US20080145271A1 - Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces - Google Patents

Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces Download PDF

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Publication number
US20080145271A1
US20080145271A1 US11/612,901 US61290106A US2008145271A1 US 20080145271 A1 US20080145271 A1 US 20080145271A1 US 61290106 A US61290106 A US 61290106A US 2008145271 A1 US2008145271 A1 US 2008145271A1
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Prior art keywords
corrosion
inhibiting
water
composition
white rust
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US11/612,901
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English (en)
Inventor
Srikanth S. Kidambi
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Ecolab USA Inc
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Nalco Co LLC
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Priority to US11/612,901 priority Critical patent/US20080145271A1/en
Assigned to NALCO COMPANY reassignment NALCO COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIDAMBI, SRIKANTH S.
Priority claimed from US11/612,702 external-priority patent/US7851655B2/en
Priority to CA2673297A priority patent/CA2673297C/en
Priority to CN2007800468081A priority patent/CN101568430B/zh
Priority to RU2009122438/05A priority patent/RU2009122438A/ru
Priority to SG2011093358A priority patent/SG177897A1/en
Priority to JP2009543098A priority patent/JP2010513724A/ja
Priority to MX2009006515A priority patent/MX2009006515A/es
Priority to EP07869274A priority patent/EP2091727A4/en
Priority to PCT/US2007/087531 priority patent/WO2008079734A1/en
Priority to BRPI0719406A priority patent/BRPI0719406A8/pt
Priority to KR1020097014944A priority patent/KR20090101249A/ko
Priority to AU2007337103A priority patent/AU2007337103A1/en
Publication of US20080145271A1 publication Critical patent/US20080145271A1/en
Assigned to BANK OF AMERICA, N.A., AS COLLATERAL AGENT reassignment BANK OF AMERICA, N.A., AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: CALGON LLC, NALCO COMPANY, NALCO CROSSBOW WATER LLC, NALCO ONE SOURCE LLC
Priority to ZA200904410A priority patent/ZA200904410B/xx
Priority to US12/944,783 priority patent/US8883073B2/en
Assigned to NALCO COMPANY reassignment NALCO COMPANY RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BANK OF AMERICA, N.A.
Assigned to NALCO COMPANY reassignment NALCO COMPANY RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BANK OF AMERICA, N.A.
Assigned to NALCO COMPANY LLC reassignment NALCO COMPANY LLC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: NALCO COMPANY
Assigned to ECOLAB USA INC. reassignment ECOLAB USA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CALGON CORPORATION, CALGON LLC, NALCO COMPANY LLC, ONDEO NALCO ENERGY SERVICES, L.P.
Assigned to ECOLAB USA INC. reassignment ECOLAB USA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NALCO COMPANY
Abandoned legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C23F11/16—Sulfur-containing compounds
    • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23F11/16—Sulfur-containing 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
    • C23F11/10—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
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans
    • 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
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations

Definitions

  • This invention relates generally to inhibiting corrosion on galvanized metal surfaces. More specifically, the invention relates to a method for inhibiting white rust corrosion on galvanized surfaces. The invention has particular relevance for inhibiting white rust corrosion by using sulfide-based compounds on galvanized metal surfaces in industrial water systems.
  • Galvanization is a protective zinc coating that is chemically bonded to a metal (usually iron or steel) surface.
  • Zinc coating is used in a variety of applications and offers a certain degree of corrosion protection for the underlying metal by providing a mechanical barrier to the elements and environment as well as electrochemical resistance to corrosion.
  • galvanizing methods exist, such as electroplating, continuous galvanization, and hot-dip galvanization.
  • Many industrial water systems such as cooling water circulation systems (sometimes referred to herein as “cooling towers”), have such galvanized surfaces.
  • white rust A common problem with galvanized coatings of all kinds is “white rust,” which manifests itself as a white, waxy, fluffy, or powdery non-protective and porous deposit that rapidly forms on galvanized surfaces when the surface is exposed to humid and/or wet conditions.
  • White rust can cause considerable damage to the zinc coating and is also detrimental to the coating's appearance. If left unchecked, white rust will continually corrode affected galvanized surfaces and eventually lead to early failure of the coating. With such a non-protective, porous deposit on the galvanized surface, the surface is not “passive” to future white rust formation and may rapidly continue to corrode.
  • This basic zinc carbonate barrier believed to be a zinc carbonate/zinc hydroxide compound (as discussed in “Guidelines for Treatment of Galvanized Cooling Towers to Prevent White Rust,” published by the Cooling Tower Institute in June 1994) typically forms within eight weeks of initial cooling tower operation with water of neutral pH (i.e., pH 6.5 to 8.0) and moderately hard water environment.
  • a typical solute content range would be calcium (CaCO 3 ) content of 100 ppm to 300 ppm as bicarbonate alkalinity and about 100 ppm CaCO 3 hardness.
  • Formation of the protective zinc carbonate barrier is important for the cooling tower to resist further corrosion. Barrier absence could result in severe white rust formation and have a significant negative impact on the cooling tower's service life.
  • White rust is also a form of zinc carbonate that has a different porous structure, rate of formation, and density than the protective zinc carbonate barrier described above. If the water hardness levels, measured by CaCO 3 hardness, reach levels below 50 ppm (i.e., soft water), accelerated zinc corrosion generally results. Certain ionic content in the water, such as sulfates, chlorides, and nitrates at levels greater than about 250 ppm may also contribute to accelerated zinc corrosion. Thus, routine inspection of the cooling tower coupled with adequate control of the water chemistry aids in the prevention of white rust formation.
  • white rust corrosion prevention programs include a combination of pre-passivating the cooling tower combined with ongoing water chemistry management to support the viability of the passivation layer.
  • white rust preventatives include pretreatment with inorganic phosphate and chromate passivation. Such inorganic solutions have limited effectiveness and are steadfastly becoming the object of federal and local regulations due to environmental concerns.
  • U.S. Pat. No. 5,407,597 provides a formulation including a mixture of an organophosphorous compound, a thiocarbamate compound, and soluble metal salt compound. The components of this formulation are used as a combination and the ingredients tested alone typically do not control white rust formation.
  • the formulation in U.S. Pat. No. 6,468,470 B1 includes a multi-component system of an organophosphorous compound, a tannin compound, and a soluble salt of a metal.
  • cooling towers have substantial evaporative water loss.
  • large quantities of “make-up” water are introduced into the system that commonly contains ionic species, such as calcium, magnesium, sulphate, and chloride.
  • Increased alkalinity e.g., carbonate, bicarbonate, and hydroxide ions
  • carbonate alkalinity may also cause white rust corrosion.
  • accumulation of carbonate alkalinity, with a concomitant pH increase creates an ideal white rust-forming environment. This accumulation is one of the major causes of white rust.
  • the presence of excess anions and/or soft water can aggravate the degree of white rust formation by, for example, reacting with the zinc coating to produce zinc hydroxide.
  • biocides are essential is preventing algal, bacterial, and fungal contamination of the systems. Some of these biocides sometimes promote white rust formation as a byproduct because they chemically react with certain white rust inhibitors and/or with the zinc coating.
  • sodium hypochlorite i.e., bleach
  • bleach is a common biocide and is highly reactive.
  • this invention provides a method of preventing corrosion on galvanized metal surfaces.
  • the method includes introducing an effective amount of a corrosion-inhibiting composition having a sulfur-based, preferably sulfide-based, white rust corrosion-inhibiting compound onto a galvanized metal surface to form a barrier on the surface.
  • the method further includes overlaying the barrier by reintroducing an effective amount of the composition onto the galvanized metal surface after one or more time intervals.
  • the invention provides a method of inhibiting corrosion in an industrial water system that is at least partially full of water and has one or more galvanized metal surfaces.
  • the method includes adjusting the water in the industrial water system to have a pH from about 6.5 to about 8.2 and introducing an effective amount of a corrosion-inhibiting composition that includes one or more sulfur-based or sulfide-based white rust corrosion-inhibiting compounds into the water of the industrial water system.
  • Implementing the method may be accomplished when the system is either under load or not under load. If the system is not under load when introducing the corrosion-inhibiting composition, the water in the system is circulated after such introduction for a time interval to contact the sulfur-based white rust corrosion-inhibiting compound with the galvanized metal surfaces of the system to form the barrier on those surfaces. After a sufficient interval, the unloaded system may be turned on or brought under load at any suitable time. If the system is under load when introducing the corrosion-inhibiting composition, the system is operated under load after such introduction for a time interval to contact the white rust corrosion-inhibiting compound with the galvanized metal surfaces of the system and form the barrier on those surfaces.
  • the invention provides a method for overlaying the barrier formed by the sulfide-based white rust-inhibiting compound.
  • This aspect includes overlaying the barrier while the system is under load or not under load. If the barrier is overlaid while the system is under load, the method includes readjusting the pH of the system to be from about 6.5 to about 8.2 and reintroducing an effective amount of the corrosion-inhibiting composition into the water of the system. The system is then operated under load for one or more additional time intervals and the barrier optionally is re-overlaid after one or more of the additional time intervals.
  • the method includes readjusting the pH of the system to be from about 6.5 to about 8.2, reintroducing an effective amount of the corrosion-inhibiting composition into the water of the system, and circulating the water of the system for a sufficient interval to contact the sulfide-based compound with the surfaces. After the sufficient interval, the unloaded system may be turned on or brought under load at any suitable time.
  • Contemplated applications include any system having galvanized metal surfaces.
  • the invention may also be combined with one or more other corrosion or scale inhibiting compositions, such as silicates, borates, molybdates, tungstates, chromate, zinc salts, orthophosphates, polyphosphates, phosphonate/phosphinate, combinations thereof, or any other suitable corrosion or scale inhibiting compound or composition, with or without one or more fluorescent tracer compounds.
  • corrosion or scale inhibiting compositions such as silicates, borates, molybdates, tungstates, chromate, zinc salts, orthophosphates, polyphosphates, phosphonate/phosphinate, combinations thereof, or any other suitable corrosion or scale inhibiting compound or composition, with or without one or more fluorescent tracer compounds.
  • An advantage of the invention is to provide a method of inhibiting corrosion, especially white rust corrosion, on galvanized metal surfaces.
  • Another advantage of the invention is to extend the lifespan of galvanized metal surfaces in various applications including industrial water systems.
  • Yet another advantage of the invention is to provide a one-step passivation method for inhibiting white rust corrosion on galvanized surfaces of industrial water systems.
  • An additional advantage of the invention is to provide a method for initially pre-passivating with a sulfur-based white rust corrosion-inhibiting composition and post-treating by overlaying the sulfur-based white rust corrosion-inhibiting composition on galvanized surfaces.
  • the invention provides a method of inhibiting corrosion on a galvanized metal surface.
  • the method includes introducing an effective amount of a corrosion-inhibiting composition onto the galvanized metal surface to form a barrier on the surface.
  • barrier includes surface modification of the galvanized surface, change of morphology of the galvanized surface, chemical interaction of any of the white rust corrosion-inhibiting compounds with the galvanized surface, or any other similar modification of or interaction with the surface.
  • an effective amount of the corrosion-inhibiting composition includes from about 0.001 weight percent to about 100 weight percent of the white rust corrosion-inhibiting compound.
  • an effective amount of the composition includes from about 0.001 weight percent to about 50 weight percent of the compound.
  • from about 0.1 weight percent of to about 30 weight percent of the compound of the composition is introduced to the galvanized surface.
  • white rust-inhibiting compounds described herein can each be used independently, simultaneously, sequentially, alternating between different compounds, or by implementing in any suitable order or fashion.
  • Representative sulfur-based white rust-inhibiting compounds include thiols, bismuthiols, dimerized bismuthiols, polymeric dithiocarbamates, xanthates, and combinations thereof.
  • introducing the corrosion-inhibiting composition onto the galvanized surface includes incorporating the method into a hot dip manufacturing process.
  • the metal would first be dipped in melted zinc at 450° C. (temperature at which iron/steel and zinc share great affinity) where the metal would be protected with a zinc coating.
  • the next step in the manufacturing process would be to dip the zinc-coated metal into the corrosion-inhibiting composition including the sulfur-based or sulfide-based white rust corrosion-inhibiting compound.
  • such introduction includes spraying a solution of the corrosion-inhibiting composition directly onto the surface, including surfaces in industrial water systems.
  • the composition is mixed with a foaming agent to form a mixture and the mixture is subsequently sprayed onto the galvanized metal surface using any suitable spraying device.
  • Foaming agents may include surfactants, such as alkoxylated alcohols, polyethylene glycol, or any other suitable surfactant.
  • the composition may be physically applied onto the surface by rolling using a paint roller or the like, brushing using a paintbrush or the like, swabbing using a mop or the like, or by using any other suitable method or technique.
  • the corrosion-inhibiting composition is reintroduced onto the surface one or more times after one or more time intervals to “overlay” the barrier or “re-passivate” the surface.
  • overlaying steps to renew the corrosion-inhibitory barrier and/or to re-passivate the galvanized surfaces are also contemplated.
  • the method may include a plurality of different corrosion-inhibiting compositions and overlaying the barrier may include introducing a different one or more of the corrosion-inhibiting compositions onto the galvanized metal surface(s).
  • an effective amount of the corrosion-inhibiting composition is introduced into the water of a cooling water circulation system (sometimes referred to herein as “cooling tower”) to form a barrier on (or passivate) any galvanized metal surfaces of the system.
  • a cooling water circulation system sometimes referred to herein as “cooling tower”
  • the corrosion-inhibiting composition of the invention may be introduced into any industrial water system as either an adjunct treatment in combination with other compositions or programs, such as scale and/or corrosion-inhibiting programs, or as a stand-alone treatment program, as described in more detail herein.
  • the industrial water system is at least partially full of water and has one or more galvanized metal surfaces.
  • the method includes adjusting the water in the system to have a pH from about 6.5 to about 8.2. In a preferred embodiment, the pH of the water in the system is adjusted to be from about 6.8 to about 7.8.
  • the method further includes introducing an effective amount of a corrosion-inhibiting composition that includes one or more white rust corrosion-inhibiting compounds into the water of the industrial water system.
  • the corrosion-inhibiting composition typically includes from about 1 ppm to about 10,000 ppm of the white rust corrosion-inhibiting compound. In a preferred embodiment, the composition includes from about 1 ppm to about 1000 ppm of the compound. In a more preferred embodiment, the composition includes from about 1 ppm to about 100 ppm of the compound.
  • an effective amount of the corrosion-inhibiting composition is introduced into the water of the industrial water system when the system is operating and under load.
  • the system is operated under load (i.e., turned on) for a time interval to contact the white rust corrosion-inhibiting compound with the galvanized surface(s) in the system to form a barrier on the surface(s).
  • overlaying the barrier may be implemented when the industrial water system is operating and under load or when the system has been turned off and thus not under load.
  • overlaying the barrier includes unloading (i.e., turning off) the system, readjusting the pH of the system, reintroducing an effective amount of the corrosion-inhibiting composition into the water of the system, and circulating the water of the system.
  • overlaying the barrier includes keeping the system under load, readjusting the pH of the system (as described above) and reintroducing an effective amount of the corrosion-inhibiting composition into the water of the system.
  • the method includes a plurality of different corrosion-inhibiting compositions and overlaying the barrier includes introducing a different one or more of the corrosion-inhibiting compositions into the industrial water system.
  • the corrosion-inhibiting composition of the invention is preferably introduced in a pre-passivation process prior to initially starting up the industrial water system. This method is preferred because such application typically provides the highest degree of passivation and protection for the galvanized surfaces in the system.
  • the corrosion-inhibiting composition may be introduced to a currently operating or running system. As described above, such an application may be implemented without turning off the system by leaving the system under load during the passivation process or by turning off and unloading the system.
  • the corrosion-inhibiting composition may be combined with one or more other corrosion inhibitors, one or more scale inhibitors, one or more fluorescent tracers, one or more water treatment polymers, one or more polyalkoxy compounds, or any other suitable adjunct or additional component. Any such adjuncts may be part of an existing corrosion-inhibitive program to which the invention becomes an additional component or program. Adjuncts may be part of the corrosion-inhibiting composition or may be another separate composition or compositions. In alternative embodiments, such adjuncts may be added simultaneously or sequentially with the corrosion-inhibiting composition of the invention.
  • Exemplary other corrosion and scale inhibitors include tungstate; molybdate; vanadate; phosphate; phosphonate; phosphinate; silicate; borate; zinc and its salts; polycarboxylates; benzoic acid; the like; combinations thereof, or any other suitable corrosion or scale inhibitors.
  • Exemplary water treatment polymers include polyacrylic acid; polymaleic acid; copolymers and terpolymers of acrylic acid, mateic acid, acrylamide, and acrylamidopropyl sulfonate; prism polymers; sulfonate-based polymers; and terpolymers or copolymers of acrylic acid, acrylamide, sulfomethylated acrylamide, the like, and combinations thereof.
  • Galvanized mild steel metal coupons were tested based on weight after exposure to “Standard 13” make-up water (Ca: 440 ppm (CaCO 3 ); Mg: 220 ppm (CaCO 3 ); M-alkalinity: 340 ppm; Cl ⁇ : 312 ppm (CaCO 3 ); (SO 4 ) 2 ⁇ : 211 ppm (CaCO 3 ); pH controlled using NaHCO 3 /Na 2 CO 3 buffer at pH 8.9). Controls and samples included a phosphonate-based scale inhibitor program. The Controls had no additional corrosion inhibitor. Both Samples 1 and 2 included about 10 ppm bismuthiol. Corrosion rates were based on coupon weight after 7 days of exposure and measured in mils per year (“mpy”), as shown in Table I.
  • Linear polarization electrochemical experiments were performed in a 10 liter cell using galvanized metal surfaces of hot-dipped galvanized (“HDG”) rotating electrodes (H-controlled at pH 7.5).
  • the control and sample included a passivation step with 100 ppm of a phosphonate, phosphate, and polymer-based multi-functional water treatment program.
  • the following synthetic water chemistry including calcium chloride dihydrate, magnesium sulfate heptahydrate, and sodium bicarbonate (based on calculated values) was used: Ca 2+ : 150 to 170 ppm (as CaCO 3 ); Mg 2+ : 75 to 85 ppm (as CaCO 3 ); M-Alkalinity: 85 to 105 ppm (as CaCO 3 ); Cl ⁇ : 105 to 120 ppm (as Cl ⁇ ); and (SO 4 ) 2 ⁇ : 72 to 82 ppm (as (SO 4 ) 2 ⁇ ).
  • the control and sample also included a second step, where the passivated electrodes were exposed to a more extreme corrosive environment, as in Example I above. Initial corrosion rate (from 0 to 24 hours) followed by a longer duration corrosion rate (24 to 72 hours) were measured in mpy. Table II describes the initial and longer duration corrosion rates.

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US11/612,901 US20080145271A1 (en) 2006-12-19 2006-12-19 Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces
KR1020097014944A KR20090101249A (ko) 2006-12-19 2007-12-14 아연도금된 금속 표면에 황화물계 부식 억제제를 사용하는 방법
AU2007337103A AU2007337103A1 (en) 2006-12-19 2007-12-14 Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces
BRPI0719406A BRPI0719406A8 (pt) 2006-12-19 2007-12-14 Método de inibição da corrosão em uma superfície de metal galvanizada
CN2007800468081A CN101568430B (zh) 2006-12-19 2007-12-14 将基于硫的腐蚀抑制剂用于镀锌的金属表面的方法
RU2009122438/05A RU2009122438A (ru) 2006-12-19 2007-12-14 Способ применения ингибиторов коррозии на основе серы для оцинкованных металлических поверхностей
SG2011093358A SG177897A1 (en) 2006-12-19 2007-12-14 Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces
JP2009543098A JP2010513724A (ja) 2006-12-19 2007-12-14 亜鉛メッキした金属面に対して硫黄ベースの腐食防止剤を使用する方法
MX2009006515A MX2009006515A (es) 2006-12-19 2007-12-14 Metodo para usar anticorrosivos a base de azufre para superficies de metal galvanizadas.
EP07869274A EP2091727A4 (en) 2006-12-19 2007-12-14 SULFUR CORROSION INHIBITORS FOR GALVANIZED METAL SURFACES
PCT/US2007/087531 WO2008079734A1 (en) 2006-12-19 2007-12-14 Method of using sulfur-based corrosion inhibitors for galvanized metal surfaces
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US9764093B2 (en) 2012-11-30 2017-09-19 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
US11406765B2 (en) 2012-11-30 2022-08-09 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
US10201660B2 (en) 2012-11-30 2019-02-12 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition on medical syringes, cartridges, and the like
US9662450B2 (en) 2013-03-01 2017-05-30 Sio2 Medical Products, Inc. Plasma or CVD pre-treatment for lubricated pharmaceutical package, coating process and apparatus
US11344473B2 (en) 2013-03-11 2022-05-31 SiO2Medical Products, Inc. Coated packaging
US9554968B2 (en) 2013-03-11 2017-01-31 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging
US11298293B2 (en) 2013-03-11 2022-04-12 Sio2 Medical Products, Inc. PECVD coated pharmaceutical packaging
US10912714B2 (en) 2013-03-11 2021-02-09 Sio2 Medical Products, Inc. PECVD coated pharmaceutical packaging
US10537494B2 (en) 2013-03-11 2020-01-21 Sio2 Medical Products, Inc. Trilayer coated blood collection tube with low oxygen transmission rate
US11684546B2 (en) 2013-03-11 2023-06-27 Sio2 Medical Products, Inc. PECVD coated pharmaceutical packaging
US10016338B2 (en) 2013-03-11 2018-07-10 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging
US9937099B2 (en) 2013-03-11 2018-04-10 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging with low oxygen transmission rate
US9863042B2 (en) 2013-03-15 2018-01-09 Sio2 Medical Products, Inc. PECVD lubricity vessel coating, coating process and apparatus providing different power levels in two phases
US11066745B2 (en) 2014-03-28 2021-07-20 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
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