WO2002043812A2 - Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition - Google Patents
Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition Download PDFInfo
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- WO2002043812A2 WO2002043812A2 PCT/US2001/030291 US0130291W WO0243812A2 WO 2002043812 A2 WO2002043812 A2 WO 2002043812A2 US 0130291 W US0130291 W US 0130291W WO 0243812 A2 WO0243812 A2 WO 0243812A2
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- ferric
- ferrous
- corrosion
- corrosion inhibiting
- insoluble
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- 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
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0035—Aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/27—Dispersions, e.g. suspensions or emulsions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- 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
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- 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
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- 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
- C23F11/188—Mixtures of inorganic inhibitors containing phosphates
Definitions
- the present invention relates to corrosion-inhibited fire retardant compositions. More specifically, the invention is directed to ammonium polyphosphate concentrates and other solutions containing suspended and/or soluble iron compounds having a reduced corrosion tendency.
- Fire retardant compositions designed for managing and controlling wildland fires are of two general types, dry-powdered concentrates that are mixed with water prior to use and concentrated liquids, which are diluted with water at the time of transfer to an application vehicle. Fire retardant concentrates that are supplied in the liquid form are preferred by some because they can be simply and easily diluted to end-use strength with little mixing hardware and manpower.
- Ammonium polyphosphate liquids have been used as aerially applied fire- retardants. These liquids have certain advantages in comparison to other fire- suppressing compositions since they can be transported and stored prior to use in the liquid form rather than being mixed from dry ingredients.
- concentrated liquid fire retardants and solutions prepared therefrom are extremely corrosive to aluminum and brass and mildly corrosive to other materials of construction used in handling, storage and application equipment.
- all metals include alloys thereof. Accordingly, aluminum includes aluminum 2024T3, 6061 and 7074, steel includes 1010 and 4130 steel and brass includes yellow and naval brass. Since wildland fire retardants are most frequently transported to the fire and applied aerially, it is imperative that corrosive damage to the materials of construction of fixed-wing aircraft and helicopters be minimized.
- the Forest Service Specifications identify the maximum amount of corrosion acceptable when both the retardant concentrate and its diluted solutions are exposed to each metal indicated above at temperatures of 70° Fahrenheit (“F") and 120°F in both totally and partially immersed configurations.
- the maximum allowable corrosivity of aerially applied fire retardant diluted solutions to aluminum is 2.0 mils per year (“mpy”) and the maximum corrosivity to brass and steel is 2.0 mpy when partially immersed and 5.0 when tested in the partially immersed condition. In the partially immersed configurations, one-half of the coupon is within the solution and one-half is exposed to the vapors in the air space over the solution.
- sodium ferrocyanide was incorporated into the corrosive compositions.
- Sodium ferrocyanide has proven to be an effective corrosion inhibitor in fire retardant compositions containing ammonium polyphosphate fertilizer solutions.
- sodium ferrocyanide is effective as a corrosion inhibitor, several disadvantages of its use make its incorporation in wildland fire retardant compositions unacceptable. Specifically, the environmental and toxicologjcal safety of ferro(i) cyanides is, at best, questionable.
- ferro(i)cyanide radical When exposed to acidic conditions and/or ultraviolet radiation from natural sunlight, the ferro(i)cyanide radical readily degrades releasing free iron and cyanide and/or hydrogen cyanide, which are toxic to humans, animals and aquatic life. Further, free iron emanating either from decomposition of a portion of the ferro(i)cyanide radical, or introduced from other components or impurities within the composition, will subsequently react with remaining non-decomposed ferro(i)cyanide to form ferricyanide (“TumbulTs Blue”) or ferrocyanide (“Prussian Blue”), which emit a persistent blue-black coloration, staining all that they contact.
- a corrosion-inhibited fire retardant composition including at least one fire retardant composition that includes at least one ammonium polyphosphate, at least one suspending agent and a corrosion inhibiting system that includes at least one corrosion inhibiting compound selected from a group of compounds consisting of azoles, insoluble ferric pyrophosphate, soluble ferric pyrophosphate (mixture or blend of sodium citrate and insoluble ferric pyrophosphate), ferrous oxalate, ferric citrate, ferrous sulfate, ferric ammonium citrate, insoluble ferric orthophosphate, soluble ferric orthophosphate, ferric ammonium oxalate, ferric ammonium sulfate, ferric bromide, ferric sodium oxalate, ferric stearate, ferric sulfate, ferrous acetate, ferrous ammonium sulfate, ferrous bromide, ferrous gluconate, ferrous iodide,
- the present invention provides a method of preparing the above-described corrosion-inhibited fire retardant compositions of the invention that includes the steps of forming an intermediate concentrate composition suitable for transportation and storage that includes the above-described corrosion-inhibited fire retardant composition of the invention,- wherein the corrosion inhibiting system is present in a minor amount effective to substantially reduce the corrosivity of the fire retardant composition of the invention and diluting the intermediate concentrate with water to form the corrosion-inhibited fire retardant compositions of the invention.
- the present invention provides a method of suppressing wildland fires that includes aerially applying to wildland vegetation, ahead of wildland fire, a fire suppressing composition that is comprised of water and the above- described corrosion-inhibited fire-retardant compositions of the invention.
- the present invention provides a method of inhibiting corrosion that includes providing a corrodible material and contacting it with an effective amount of the above-described corrosion inhibiting system of the invention.
- the present invention provides a corrosion-inhibited agricultural plant nutrient that includes at least one agricultural plant nutrient and the above-described corrosion inhibiting system of the invention.
- the corrosion inhibiting system is present in a minor amount effective to substantially reduce the corrosiveness of the agricultural plant nutrient.
- a fire- retardant composition can be prepared that has a reduced tendency to corrode various metals, including aluminum, that is superior to known fire retardants in toxicological and environmental safety.
- the corrosion-inhibited fire retardant of the invention includes at least one fire retardant composition comprised of at least one ammonium polyphosphate, at least one suspending agent and a corrosion inhibiting system comprised of at least one corrosion inhibiting compound selected from a group of corrosion inhibiting compounds consisting of azoles, insoluble ferric pyrophosphate, soluble ferric pyrophosphate, ferrous oxalate, ferric citrate, ferrous sulfate, ferric ammonium citrate, insoluble ferric orthophosphate, soluble ferric orthophosphate, ferric ammonium oxalate, ferric ammonium sulfate, ferric bromide, ferric sodium oxalate, ferric stearate, ferric sulfate, ferrous acetate, ferrous ammonium sulfate, ferrous bromide, ferrous gluconate, ferrous iodide, ferric acetate, ferric fluoroborate, ferric hydroxide, ferrous fumarate, ferr
- the corrosion-inhibited fire retardant compositions of the invention is prepared by forming an intermediate concentrate composition comprising at least one fire retardant composition comprised of at least one ammonium polyphosphate, at least one suspending agent, and the above-described corrosion inhibiting system.
- the intermediate concentrate is then diluted with water to form the corrosion-inhibited fire retardant composition of the invention.
- the corrosion inhibiting system is present in the corrosion- inhibited fire retardant of the invention in a minor amount effective to substantially reduce the corrosiveness of the fire retardant composition.
- the corrosion-inhibited fire retardant of the invention includes a fire retardant comprised of at least one ammonium polyphosphate.
- Ammonium polyphosphate is also referred to as polyammonium phosphate and may include both ortho- and polyphosphate, other ammonium phosphates such as pyro- and metaphosphates, the alkali metal equivalents thereof, as well as a blend of phosphate polymers.
- ammonium polyphosphate solutions that are used as agricultural fertilizer and wildland (vegetative) fire retardants are manufactured by neutralizing aqueous solutions of wet-process phosphoric acid, generally containing about 68% to about 74% phosphorus pentoxide with anhydrous ammonia in such a manner that both high temperature and pressure are experienced.
- wet-process phosphoric acid generally containing about 68% to about 74% phosphorus pentoxide with anhydrous ammonia in such a manner that both high temperature and pressure are experienced.
- a portion of the impure orthophosphoric acid polymerizes or condenses, resulting in the formation of pyrophosphate, short chain polyphosphates and, in most instances, small amounts of cyclic or metaphosphates. That portion of the acid which does not polymerize, of course, remains as orthophosphoric acid.
- ammonium polyphosphate concentrates and their solutions may vary in species composition as received and as time progresses during their subsequent storage.
- These liquid concentrates may additionally contain small amounts of diammonium sulfate and a host of metal and alkali-metal impurities.
- the quantity and quality of these impurities vary with the composition of the phosphate ore, the utilized process and the extent of purification that is conducted during manufacture of the wet-process phosphoric acid. Since these solutions are manufactured primarily as nutrients, the quality control parameters of greatest interest are the percentages of their contained nutrients - nitrogen and phosphorus - and the clarity, stability and color of the solution rather than purity per se.
- the corrosion inhibiting system of the invention is comprised of at least one corrosion inhibiting compound selected from a group of corrosion inhibiting compounds consisting of azoles, insoluble ferric pyrophosphate, soluble ferric pyrophosphate, ferrous oxalate, ferric citrate, ferrous sulfate, ferric ammonium citrate, insoluble ferric orthophosphate, soluble ferric orthophosphate, ferric ammonium oxalate, ferric ammonium sulfate, ferric bromide, ferric sodium oxalate, ferric stearate, ferric sulfate, ferrous acetate, ferrous ammonium sulfate, ferrous bromide, ferrous gluconate, ferrous iodide, ferric acetate, ferric fluoroborate, ferric hydroxide, ferric oleate, ferrous fumarate, ferrous oxalate, ferrous oxide, ferric lactate, ferric resinate, and any combination thereof.
- a minor amount of the corrosion inhibiting system of the invention effective to substantially reduce the corrosiveness of the fire retardant composition is included in the corrosion-inhibited fire retardant composition of the invention.
- a minor effective amount of the corrosion inhibiting system is that amount which substantially reduces the corrosivity of the fire retardant.
- what constitutes a substantial reduction in corrosivity is largely dependent on the specific fire retardant used in the fire retardant composition of the invention, as well as the specific composition of the corrosion inhibiting system and can be readily determined without undue experimentation.
- the corrosion inhibiting system of the invention is present in a minor amount effective in the corrosion-inhibited fire retardant composition, in concentrate, to obtain at least one of a maximum corrosivity of aluminum to 5.0 mpy, yellow brass to 5.0 mpy, and steel to 5.0 mpy, as determined by the "Uniform Corrosion Test" set forth in Section 4.5.6.1.2 of "Specification 5100-304b (July 1999) Superseding Specification 5100-304a (February 1986),” entitled “Specification For Long Term Retardant, Wildland Fire, Aircraft or Ground Application,” issued by the USDA.
- the corrosion inhibiting system of the invention comprises in the range of about .01% to about 10.0% of the total corrosion-inhibited fire retardant. In another specific embodiment, the corrosion inhibiting system of the invention comprises in the range of about 0.3% to about 6.0% of the total corrosion- inhibited fire retardant. In yet another specific embodiment, the corrosion inhibiting system of the invention comprises in the range of about 0.6% to about 5.0% of the total corrosion-inhibited fire retardant.
- the corrosion-inhibited compositions of the invention Prior to use, and in one embodiment of the invention, are blended with water to form dilute solutions containing the amount of phosphorus pentoxide required to achieve the maximum amount of vegetation coverage at an application rate sufficient to reduce the flammability of the vegetative fuels to the desired level.
- the water used in the composition of the invention may be tap water or water from other convenient water sources.
- compositions of the invention are blended with water to form dilute solutions containing the amount of phosphorus pentoxide required to meet USDA, Forest Service Specification fire-retardant effectiveness requirements. This concentration, which is determined via combustion-retarding effectiveness testing described in USDA, Forest Service Specification 5100-304b,
- Combustion Retarding Effectiveness Test will generally depend on the percentage of phosphorus pentoxide present in the concentrated composition and the extent of its availability for retarding reactions.
- the corrosion-inhibited fire retardant composition of the invention is typically diluted to an amount effective to achieve maximum coverage of vegetation at an application rate sufficient to reduce the flammable fuels to a desired level.
- the minium USDA, Forest Service Specifications, for combustion retarding effectiveness, as specified in Specification 5100-304b, is generally obtained when the corrosion-inhibited fire retardant concentrate of the invention is diluted with about 1 to about 8 volumes of water.
- the corrosion-inhibited fire retardant compositions of the invention are diluted with water and applied on threatened vegetation, ahead of approaching wildland fire.
- Ammonia from both the ammonium phosphate and the ammonium sulfate are liberated at temperatures below the ignition temperature of the fuel.
- the phosphoric and sulfuric acids are both initially effective fire retarding acids.
- the phosphoric acid will remain present and effective with the vegetative fuel until temperatures exceed 600°C.
- the boiling point of sulfuric acid is much lower and the amount present will decrease as fuel temperature increases.
- at least a portion of the sulfuric acid is still present at the ignition temperature of the fuel.
- the resultant mineral acids subsequently react with the cellulosic components of vegetative fuels on which they are applied.
- the fire retardant compositions of the invention also contain suspending agents. Suspending agents effectively reduce the rate of separation and settling during long term storage. Thus, as one skilled in the art would appreciate, the amount of suspending agent depends upon its relative effectiveness per unit applied, the desired length of storage and the additional additives incorporated into the compositions of the invention.
- suspending agents useful in the compositions of the invention include colloidal clays, for example, Attapulgus, Fuller's earth, sepiolite, montomorillonite, and Kaolin clay.
- Attapulgus clay includes, but is not limited to attapulgite and palygorskite.
- Kaolin clay includes, but is not limited to Kaolinite, [Al 2 Si 2 O7-2(H 2 O)] and [Al 2 O 3 -2SiO 2 -2(H 2 O)].
- the corrosion-inhibited fire retardant of the invention may contain or be mixed with other functional components such as coloring agents, surfactants, stabilizers, opacifying agents, other corrosion inhibitors, any combination thereof, or with other functional components.
- the corrosion-inhibited fire retardant composition of the invention includes at least one highly colored pigment.
- the colored pigment is incorporated to assist in the visual identification of treated and untreated vegetation.
- Suitable highly colored pigments include iron oxide, which produces many colors like brown and red, titanium dioxide pigments, which produce a white color, or an ultra-violet sensitive dye dispersed in biodegradable plastic.
- iron oxide which produces many colors like brown and red
- titanium dioxide pigments which produce a white color
- ultra-violet sensitive dye dispersed in biodegradable plastic for certain uses, like along roadsides or in parks, it may be desirable to exclude any colorant from the mixture. Accordingly, as one skilled in the art would appreciate, the amount of colorant or pigment incorporated into the compositions of the invention depends on the degree of the dilution and visibility contemplated by the user.
- the present invention includes at least one of red iron oxide or brown iron oxide, or a combination thereof.
- the present invention includes a fugitive coloring agent, whose color fades upon exposure to the elements.
- the present invention includes opacifying pigments, which are generally not highly colored, but have the ability to cover and hide that on which it is deposited so that a highly colored pigment becomes more visible.
- Surfactants may also be added to increase visibility, through the generation of a foam, and to improve penetration of the retardant solution into porous fuels. Accordingly, as one skilled in the art would appreciate, the amount and type of surfactant incorporated into the compositions of the invention depends on the degree of the dilution and visibility contemplated by the user.
- compositions of the invention comprise at least one azole.
- an azole is any of a group of chemical compounds with a five-membered ring containing one or more nitrogen atoms.
- Azoles suitable for use in the corrosion-inhibited fire retardants of the invention include, but are not limited to tolytriazole, benzotriazole, mercaptobenzothiazole, dimercaptomthiadiazole, l,2 benzisothiazoline-3-l, 2-benzimidazolone, 4,5,6,7- tetrahydrobenzotriazole, tolylimidazole, 2-(5-ethyl-2-pyridyl) benzimidazole, phthalimide, any alkali metal salts thereof and combinations thereof.
- the corrosion-inhibited fire retardant concentrates of the invention include at least one azole, present in a minor amount effective to obtain a corrosivity of yellow brass to a maximum of 5.0 mpy, as determined by the "Uniform Corrosion Test" set forth in Section 4.5.6.1 of "Specification 5100-304b (July 1999) Superseding Specification 5100-304a (February
- the fire retardant concentrate of the invention comprises in the range of about .01% to about 1.0% tolytriazole.
- the composition of the invention includes in the range of about 0.2% to about 0.6% tolytriazole.
- the composition of the invention includes in the range of about 0.3% to about 0.5% tolytriazole.
- the above described corrosion-inhibited fire retardant composition is used as an agricultural plant nutrient.
- the corrosion inhibiting system is present in a minor effective amount to substantially reduce corrosiveness of the agricultural plant nutrient.
- the effective amount varies depending on the specific plant nutrient formulated. However, one skilled in the art can determine the amount without undue experimentation.
- a method of inhibiting corrosion using the above-described corrosion inhibiting system of the invention is also provided.
- a corrodible material is provided and contacted with at least one suspending agent, and an effective amount of the corrosion inhibiting system of the invention to substantially reduce the corrosiveness of the agricultural plant nutrient.
- any corrodible material may be used according to the method of inhibiting corrosion of the invention.
- the corrodible material is selected from a group of corrodible materials consisting of steel, brass, aluminum and any alloy thereof.
- the corrosion inhibiting system Prior to use, and in one embodiment of the invention, is blended with water prior to or during contact with the corrodible material.
- the water used in the composition of the invention may be tap water or water from other convenient water sources.
- the corrosion inhibiting system includes at least one additive selected from a group of additives including coloring agents, surfactants, opacifying pigments, stabilizers, corrosion inhibitors and any combination thereof.
- additives including coloring agents, surfactants, opacifying pigments, stabilizers, corrosion inhibitors and any combination thereof.
- Table 1 illustrates the corrosion characteristics of neat, unadulterated fertilizer grade 10-34-0 and 11-37-0 ammonium polyphosphate liquid concentrates obtained from three different sources. All of the samples are either 10-34-0 or 11-37-0, as received with no additions. The corrosivity of the samples were expressed in mils of metal loss on exposed metal surface extrapolated from 90 to 365 days (mpy) and ascertained using the aforementioned USDA, Forest Service Specifications for determining corrosivity. Both the concentrated retardant and its diluted solutions were tested at each temperature and condition indicated.
- the diluted solutions were prepared by admixing four to five volumes of water with one volume of the concentrated solution. Thus, the diluted solutions were in the range of between about 15% to about 20% by volume of the concentrate.
- Forest Service Specifications for corrosion testing of fire retardants a one inch wide, four inches long, one-eight inch thick coupon of the aluminum was obtained from a standard source. The coupon is cleaned, dried and weighed according to standard USDA, Forest Service Specifications and suspended in a one quart, straight sided jar filled either 50% (partially) or 100% (totally) full using a piece of nylon string. When suspended in a partially full jar, the coupon was 50%
- the calculated weight loss and density of the metal coupon were used to extrapolate to mils (0.001 inches) of aluminum that would be lost during a one-year period at the test condition.
- the corrosion rate of both the partially and totally immersed coupons were calculated using the total surface area of the coupon. The samples at each condition were then averaged and reported as the corrosion rate. The results are shown in Table 1.
- Tables 3a and 3b illustrate the relative effectiveness of a number of corrosion inhibitor systems containing water soluble and water insoluble sources of iron, and mixtures thereof, in several sources and types of ammonium polyphosphate concentrates and their diluted solutions.
- the samples were prepared by admixing either 10-34-0 or 11-37-0 type ammonium polyphosphate solutions from various sources with varying concentrations of insoluble red iron oxide or brown iron oxide additives and Attapulgus clay additives and varying the concentrations of other iron containing additives, as indicated.
- Samples 1, 2, 3 and 4 are 10-34-0 ammonium polyphosphate concentrates from different sources. The solutions were subjected to high shear mixing in order to activate or hydrate the clay. Each concentrate and its diluted solution was tested for aluminum corrosivity in accordance with the Forest Service Specification protocols. The results are shown in Tables 3a and 3b.
- T ese compositions contain 0305% toylt ⁇ azole for brass corrosion inhibition
- compositions contain u ⁇ u ->7i- toiyit ⁇ azoie 5 corrosion inhibition D type Ammomum Polyphosphate Sample
- line 1 illustrates the average corrosion characteristics of neat concentrate and dilute solutions from Sample 1, taken from Table 1
- line 2 illustrates the corrosion of the concentrate and diluted solutions when 1.2% iron oxide and 1.4% Attapulgus clay, with the exception of the formulations on line 9 which contained 0.7% Attapulgus clay and the formulation on line 11, which contained 2.8% Attapulgus clay, was mixed with the neat concentrate solution, see Table 2.
- Samples 1-4 were 10-34-0 type ammonium polyphosphate samples obtained from various sources.
- Samples 5-7 were 11-37-0 type ammonium polyphosphate samples obtained from various sources.
- Lines 7 through 12 illustrate the effectiveness of corrosion inhibiting systems similar to those described in the preceding paragraph, except red iron oxide is substituted for brown iron oxide.
- red iron oxide is effective in reducing the aluminum corrosion of the concentrated and diluted ammonium polyphosphate although perhaps not quite as effective as the brown iron oxide.
- Lines 13-22 illustrate the corrosion inhibiting effectiveness of mixtures of insoluble iron oxide and soluble ferric citrate.
- ferric citrate was an equally effective substitute for soluble ferric pyrophosphate.
- results indicate that a mixture of brown iron oxide and 3.0% soluble ferric citrate was capable of reducing the corrosivity of the ammonium polyphosphate samples to within acceptable levels for compliance with Forest Service Specifications for corrosivity of fire retardants.
- Lines 23 and 24 illustrate the use of ferric ammonium citrate as a substitute for ferric citrate.
- Lines 27 through 38 illustrate the effectiveness of systems in which only uncolored, soluble and insoluble iron containing compounds are used rather than the relatively highly colored persistent iron oxides. This is important where true fugitive retardants are desired, whereby the color gradually fades when exposed to natural sunlight and disappears so as not to permanently stain that on which it is applied.
- Lines 26 through 38 illustrate the effectiveness of mixtures of soluble and insoluble ferric pyrophosphate.
- Lines 45 through 54 illustrate the aluminum corrosion inhibiting effectiveness of the subject compounds when used in various sources of 11-37-0 type ammonium polyphosphate concentrate and their diluted solutions.
- Example 4 illustrates the effectiveness of water-soluble ferric pyrophosphate, ferric citrate and ferrous sulfate as aluminum corrosion inhibitors in ammonium polyphosphate solutions.
- the indicated soluble iron compounds and 1.4% Attapulgus clay were admixed with neat ammonium polyphosphate. Aliquots were subsequently drawn from the concentrate and diluted with the prescribed amount of water. The aluminum corrosivity of both the concentrated fire retardants and their diluted solutions was determined in accordance with the aforementioned Forest Service Specifications. The results of this testing is shown in Table 4. 41482/28665
- Table 5 illustrates the effectiveness of water insoluble ferric orthophosphate, ferric pyrophosphate and ferrous oxalate as aluminum corrosion inhibitors in ammonium polyphosphate concentrates and their diluted solutions. 1.4% Attapulgus clay was mixed with the concentrated ammonium polyphosphate, with the exception of Samples 6 and 7 which contained 0.7% and 2.8% Attapulgus clay, respectively.
- Samples 13, 18 and 24 contained, also, an insoluble iron oxide as a solution colorant.
- insoluble ferric pyrophosphate as an aluminum corrosion inhibitor for concentrated ammonium polyphosphate and its solutions. It was shown to be superior to red iron oxide when compared on an equal ferric iron level. Accordingly, the insoluble ferric pyrophosphate would be preferred in many applications since it is not highly colored like the conventional iron oxides, which result in highly visible and persistent discoloration of that on which it is applied. Consequently, inhibitor systems containing these components would be suitable for use in fugitive colored fire retardant formulations.
- Lines 15-19 illustrate the further reduction in aluminum corrosion, which was obtained by combining iron oxide and ferric pyrophosphate in the same corrosion inhibiting system. The results indicated that several of these formulations met the
- Line 25 in Table 5 illustrates the aluminum corrosion inhibiting effectiveness of small amounts of ferrous (Fell) iron when incorporated in ammonium polyphosphate concentrates and their diluted solutions.
- Example 6 illustrates the effectiveness of azoles as yellow brass corrosion inhibitors in concentrated ammonium polyphosphate based fire retardant formulations and in their diluted solutions. Each sample was prepared by mixing
- T and P refer to total of partial immersion of the metal coupon in the retardant solution during storage. from a 50% aqueous solution of sodium tolyltriazole.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01985472A EP1341586B9 (en) | 2000-11-28 | 2001-09-27 | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
CA002429806A CA2429806C (en) | 2000-11-28 | 2001-09-27 | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
AU2002235123A AU2002235123B2 (en) | 2000-11-28 | 2001-09-27 | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
AU3512302A AU3512302A (en) | 2000-11-28 | 2001-09-27 | Fire retardant compositions containing ammonium polyphosphate and iron additivesfor corrosion inhibition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/723,567 | 2000-11-28 | ||
US09/723,567 US6802994B1 (en) | 2000-11-28 | 2000-11-28 | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
Publications (2)
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WO2002043812A2 true WO2002043812A2 (en) | 2002-06-06 |
WO2002043812A3 WO2002043812A3 (en) | 2003-03-06 |
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PCT/US2001/030291 WO2002043812A2 (en) | 2000-11-28 | 2001-09-27 | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
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US (1) | US6802994B1 (en) |
EP (2) | EP1341586B9 (en) |
AU (2) | AU2002235123B2 (en) |
CA (1) | CA2429806C (en) |
ES (1) | ES2280414T4 (en) |
WO (1) | WO2002043812A2 (en) |
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Also Published As
Publication number | Publication date |
---|---|
AU2002235123B2 (en) | 2005-09-22 |
CA2429806C (en) | 2009-09-01 |
AU3512302A (en) | 2002-06-11 |
EP1341586A2 (en) | 2003-09-10 |
ES2280414T3 (en) | 2007-09-16 |
US6802994B1 (en) | 2004-10-12 |
EP1341586B1 (en) | 2007-03-28 |
EP1341586B9 (en) | 2007-11-21 |
EP2280055B1 (en) | 2013-04-17 |
WO2002043812A3 (en) | 2003-03-06 |
ES2280414T4 (en) | 2008-03-16 |
CA2429806A1 (en) | 2002-06-06 |
EP2280055A1 (en) | 2011-02-02 |
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