit corrosion caused by the hypochlorite solution.
  • the method can include preparing an aqueous use composition of the present corrosion inhibitor composition.
  • the method may further include contacting a surface, such as a hard metal surface, in need of corrosion inhibition due to contact with a hypochlorite solution.
  • suitable surfaces may be contacted with the corrosion inhibitor composition according to the invention.
  • Particularly suitable surfaces for treatment with the corrosion inhibitor compositions according to the invention include metallic and metal-containing surfaces, including steel, rolled steel and stainless steel.
  • Surfaces may be contacted according to the methods of the present invention for use as a hard surface cleaner or sanitizer, including for example, industrial surfaces, food and beverage surfaces, food service and restaurant surfaces, and health care surfaces.
  • the corrosion of washers such as tunnel washers for washing textiles, may be inhibited according to methods of the claimed invention.
  • compositions and methods of the invention include those in need of disinfectant treatment, such as hospital and other medical facility markets.
  • Exemplary surfaces commonly found in such settings include, for example, 6061 aluminum, 304 stainless steel, polished nickel and plated chrome.
  • sodium hypochlorite has been shown to be beneficial to disinfecting Clostridium difficile as well as other organisms it is recommended for use in contaminated areas. (See Guide to the Elimination of Clostridium Difficile in Healthcare Settings, 2008, Association for Professionals in Infection Control Epidemiology, Inc. ; Guidelines for Environmental Infection Control in Health-Care Facilities, 2003, Centers for Disease Control and the Healthcare Infection Control Practices Advisory Committee).
  • health care surfaces are well suited as they often contain metal surfaces that can be easily damaged by contact with sodium hypochlorite.
  • An exemplary surface is a medical instrument with metals in the construction.
  • the present invention of a corrosion inhibitor composition allows for the use of sodium hypochlorite on such hospital and other surfaces where it cannot otherwise be utilized.
  • the methods of applying the corrosion inhibitor composition may include, for example, the use of a spray or a wipe method (e.g. use of a pre- saturated wipe configuration).
  • a wipe method is particularly desirable as a result of concerns of respirator difficulties for those using the compositions containing sodium hypochlorite.
  • surfaces may be contacted according to the methods of the present invention for use in low temperature dish and/or warewash sanitizing final rinse, toilet bowl cleaners, and laundry bleaches.
  • the corrosion inhibitor compositions and the claimed methods are used as sanitizers for pools, spas, and hot tubs. According to further embodiments of the invention, the methods are used to treat metal surfaces, such as ware, cleaned and/or sanitized with corrosive hypochlorite sources.
  • the commercially-available concentrated hypochlorite bleach product XY-12 (Ecolab, Inc.), containing 12% sodium hypochlorite and about 12% sodium chloride and a use solution of the bleach product diluted to 100 ppm hypochlorite were applied to the stainless steel coupons. Both hypochlorite solutions caused heavily discolored (dark brown) coupons.
  • the stainless steel coupons treated with the concentrated bleach/hypochlorite solution showed further corrosion signs of pitting and rust.
  • EXAMPLE 2 Comparison of corrosive effects of hypochlorite solutions with corrosion inhibitor compositions. The weight loss of the coupons was determined, with higher weight loss corresponding to loss of metal due to corrosion.
  • the commercially-available concentrated bleach product was modified to contain a non-thickening polyacrylate.
  • the commercially-available polyacrylate Acusol 445N (available from Rohm and Haas) was tested for anti-corrosion efficacy alone, in combination with calcium chloride and compared to calcium chloride alone. Formulations for the various tests are shown in Table 1 below. TABLE 1
  • Example 1 The commercially available hypochlorite solution of Example 1 was diluted to 100 ppm hypochlorite and further modified according to the corrosion inhibition test systems described in Table 1. Non-significant, very slight discoloration of the stainless steel coupon at the air/liquid interact was obtained after three days at 120°F. No pitting and/or rusting corrosion was obtained. The combination of polyacrylate and calcium chloride showed synergistic reduction in the attack of hypochlorite on stainless steel surfaces. Synergy was determined from the data obtained from designed experiments and an analysis specifically focused on finding synergy. The synergy and rations of ingredients of a corrosion inhibitor package that achieve such synergy are described further herein below.
  • the corrosion inhibition packages according to the invention provide simultaneous control of all corrosive mechanisms of sodium hypochlorite, sodium chloride, and sodium hydroxide (or any combination of the same that may be found in a bleach or hypochlorite source).
  • the corrosion inhibition does not result in any inhibition, inactivation or other modification to the stability of the hypochlorite source, as may be readily measured by one skilled in the art to which the invention pertains.
  • Example 1 The commercially available hypochlorite solution of Example 1 was diluted to 100 ppm hypochlorite and further modified according to the corrosion inhibition test systems described in Table 1. Non-significant, very slight discoloration of the stainless steel coupon at the air/liquid interact was obtained after three days at 120°F. No pitting and/or rusting corrosion was obtained.
  • sugar acid ascorbic acid
  • calcium chloride showed synergistic reduction in the attack of hypochlorite on stainless steel surfaces.
  • Synergy was determined from the data obtained from designed experiments and an analysis specifically focused on finding synergy.
  • the synergy and rations of ingredients of a corrosion inhibitor package that achieve such synergy are described further herein below.
  • the results were unexpected as a result of the use of the ascorbic acid with the hypochlorite solution showed some accelerated attack of hypochlorite on the steel surfaces.
  • the calcium by itself did not show any efficacy for corrosion inhibition of hypochlorite solutions.
  • the corrosion inhibition packages according to the invention provide simultaneous control of all corrosive mechanisms of sodium hypochlorite, sodium chloride, and sodium hydroxide (or any combination of the same that may be found in a bleach or hypochlorite source).
  • the corrosion inhibition does not result in any inhibition, inactivation or other modification to the stability of the hypochlorite source, as may be readily measured by one skilled in the art to which the invention pertains.
  • the commercially-available concentrated bleach product was further diluted to 100 ppm hypochlorite and modified to contain 1 ppm of 4:1 parts by weight of zinc chloride to calcium chloride. Again, no sign of discoloration, pitting and/or rusting corrosion was obtained.
  • Example 1 The effect of zinc to calcium ratio on corrosiveness of bleach concentrate was tested using the experimental conditions set forth in Example 1. The impact of the zinc to calcium ratio on effectiveness as a corrosion inhibitor was tested versus concentration of total corrosion inhibitor used. FIG. 1 shows the change in the weight of the aged stainless steel coupons and the total corrosion inhibitor concentration.
  • the graph in FIG. 2 illustrate that areas of effective corrosion inhibitor protection of the stainless steel coupons were achieved at both neutral and alkaline pH ranges regardless of the ratio of zinc to calcium.
  • EXAMPLE 7 The synergy between zinc and calcium corrosion inhibitors was tested using the experimental conditions set forth in Example 1. The effect of the levels of zinc and calcium were evaluated and the synergy of the combination of the total corrosion inhibitor package against corrosion by a commercial bleach concentrate are demonstrated in Table 3. In addition, the corrosion inhibition obtained from calcium salts alone, in the absence of zinc salts, was ineffective for hypochlorite solutions.
  • sodium hypochlorite solutions as a disinfectant were analyzed in combination with the corrosion inhibitor compositions according to the invention demonstrating efficacy and applications for use in hospital settings and other medical facility markets.
  • the damaging effects of un-inhibited sodium hypochlorite sources were evaluated for use in contaminated areas compared to compositions according to the invention.
  • the damaging effects of sodium hypochlorite to metal surfaces were evaluated.
  • a corrosion inhibiting sodium hypochlorite formulas according to embodiments of the invention were utilized (compared to a control of sodium hypochlorite composition without the corrosion inhibiting portion of the compositions).
  • Exemplary disinfectant compositions utilized are set forth in Table
  • a pre-saturated wipe was evaluated for delivering the corrosion inhibitor compositions and control compositions.
  • the pre-saturated wipe material was generated by soaking a wipe to generate approximately 400 times its weight to ensure proper wetness.
  • One wipe from each tested variable was then used to wipe each coupon set (e.g. 6061 aluminum, 304 stainless steel, polished nickel and plated chrome).
  • Metal coupons were swept horizontally with the wipe to apply the solution. The entire coupon was covered with the solution and allowed to visibly dry in between applications (approximately 4-5 minutes). The steps were repeated before rinsing the coupons with deionized water and allowed to dry.

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Abstract

Cette invention concerne des compositions d'inhibiteurs de corrosion et des procédés pour les utiliser. Les inhibiteurs de corrosion selon l'invention sont choisis parmi le polyacrylate et les inhibiteurs de corrosion à base de calcium, les inhibiteurs de corrosion à base de zinc et de calcium et/ou les acides de sucres et les inhibiteurs de corrosion à base de calcium qui, combinés à des sources d'hypochlorite, donnent des solutions utiles pour une inhibition efficace de la corrosion sur des surfaces métalliques.
PCT/IB2011/055798 2010-12-21 2011-12-19 Inhibition de la corrosion par des solutions d'hypochlorite contenant un polyacrylate et ca, zn et ca, des acides de sucres et ca WO2012085830A2 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US12/974,468 2010-12-21
US12/974,560 2010-12-21
US12/974,520 US8114344B1 (en) 2010-12-21 2010-12-21 Corrosion inhibition of hypochlorite solutions using sugar acids and Ca
US12/974,468 US8114343B1 (en) 2010-12-21 2010-12-21 Corrosion inhibition of hypochlorite solutions using Zn and Ca
US12/974,560 US8105531B1 (en) 2010-12-21 2010-12-21 Corrosion inhibition of hypochlorite solutions using polyacrylate and Ca
US12/974,520 2010-12-21
US13/292,598 US8343380B2 (en) 2010-12-21 2011-11-09 Corrosion inhibition of hypochlorite solutions using sugar acids and Ca
US13/292,598 2011-11-09
US201113314922A 2011-12-08 2011-12-08
US13/314,922 2011-12-08

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014172318A1 (fr) * 2013-04-17 2014-10-23 Rohm And Haas Company Acides polyacryliques de masse moléculaire élevée comme inhibiteurs de corrosion dans une composition aqueuse d'hypochlorite alcalin et procédé correspondant
CN104357849A (zh) * 2014-11-17 2015-02-18 芜湖市民泰铜业有限责任公司 一种有色金属表面处理剂
WO2018217697A1 (fr) * 2017-05-24 2018-11-29 General Electric Company Polymères de polyacrylate de maîtrise de corrosion d'acier à faible teneur en carbone

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US2121501A (en) * 1936-03-17 1938-06-21 Oakite Prod Inc Hypochlorite composition
US4664836A (en) * 1985-09-18 1987-05-12 Amway Corporation Drain cleaner
US5731276A (en) * 1996-07-30 1998-03-24 The Clorox Company Thickened aqueous cleaning composition and methods of preparation thereof and cleaning therewith
US7749329B2 (en) * 2007-05-04 2010-07-06 Ecolab Inc. Cleaning compositions containing water soluble magnesium compounds and methods of using them

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014172318A1 (fr) * 2013-04-17 2014-10-23 Rohm And Haas Company Acides polyacryliques de masse moléculaire élevée comme inhibiteurs de corrosion dans une composition aqueuse d'hypochlorite alcalin et procédé correspondant
CN104357849A (zh) * 2014-11-17 2015-02-18 芜湖市民泰铜业有限责任公司 一种有色金属表面处理剂
WO2018217697A1 (fr) * 2017-05-24 2018-11-29 General Electric Company Polymères de polyacrylate de maîtrise de corrosion d'acier à faible teneur en carbone
CN110691866A (zh) * 2017-05-24 2020-01-14 Bl 科技公司 用于低碳钢腐蚀控制的聚丙烯酸盐聚合物
US11634635B2 (en) 2017-05-24 2023-04-25 Bl Technologies, Inc. Polyacrylate polymers for low carbon steel corrosion control
AU2018271842B2 (en) * 2017-05-24 2023-07-27 Bl Technologies, Inc. Polyacrylate polymers for low carbon steel corrosion control

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