CA2154122C - Fugitive colour fire retardant composition for aerial application - Google Patents
Fugitive colour fire retardant composition for aerial application Download PDFInfo
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- CA2154122C CA2154122C CA002154122A CA2154122A CA2154122C CA 2154122 C CA2154122 C CA 2154122C CA 002154122 A CA002154122 A CA 002154122A CA 2154122 A CA2154122 A CA 2154122A CA 2154122 C CA2154122 C CA 2154122C
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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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- 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
- A62D1/0007—Solid extinguishing substances
- A62D1/0014—Powders; Granules
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- Business, Economics & Management (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
In a fugitive colour fire retardant composition, the colourant initially colours the composition to a hue which contrasts with the hue of ground vegetation. A non-fugitive component is included in the colourant, in an amount which is sufficient to provide improved aerial visibility when the composition is first aerially applied to the vegetation.
However, the amount of non-fugitive pigment is less than an amount which would prevent the composition from fading after application to an acceptable hue.
However, the amount of non-fugitive pigment is less than an amount which would prevent the composition from fading after application to an acceptable hue.
Description
FUGITIVE COLOUR FIRE RETARDANT COMPOSITION FOR AERIAL
APPLICATION
This invention relates to fire retardant compositions which are specially adapted for aerial application, to combat or prevent the spread of wildfires. More particularly, the invention concerns a fugitive colour fire retardant composition, having improved aerial visibility after it is first aerially applied to ground vegetation, but which fades over time and under ambient conditions to another colour (hue).
In the early 1960's, aerial application of fire retardant compositions to prevent or re~rd the spread of forest fires, range fires, etc., became very widespread.
Typically, these fire retardant compositions contained an electrolytic fire-suppressing salt, e.g., ammonium phosphate, ammonium sulphate, and the like, and also included other components, e.g., viscosity modifiers, corrosion inhibitors and colouring agents, e.g., pigments or dyes. Typical fire retardant compositions of the type described above are disclosed in U.S. Patent No. 3,196,10$, to Nelson and U.S. Patents Nos.
3,257,316 and 3,309,324 to Langouth, et al. These compositions generally consisted of an aqueous slurry or solution of a fire-suppressing salt, e, g. , ammonium phosphate or ammonium sulphate and a thickening agent, e.g., attapulgite clay, guar gum or the like.
Colouring agents, e.g., red iron oxide, were included to improve the visibility of the material after it was dropped. More recently, ammonium polyphosphate liquids, containing colouring agents and corrosion inhibitors, have been widely employed. Such liquid polyphosphate fire retardant compositions are disclosed in U.S. Patent No. 3,370,890 to Nelson and U.S. Patent No. 3,960,735 to Lacey.
Fire retardant compositions containing other thickeners, stabilizers and the like are disclosed in the following patents: U.S. Patent No. 4,822,524 to Strickland, U.S.
Patent No. 3,634,234 to Morganthaler, U.S. Patent No. 4,606,831 to Kegler, et al., U.S. Patent No. 4,447.,336 to Vandersall, U.S. Patent No. 4,447,338 to Adl, et al., and U.S. Patent Nos. 4,83!x,065 and 4,983,326 to Vandersall.
Fire retardant compositions are typically manufactured as dry or liquid "concentrates". These concentrates are shipped and stored in such form until just prior to use. Then, the concentrate is mixed with water to form the final diluted "mixed" fire retardant composition. This mixed retardant composition is then pumped in the tanker aircraft for transport, and dropping at, the wildfire site. In some instances, a dry concentrate is first muted with an initial quantity of water to provide an intermediate liquid concentrate and this intermediate liquid concentrate is then further diluted just before use to the final diluted mixed form.
The active fine-suppressing components employed in such fire retardant compositions include any of the well-known electrolytic fire-suppressing salts, e.g. , those which are disclosed in i1. S. Patent No. 3,196,108 to Nelson, as well as the more recently employed liquid ammonium polyphosphate materials, as disclosed in U.S. Patent No.
APPLICATION
This invention relates to fire retardant compositions which are specially adapted for aerial application, to combat or prevent the spread of wildfires. More particularly, the invention concerns a fugitive colour fire retardant composition, having improved aerial visibility after it is first aerially applied to ground vegetation, but which fades over time and under ambient conditions to another colour (hue).
In the early 1960's, aerial application of fire retardant compositions to prevent or re~rd the spread of forest fires, range fires, etc., became very widespread.
Typically, these fire retardant compositions contained an electrolytic fire-suppressing salt, e.g., ammonium phosphate, ammonium sulphate, and the like, and also included other components, e.g., viscosity modifiers, corrosion inhibitors and colouring agents, e.g., pigments or dyes. Typical fire retardant compositions of the type described above are disclosed in U.S. Patent No. 3,196,10$, to Nelson and U.S. Patents Nos.
3,257,316 and 3,309,324 to Langouth, et al. These compositions generally consisted of an aqueous slurry or solution of a fire-suppressing salt, e, g. , ammonium phosphate or ammonium sulphate and a thickening agent, e.g., attapulgite clay, guar gum or the like.
Colouring agents, e.g., red iron oxide, were included to improve the visibility of the material after it was dropped. More recently, ammonium polyphosphate liquids, containing colouring agents and corrosion inhibitors, have been widely employed. Such liquid polyphosphate fire retardant compositions are disclosed in U.S. Patent No. 3,370,890 to Nelson and U.S. Patent No. 3,960,735 to Lacey.
Fire retardant compositions containing other thickeners, stabilizers and the like are disclosed in the following patents: U.S. Patent No. 4,822,524 to Strickland, U.S.
Patent No. 3,634,234 to Morganthaler, U.S. Patent No. 4,606,831 to Kegler, et al., U.S. Patent No. 4,447.,336 to Vandersall, U.S. Patent No. 4,447,338 to Adl, et al., and U.S. Patent Nos. 4,83!x,065 and 4,983,326 to Vandersall.
Fire retardant compositions are typically manufactured as dry or liquid "concentrates". These concentrates are shipped and stored in such form until just prior to use. Then, the concentrate is mixed with water to form the final diluted "mixed" fire retardant composition. This mixed retardant composition is then pumped in the tanker aircraft for transport, and dropping at, the wildfire site. In some instances, a dry concentrate is first muted with an initial quantity of water to provide an intermediate liquid concentrate and this intermediate liquid concentrate is then further diluted just before use to the final diluted mixed form.
The active fine-suppressing components employed in such fire retardant compositions include any of the well-known electrolytic fire-suppressing salts, e.g. , those which are disclosed in i1. S. Patent No. 3,196,108 to Nelson, as well as the more recently employed liquid ammonium polyphosphate materials, as disclosed in U.S. Patent No.
3,960,735 to Lacey, ammonium sulphate, as disclosed in U.S. Patent No.
4,176,071 to Crouch, and mixtures of these salts with themselves and with other salts.
In general, the active fire retardant components are compounds or a mixture of compounds that degrafe or decompose at temperatures which are below the ignition temperature of the fuels to be protected (e.g., cellulose), thereby releasing a mineral acid, e.g., phosphoric acid or sulphuric acid. Among the various fire retardants typically used in fire retardant mixtures and which might be used in the compositions of aspects of this invention are rnonoammonium orthophosphate, diammonium orthophosphate, monoammonium pyrophosphate, diammonium pyrophosphate, triammonium pyrophosphate, tetraammonium pyrophosphate, ammonium polyphosphate, substituted ammonium polyphosphate, amide polyphosphate, melamine polyphosphate, ammonium-alkali metal mixed salts of orthophosphate, ammonium-alkali metal mixed salts of pyrophosphate, ammonium-alkalimetal mixed salts of polyphosphate, ammonium-alkaline earth metal mixed salts of orthophosphate, ammonium-alkaline earth metal mixed salts of pyrophosphate, ammonium-alkaline earth metal mixed salts of polyphosphate, ammonium sulphate, liquid ammonium polyphosphates and blends thereof. Some liquid ammonium polyphosphates may be too dilute in their commercial forms for application as fire retardants but, other retardants, e.g., those noted above, may be mixed with a liquid ammonium polyphosphate until a minimum acceptable concentration is obtained.
Ammonium polyphosphate is often called polyammonium phosphate, and commonly contains other ammonium phosphates, e.g., pyro- and metaphosphates, and the alkali metal equivalents thereof, as well as a blend of phosphate polymers. Such polyammonium phosphates are often referred to as 10-34-0, 11-37-0, 12-40-0, 13-or the like, where the first number indicates the percentage of nitrogen in the blend, the middle number indicates the percentage phosphate in the blend and the last number indicates the percentagc: potash in the blend.
The fire retardmt companents may also include thickening agents, which include standard thickeners, e. g:. , galactomannan guar gum compositions and derivatives thereof, attapulgite clay, carbo:Kymethylcellulose and derivatives thereof, and the like. The thickening agent is employed to maintain the viscosity of the diluted mixed fire retardant composition, for example, at between 50 centipoise and 2000 centipoise for aerial application. In addition, the fire retardant components, in the concentrate or in the final diluted mixed form, rnay also typically include various adjuvants, e.g., corrosion inhibitors, flow conditioners, spoilage inhibitors, stabilizers and the like, and carriers for these adjuvants, in accordance with art-recognized principles.
When such fire retardant compositions, in final diluted mixed form for aerial application, are applied by dropping from fixed-wing or helicopter aircraft, successive "drops" are often made by the aircraft to form a fire-fighting line. Under these circumstances, it is important for the pilot of the aircraft to be able to determine visually where the preceding loads were dropped, such that the pilot can drop the load from the aircraft to form a continuation of this line. Since the fire retardant components (described above) may be colourless or may be of colours which do not contrast well with the ground or vegetation, it has been common practice to mix colouring agents with the fire retardant composition components. Colouring agents are used to give the fire retardant compositions a colour (hue) which contrasts with the hue of the ground vegetation, thereby enhancing the ability of the aircraft pilot to determine where the last loads of fire retardants were dropped in constructing a fire-fighting line.
Prior art colouring agents have included pigments which are dispersible in the liquid fire retardant compositions or soluble therein, most commonly red iron oxide or various water-soluble dyes. Such colouring agents were remarkably effective in enhancing the aerial visibility of fire retardant compositions after they were applied. However, certain prior art colouring agents, especially red irow oxide, were very "colourfast" , such that the ground and structures (if any) to which the prior art fore retardant compositions were applied, remained permanently or semi-peruanently stained. Consequently, certain government fire-fighting agencies have, more recently, required that aerially-applied fire retardant compositions have so-called "fugitive" colouring agents, such that the colour of the compositions would fade over a short time, e.g., 30 days, to a colour which did not objectionably contrast with the ground and ground vegetation.
Several dyes and pigments (encapsulated dyes) have been identified which impart a distinctive hue to fire retardant compositions, which contrasts with ground vegetation, but which fade in a short time to a "neutral" colour, i.e., such that the fire retardant compositions exhibit the colour they would have exhibited without the addition of such fugitive agents. However, although the fire retardant compositions themselves might be brilliantly colours by fugitive agents, after first application it was often difficult to locate the fire retardant drop zone. It has been found that the reduced visibility of these highly coloured fugitive compositions is somewhat related to the viscosity of the fire retardant compositions themselves. Thus, more highly viscous fugitive compositions are somewhat easier to see on the vegetation, because they form a thicker coating.
However, even highly viscous fugitive colour compositions are sometimes difficult to visualize from an aircraft after dropping on various kinds of vegetation and under various lighting conditions.
It would be advantageous to provide fugitive colour fire retardant compositions which exhibit improved aerial visibility after dropping. It would also be advantageous to achieve this result in an economical manner and without using any materials which are toxic to humans, animals, to fish or to vegetation.
Briefly, a fugitive color liquid fire retardant composition has been discovered for aerial application to ground vegetation which achieves these objectives.
According to one aspect of the present invention there is provided a fugitive color liquid from retardant composition for aerial application to ground vegetation, said composition comprising: a) fire retardant components having a first hue, comprising a fire retardant salt; b)a colorant which initially colors said composition to a second hue which contrasts with the hue of said vegetation, said colorant comprising: i) a fugitive color component; ii) a non-fugitive component which is present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application; arid c) an aqueous carrier.
According to another aspect of the present invention there is provided a concentrate composition for preparing a fugitive color liquid fire retardant composition for aerial application to ground vegetation, by dilution thereof with an aqueous carrier, said concentrate composition comprising:
a) fire retardant components having a first hue, comprising a fire retardant salt; and b) a colorant which initially colors said composition to a second hue which contrast with the hue of said vegetation, said colorant comprising: i) a fugitive color component, and ii) a non-fugitive component present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application.
According to a further aspect of the present invention there is provided a fugitive color liquid fire retardant composition for aerial application to ground vegetation, said composition comprising: a) fare retardant components including a fire retardant salt; b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with normal vegetation or ground; and c) titanium dioxide, in an amount sufficient to improve the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to a neutral color which blends with normal vegetation or ground.
According to another aspect of the present invention there is provided a method for fighting wildfires comprising the steps of: applying a fire retardant composition to ground vegetation, which composition includes: a) fire retardant components including a fire retardant salt; b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with the vegetation or ground; and c) a non-fugitive color component insoluble in an aqueous carrier which improves the aerial visibility of said composition, and said non-fugitive color component provided in less than an amount which prevents said composition from fading to a neutral color which blends with the vegetation or ground.
By two variants of this second broad aspect of this invention, the concentrate composition is a dry composition, or is a liquid concentrate composition.
By a variant of these two broad aspects of this invention, the non-fugitive component is red iron oxide.
By a second variant of these two broad aspects of this invention, and/or the above variants thereof, the fire retardant salt comprises a liquid ammonium polyphosphate.
In other words, the compositions of aspects of this invention generally comprise fire retardant components, a colorant and a liquid carrier, a typically an aqueous carrier.
'The fire retardant components include a fire-suppressing salt and have a first hue. The colourant comprises a fugitive component and a non-fugitive component.
The colourant used in aspects of thus invention initially colours the fire retardant composition components to a second hue which contrasts with the hue of the ground vegetation. This may be due solely to the colour which is imparted by the fugitive component, or to the colour which is imparted by the combined fugitivelnon-fugitive components .
The non-fugitive component of the colourant of an aspect of this invention is ' present in an amount which is sufficient to improve the aerial visibility of the composition when it is first applied to the vegetation. However, the non-fugitive component is the composition of an aspect of this invention is present in less than an amount which prevents the composition froth thereafter fading to the first hue, i.e., the hue of the fire retardant composition components without the colourant.
According to another embodiment of a general aspect of this invention, a concentrate composition is provided for preparing the liquid composition described above by dilution thereof with the aqueous carrier. The concentrate composition of this aspect of this invention generally comprises the fire retardant components and the colourant.
In one embodiment, the concentrate is a dry composition. In another embodiment, the concentrate is a liquid which is suitable for later dilution with water to form the final mixed liquid fire retardant composition.
As used herein, the term "Errs retardant components" means all of the components of the composition except the "colourant" and the liquid carrier, if any. The fire retardant components will include a fire retardant salt and may optionally include (and usually will include) other common ingredients of fue retardant formulations, e.g., corrosion inhibitors, spoilage inhibitors, flow conditioners, anti-foaming agents, foaming agents, stability additives and thickening agents.
The term "coiourant" means a combination of at least two components, namely, a fugitive component and a non-fugitive component.
The "fugitive component" is a dye, or a dye which is dispersed in a matrix (i.e., a pigment), which fade, over time and under ambient field conditions to a colourless or less-highly-coloured hue. A number of such dyes and pigments are well-known in the art. For example, many water-soluble dyes fade rapidly and there are so-called fluorescent pigments (fluorescent dyes which are encapsulated in a resin integument) which are suspendible in the fire retardant compositions of aspects of this invention and which also fade rapidlw to provide the "fugitive" effect. Typical examples of prior art fugitive dyes and pigments include C.I. Basic Red I dye, 6BL dye, Basic Violet II dye, Basic Yellow 40 and encapsulated-dye pigments which are available commercially, e.g., the pigments known by the trade name of the AXTM series pigments, supplied by Day-Glo Color Corp., Cleveland, Ohio. At present, it is preferred to employ encapsulated-dye fugitive pigments v~rithout uv absorbers, rather than using water-soluble dyes because the encapsulated-dye pigments are less likely to stain.
The colourant is present in an amount which provides a colour ("second hue") to the composition which is different from the colour of the composition without the colourant ("first hue"). The second hue contrasts with the hue of the vegetation (normally green and/or brown). Advantageously, the second hue is red, orange or pink.
The colourant also includes a "non-fugitive" component, i.e., a component which is insoluble in the carrier liquid and which, if coloured, does not necessarily fade after aerial application of the fire retardant composition.
The non-fugitive component preferably has an index of refraction of at least 2Ø
For example, prior art: fire retardant compositions containing fugitive colourants and which also contain various clays and other insoluble materials, e.g., attapulgite clay, tricalcium phosphate, (c:omponents which have refractive indices below 2.0), did not have the improved aerial visibility which is exhibited by the compositions of aspects of the present invention unless the amounts of such lower-index materials are so large that the compositions are not "fugitive". To achieve improved aerial visibility, smaller quantities of non-fugitive compor,~ents can be employed if the refractive index is higher and larger quantities of lower-index materials are required to achieve desirable results.
g The non-fugitive component of an aspect of this invention is included in the colourant in an amount which is sufficient to provide improved aerial visibility of the composition when it is first aerially applied to the vegetation. However, the amount of the non-fugitive component in the fire retardant composition of an aspect of this invention is less than the amount which would prevent the fire retardant composition of an aspect of this invention from fading to the first hue after application.
The non-fugitive component is dispersible or suspendible in the final fire retardant composition of an aspect of this invention and in a liquid concentrate of an aspect of this invention of such composition. The dispersibility or suspendibility of such a component is primarily dependent upon particle size and particle size distribution and the nature of the other components which are present in the fire retardant composition of an aspect of this invention, e.g., thickeners, etc.
Also, the chemical structure and characteristics of the non-fugitive pigment in the fire retardant composition of an aspect of this invention must be compatible with the other components, espE:cially with the carrier liquid. It must be sufficiently chemically-inert that it does not lose its functional capability when combined with the other components of the fire: retardant composition of an aspect of this invention.
It should also be non-toxic, and, if coloured, should not undesirably affect the hue established by the fugitive component: of an aspect of this invention.
For example, in a presently preferred practice of aspects of this invention, red iron oxide pigments are employed as the non-fugitive component. Yellow iron oxide pigments and white pigments, e. g. , titanium dioxide can also be employed.
Although coloured pigments, e.g., red or yellow iron oxide do not fade appreciably, the amounts of such pigments in tree fire retardant compositions of an aspect of this invention are small enough that the overall composition of an aspect of this invention ultimately fades to a neutral colour, i.e., substantially the same colour which the composition of an aspect of this invention would have exhibited if no colourant had been added.
For example, if a red fugitive component and red iron oxide (non-fugitive component) are employed, the initial colour (second hue) of the resultant fire retardant composition of an aspect of this invention will be red. If a red fugitive component and yellow iron oxide (non-fugitive component) are employed, the second hue will be orange.
If a red fugitive component and a white non-fugitive component are employed, the second hue will be pink. Any of these second hues may provide sufficient contrast with the hue of the ground vegetation to provide acceptable aerial visibility. At present, it is preferred to employ red iron oxide in combination with a red fugitive component to form the colourant of an aspect of this invention.
The maximum quantity of non-fugitive pigment which can be employed, which will still maintain the overall fugitive (fading) characteristics of the fire retardant composition of an aspect of this invention, will vary, depending on the natural or "neutral" colour of the fire retardant composition components and the natural colours of the terrain and vegetation. For example, if a blue-coloured fire retardant composition, e.g., that disclosed in U.S. Patent No. 3,960,735 to Lacey, is employed on darkly-coloured vegetation, e.g., spruce fir, a greater quantity of a coloured non-fugitive colourant, e.g., red iron oxide, can be employed. On the other hand, less of a coloured non-fugitive component can be employed if the base composition is highly viscous, or if the composition is applied on less highly coloured vegetation or terrain, e.g., chaparral. It appears that the maximum quantity of coloured non-fugitive component is higher when using a clay thickener than when using a gum thickener in the fire retardant composition of an aspeca of this invention. In general, it appears that the coloured non-fugitive pigment can be no more than 20 % to 30 % by weight of the total colourant. The maximum amount of the total colourant which is employed will be less than the amount which would prevent the fire retardant compositions of an aspect of this invention from fading to a neutral colour. These amounts can be determined by routine tests by persons skilled in the art having; regard to this disclosure.
For example, the maximum amount of red iron oxide which can be employed, irrespective of the amount of fugitive component presently appears to be 0.5 %
by weight of the liquid concentrate: formulations and 0.10 % by weight in diluted mixed concentrate compositions. However, for any given base composition of fire retardant composition components (fire retardant salt, thickener, corrosion inhibitor, etc.), the optimum and maximum concentrations of colourant components of an aspect of this invention can be determined by those skilled in the art without undue experimentation, having regard to the disclosure hereof. :For example, suitable procedures for assessing the aerial visibility and fugitive fading characteristics of these compositions are set forth in Sections 3.8 and 4.3.7 of Specification 5100-304a, February 1986, U.S. Department of Agriculture Forest 5 Service Specification for Long Term Retardant, Forest Fire, Aircraft or Ground Application.
The use of both a dye and a pigment in the same fire retardant composition is disclosed by U.S. Pate:nt No. 3,960,735, issued June l, 1976 to Lacey. In the Lacey patent (Example III) both "red iron oxide" and "6BL dye" are included in a fire retardant 10 concentrate composition. However, the primary colouring agent, red iron oxide, was present in an amount which was far in excess of that which would permit the composition to fade to the hue which it would exhibit if the dye/iron oxide had not be added, i.e., in U.S. Patent No. 3,960,735, to Lacey, the compositions were not "fugitive". The dye was added to the composition of Example III disclosed in that patent for the purpose of supplementing the re:d colour of the iron oxide, i.e., making the composition "redder", because the iron cyanide blue corrosion inhibitor of Lacey (Col. 2, lines 5 et seq. ) and the red iron oxide otherwise provided a "purplish" composition.
A prior art composition was known and used in the United States prior to the present invention whiclh may have included a colourant consisting of a mixture of a dye and a small quantity of Ti02, which was encapsulated in a polymeric matrix.
This prior composition was manufactured and shipped as a dry powder "concentrate" which was then diluted with water for field application. The quantity of Ti02 in this product was only 40ppm to SOppm in the final diluted concentrate, which was far less than the amount which is required to provide the enhanced visibility which is achieved by the compositions of aspects of the present invention.
The determination of whether the hue of the fugitive composition (second hue) fades to the hue of the fire retardant composition of an aspect of this invention without any colourant (first hue;) can be determined by the method which is described in Section 4.3.7.2 of Specification 5100-3U4a (February 1986), "USDA Forest Service Specification for Specification for Lcrng Term Retardant, Forest Fire Aircraft or Ground Application" .
The following examples are presented to illustrate principles of the present invention further to those skilled in the art. These examples do not, however, constitute limitations on the scope of aspects of this invention.
This example illustrates the practice of an aspect of this invention in the manufacture of so-called "liquid concentrate"-type fire retardant products.
The products are prepared in accordance with the procedure described U.S. Patent No.
3,960,735 to Lacey, except that the colourant in the fire retardant composition of an aspect of the present invention is substituted for the colouring agents described therein.
A concentrate composition is manufactured using two different types of ammonium polyphosphate liquid. The ingredients of each of these compositions are set forth in Tables A and 1B. Both of these compositions have improved aerial visibility in comparison to the same compositions which do not contain the red iron oxide pigment.
However, these fire retardant compositions of aspects of this invention have acceptable fading characteristics, i.e., fade to hue which are substantially the same as the compositions would exhibit without addition of the colourant.
TABLE A
Wt. % in Wt. % in Final Concentrate Diluted (5:1) Composition FIRE RETARDANT
COMPONENTS
Ammonium Polyphosphate Liquid (11-37-0) 99.3 - 78.6 22.2 - 17.58 Attapulgite Clay (AA Special) 0 - 10.0 0 - 2.24 TABLE A (Continued) Wt. % in Wt. % in Final Concentrate Diluted (5:1) Composition COLOURANT
COMPONENTS
Corrosion, Inhibitor Reagent(s), Stabilizers, Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.0 0 - 2.24 Fugitive Pigment (DAY-GLOTM 122-9180) 0.5 - 1.0 0.22 - 0.22 Non-Fugitive Pigment (Titanium Dioxide) 0.2 - 0.4 0.04 - 0.09 LI(,~UID CARRIER
Water None Balance TOTAL 100.00 100.00 TABLE B
Wt. % in Wt. % in Final Concentrate Diluted (4.25:1) Composition FIRE RETARDANT
COMPONENTS
Ammonium Polyphosphate Liquid (10-34-0) 99.3 - 77.4 24.74 - 19.28 Attapulgite Clay (AA Special) 0 - 10.0 0 - 2.49 TABLE B (Continued) Wt. % in Wt. % in Final Concentrate Diluted (4.25:1) Composition FIRE RETARDANT
COMPONENTS
Corrosion Inhibitor Reagent(s), Stabilizers., Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.0 0 - 2.49 COLOURANT COMPO NENTS
Fugitive Pigment (DAY-GLOTM 122-91 0. 5 - 2.0 0.12 - 0. 50 &0) Non-Fugitive Pigment (Yellow Iron Oxide) 0.2 - 0.6 0.05 - 0.15 LI(,~UID CARRIER
Water none balance TOTAL 100.00 100.00 This example illustrates the practice of an aspect of this invention by the manufacture of so-called dry or powder concentrate compositions. These dry compositions are thereafter mixed with water to form a final diluted fire retardant composition which is suitable for aerial application. These compositions are manufactured in accordance with the methods disclosed in U.S. Patent No.
4,176,071 to Crouch. The ingredients in each composition are set forth in Tables C, D
and E.
Each of these fire retardant compositions of aspects of this invention has acceptable aerial visibility and fugitive fading characteristics.
TABLE C
Wt. % in Wt. % in Final Concentrate Composition FIRE RETARDANT
COMPONENTS
Ammonium Sulphate 78.20 14.5 Diammonium Phosphate 3.78 0.7 Guar Gum 4.20 0,g Xanthan Gum 0.11 0.2 Corrosion Inhibitors 1.08 0.20 Spoilage Inhibitor 0.54 0.10 Defoamer/Anti-Oxidant 10.79 2.00 COLOURANT COMPONENTS
Fugitive Pigment 1.08 0.20 Non-Fugitive Pigment (Red Iron Oxide) 0.22 0.04 LIOUID CARRIER
Water none balance TOTAL 100.00 100.00 TABLE D
Wt. % in Wt. % in Final 5 Concentrate Composition FIRE RETARDANT
COMPONENTS
10 Ammonium Sulphate 24.52 3.2 Diammonium Phosphate 65.90 8.6 Guar Gum 5.98 .8 Stabilizer/Corrosion Inhibitor 2.30 .3 COLOURANT COMPONENTS
Fugitive Pigment 1.00 0.13 Non-Fugitive Pigment 0.30 0.04 LIt,~UID CARRIER
Water None Balance TOTAL 100.00 100.00 TABLE E
Wt. % in Wt. % in Final Concentrate Composition FIRE RETARDANT
COMPONENTS
Ammonium Sulphate x,15 g.5 Diammonium Phosphate 24.15 3.2 Guar Gum ( , pp , g Spoilage Inhibitor 0, 75 .1 Stabilizer/Corrosion Inhibitor 0 - 3.77 0 - 0.5 (variable) COLOURANT COMPONENTS
Fugitive Pigment 0.98 0.13 Non-Fugitive Pigment (Red Iron Oxide) 0.20 0.03 LIOUID CARRIER
Water None Balance TOTAL 100.00 100.00 This example illustrates the practice of aspects of the invention in the manufacture of fugitive compositions of the general type which is disclosed in U.S. Patent No.
4,983,326 to Vandersa,ll. A blended dry powder concentrate is prepared in accordance with Example 4B of U'.S. Patent No. 4,983,326 to Vandersall. The dry concentrate is mixed with water to form an intermediate low-viscosity liquid concentrate, which is then further diluted to form a high-viscosity final mixed fire retardant composition of aspects of this invention having improved aerial visibility in comparison to the same fire retardant compositions. without the iron oxide pigment and has acceptable "fugitive"
fading characteristics. Table F depicts the weight percentages of the components of the dry concentrate, interir~ediate liquid or so-called "fluid" concentrate and the final diluted mixed retardant composition of aspects of this invention.
TABLE F
Dry Con- Liquid Con- Final centrate centxate Mix FIRE RETARDANT COMPONENTS
Monoammonium phosphate 52.24 24.46 5.62 Diammonium phosphate 34.81 16.30 3.74 Guar Gum 7.24 3.39 0.78 Sodium Molybdate 0.19 0.09 0.02 Tricalcium Phosphate 2.01 0.94 0.22 Sodium Silicofluoride 0.47 0.22 0.05 Mercaptobenzothiazole 0.30 0.14 0.03 Dimercaptothiadiazole 0.72 0.34 0.08 TABLE F (Continued) Dry Con- Liquid Con- Final centrate centrate Mix FIRE RETARDANT COMPONENTS
Polyalkylene Derivatives of Propylene Glycol 0.13 0.06 0.01 COLOURANT
Fugitive Component 1.61 0.75 0.17 Red Iron Oxide 0.28 0.13 0.03 LIOUID CARRIER
Water none 53.18 balance TOTAL 100.00 100.00 100.00 Example 4 illustrates the best mode presently known for practising an aspect of the present invention. Each of the products described in Examples 4 and 5 has acceptable aerial visibility and fugitive fading. If the red iron oxide is deleted from the compositions or reduced below 0.20 wt % in the concentrate, the compositions will not have acceptable aerial visibility, even if the red iron oxide which is deleted is replaced by equal amounts of the fugitive pigment. If the fugitive pigment is eliminated or reduced and the red iron oxide content is increased to provide sufficient aerial visibility, then the compositions do not have acceptable fugitive fading.
The following compositions were prepared in accordance with method described in the U.S. Patent No. :3,960,735 to Lacey, except that the colourant in the fire retardant composition of aspects of the present invention is substituted for the colouring agents described therein. The ingredients used in preparing the liquid concentrates and the final diluted mixed fire retardant are listed in Tables G, H and I.
TABLE G
Wt % in Liquid Wt % in Dih~ted Concentrate Mixed Retardarn FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (ARCADIANTN~ 11-37-0) 90.60 20.29 Attapulgite Clay (FLORIDINTM AA Special) 3.50 0.78 Sodium Ferrocyanide (WEGOTM Technical) 4.50 1.01 TABLE G (Continued) Wt % in Liquid Wt % ~
Concentrate COLOURANT
10 Fugitive Pigment (DAY-GLOTM #122-9180) 1.00 0.22 Non-Fugitive Pigment (Mobay Corp. BAYFERROXTM
15 Red Iron Oxide 130M) 0.40 0.09 LIOUID CARRIER
20 Water none balance TOTAL 100.00 100.00 TABLE H
Wt % in Liquid Wt % in Dihited Concentrate Mixed Retai~ai~
FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (SIMPLOTTM 11)-34-0) 90.70 22.98 Attapulgite Clay (FLORIDINTM AA Special) 4.00 1.01 Sodium Ferrocyanide (WEGOTM Technical) 3.90 0.99 COLOURANT
Fugitive Pigment (DAY-GLOTM #122-91!30) 1.00 0.25 Non-Fugitive Pigment (Mobay Corp. BAYFERROXTM
Red Iron Oxide 130M) 0.40 0.10 LI(~UID CARRIER
Water none balance TOTAL 100.00 100.00 TABLE I
Wt % in Liquid Wt % in Dihited Concentrate Mixed R~darn FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (MACGREGORTM 11-37-0) 90.60 21.10 Attapulgite Clay (FLORIDINTM AA Special) 3.50 0.82 Sodium Ferrocyanide (WEGOTM Technical) 4.50 1.05 COLOURANT
Fugitive Pigment (DAY-GLOTM #122-9180) 1.00 0.23 Non-Fugitive Pigment (Mobay Corp. BAYF)=;RROXTM
Red Iron Oxide 130M) 0.40 0.09 LIQUID CARRIER
Water none balance TOTAL 100.00 100.00 This example illustrates the practice of an aspect of this invention by the manufacture of liquid concentrate products from ammonium polyphosphate liquids, using non-fugitive components other than red iron oxide. These fire retardant compositions of aspects of this invention have acceptable aerial visibility and fugitive fading characteristics. The fire retardant compositions of aspects of this invention are prepared in accordance with the: procedure of Example 1, with the components listed in Table J
and Table K.
TABLE J
Wt. % in Concentrate Wt. % in Solution Ammonium Polyphosphate90.6 20.26 (11-37-0) Attapulgite Clay 3.5 0.78 Corrosion Inhibitor 4.5 1.01 Water none balance Fugitive Pigment 1.0 0.22 Titanium Dioxide 0.4 0.09 TOTAL 100.00 100.00 TABLE K
Wt. % in Concentrate Wt. % in Solution Ammonium Polyphospate 90.7 22.83 ( 10-34-0) Attapulgite Clay 4.0 1.01 Corrosion Inhibitor 3.9 0.99 Water none balance Fugitive Pigment 1.0 0.25 Yellow Iron Oxide 0.4 0.10 'TOTAL 100.00 100.00 a a , This example illustrates the practice of aspects of this invention by the manufacture of dry concentrate products from ammonium phosphate and ammonium sulphate, using non-fugitive components other than red iron oxide. These fire retardant compositions of aspects of this invention have acceptable aerial visibility and fugitive fading characteristics. The fire retardant compositions of aspects of this invention are prepared in accordance with the procedure of Example 2, with the components listed in Tables L-O.
TABLE L
Wt. % in Concentrate Wt. % in Solution Ammonium Sulphate 94.47 - 82.21 14.70 Diammonium Phosphate 4.56 - 3.97 0.71 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 8.40 0 - 1.5 Fugitive Pigment 0.84 - 0.73 0.13 Yellow Iron Oxide 0.13 - 0.22 0.02 - 0.04 Water None 84.44 - 82.14 TOTAL 100.00 100.00 c TABLE M
Wt. % in ConcentrateWt. % in Solution Ammonium Sulphate 93.90 - 83.44 10.00 - 20.00 Diammonium Phosphate 4.69 - 6.25 0.50 - 1.50 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion.
Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 6.26 0 - 1.5 Fugitive Pigment 1.22 - 0.54 0.13 Titanium Dioxide 0.19 - 0.17 0.02 - 0.04 Water None 89.35 - 76.03 'TOTAL 100.00 100.00 TABLE N
Wt. % in ConcentrateWt. % in Solution Ammonium Sulphate 71.61 - 59.98 8.5 Diammonium Phosphate 26.96 - 22.58 3.2 Guar Gum 0 - 5.65 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.59 0 - 1.5 Fugitive Pigment 1.09 - 0.92 0.13 Yellow Iron Oxide 0.34 - 0.28 0.04 Water None 88.13 - 85.83 TOTAL 100.00 100.00 c TABLE O
Wt. % in Concentrate Wt. % in Solution S
Ammonium Sulphate 69.47 - 53.53 14.00 - 5.00 Diammonium Phosphate 29.78 - 20.02 6.0 - 1.87 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 16.06 0 - 1.5 Fugitive Pigment 1.65 - 1.40 0.13 Titanium Dioxide 0.10 - 0.43 0.02 - 0.04 Water None 79.85 - 90.66 TOTAL 100.00 100.00
In general, the active fire retardant components are compounds or a mixture of compounds that degrafe or decompose at temperatures which are below the ignition temperature of the fuels to be protected (e.g., cellulose), thereby releasing a mineral acid, e.g., phosphoric acid or sulphuric acid. Among the various fire retardants typically used in fire retardant mixtures and which might be used in the compositions of aspects of this invention are rnonoammonium orthophosphate, diammonium orthophosphate, monoammonium pyrophosphate, diammonium pyrophosphate, triammonium pyrophosphate, tetraammonium pyrophosphate, ammonium polyphosphate, substituted ammonium polyphosphate, amide polyphosphate, melamine polyphosphate, ammonium-alkali metal mixed salts of orthophosphate, ammonium-alkali metal mixed salts of pyrophosphate, ammonium-alkalimetal mixed salts of polyphosphate, ammonium-alkaline earth metal mixed salts of orthophosphate, ammonium-alkaline earth metal mixed salts of pyrophosphate, ammonium-alkaline earth metal mixed salts of polyphosphate, ammonium sulphate, liquid ammonium polyphosphates and blends thereof. Some liquid ammonium polyphosphates may be too dilute in their commercial forms for application as fire retardants but, other retardants, e.g., those noted above, may be mixed with a liquid ammonium polyphosphate until a minimum acceptable concentration is obtained.
Ammonium polyphosphate is often called polyammonium phosphate, and commonly contains other ammonium phosphates, e.g., pyro- and metaphosphates, and the alkali metal equivalents thereof, as well as a blend of phosphate polymers. Such polyammonium phosphates are often referred to as 10-34-0, 11-37-0, 12-40-0, 13-or the like, where the first number indicates the percentage of nitrogen in the blend, the middle number indicates the percentage phosphate in the blend and the last number indicates the percentagc: potash in the blend.
The fire retardmt companents may also include thickening agents, which include standard thickeners, e. g:. , galactomannan guar gum compositions and derivatives thereof, attapulgite clay, carbo:Kymethylcellulose and derivatives thereof, and the like. The thickening agent is employed to maintain the viscosity of the diluted mixed fire retardant composition, for example, at between 50 centipoise and 2000 centipoise for aerial application. In addition, the fire retardant components, in the concentrate or in the final diluted mixed form, rnay also typically include various adjuvants, e.g., corrosion inhibitors, flow conditioners, spoilage inhibitors, stabilizers and the like, and carriers for these adjuvants, in accordance with art-recognized principles.
When such fire retardant compositions, in final diluted mixed form for aerial application, are applied by dropping from fixed-wing or helicopter aircraft, successive "drops" are often made by the aircraft to form a fire-fighting line. Under these circumstances, it is important for the pilot of the aircraft to be able to determine visually where the preceding loads were dropped, such that the pilot can drop the load from the aircraft to form a continuation of this line. Since the fire retardant components (described above) may be colourless or may be of colours which do not contrast well with the ground or vegetation, it has been common practice to mix colouring agents with the fire retardant composition components. Colouring agents are used to give the fire retardant compositions a colour (hue) which contrasts with the hue of the ground vegetation, thereby enhancing the ability of the aircraft pilot to determine where the last loads of fire retardants were dropped in constructing a fire-fighting line.
Prior art colouring agents have included pigments which are dispersible in the liquid fire retardant compositions or soluble therein, most commonly red iron oxide or various water-soluble dyes. Such colouring agents were remarkably effective in enhancing the aerial visibility of fire retardant compositions after they were applied. However, certain prior art colouring agents, especially red irow oxide, were very "colourfast" , such that the ground and structures (if any) to which the prior art fore retardant compositions were applied, remained permanently or semi-peruanently stained. Consequently, certain government fire-fighting agencies have, more recently, required that aerially-applied fire retardant compositions have so-called "fugitive" colouring agents, such that the colour of the compositions would fade over a short time, e.g., 30 days, to a colour which did not objectionably contrast with the ground and ground vegetation.
Several dyes and pigments (encapsulated dyes) have been identified which impart a distinctive hue to fire retardant compositions, which contrasts with ground vegetation, but which fade in a short time to a "neutral" colour, i.e., such that the fire retardant compositions exhibit the colour they would have exhibited without the addition of such fugitive agents. However, although the fire retardant compositions themselves might be brilliantly colours by fugitive agents, after first application it was often difficult to locate the fire retardant drop zone. It has been found that the reduced visibility of these highly coloured fugitive compositions is somewhat related to the viscosity of the fire retardant compositions themselves. Thus, more highly viscous fugitive compositions are somewhat easier to see on the vegetation, because they form a thicker coating.
However, even highly viscous fugitive colour compositions are sometimes difficult to visualize from an aircraft after dropping on various kinds of vegetation and under various lighting conditions.
It would be advantageous to provide fugitive colour fire retardant compositions which exhibit improved aerial visibility after dropping. It would also be advantageous to achieve this result in an economical manner and without using any materials which are toxic to humans, animals, to fish or to vegetation.
Briefly, a fugitive color liquid fire retardant composition has been discovered for aerial application to ground vegetation which achieves these objectives.
According to one aspect of the present invention there is provided a fugitive color liquid from retardant composition for aerial application to ground vegetation, said composition comprising: a) fire retardant components having a first hue, comprising a fire retardant salt; b)a colorant which initially colors said composition to a second hue which contrasts with the hue of said vegetation, said colorant comprising: i) a fugitive color component; ii) a non-fugitive component which is present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application; arid c) an aqueous carrier.
According to another aspect of the present invention there is provided a concentrate composition for preparing a fugitive color liquid fire retardant composition for aerial application to ground vegetation, by dilution thereof with an aqueous carrier, said concentrate composition comprising:
a) fire retardant components having a first hue, comprising a fire retardant salt; and b) a colorant which initially colors said composition to a second hue which contrast with the hue of said vegetation, said colorant comprising: i) a fugitive color component, and ii) a non-fugitive component present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application.
According to a further aspect of the present invention there is provided a fugitive color liquid fire retardant composition for aerial application to ground vegetation, said composition comprising: a) fare retardant components including a fire retardant salt; b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with normal vegetation or ground; and c) titanium dioxide, in an amount sufficient to improve the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to a neutral color which blends with normal vegetation or ground.
According to another aspect of the present invention there is provided a method for fighting wildfires comprising the steps of: applying a fire retardant composition to ground vegetation, which composition includes: a) fire retardant components including a fire retardant salt; b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with the vegetation or ground; and c) a non-fugitive color component insoluble in an aqueous carrier which improves the aerial visibility of said composition, and said non-fugitive color component provided in less than an amount which prevents said composition from fading to a neutral color which blends with the vegetation or ground.
By two variants of this second broad aspect of this invention, the concentrate composition is a dry composition, or is a liquid concentrate composition.
By a variant of these two broad aspects of this invention, the non-fugitive component is red iron oxide.
By a second variant of these two broad aspects of this invention, and/or the above variants thereof, the fire retardant salt comprises a liquid ammonium polyphosphate.
In other words, the compositions of aspects of this invention generally comprise fire retardant components, a colorant and a liquid carrier, a typically an aqueous carrier.
'The fire retardant components include a fire-suppressing salt and have a first hue. The colourant comprises a fugitive component and a non-fugitive component.
The colourant used in aspects of thus invention initially colours the fire retardant composition components to a second hue which contrasts with the hue of the ground vegetation. This may be due solely to the colour which is imparted by the fugitive component, or to the colour which is imparted by the combined fugitivelnon-fugitive components .
The non-fugitive component of the colourant of an aspect of this invention is ' present in an amount which is sufficient to improve the aerial visibility of the composition when it is first applied to the vegetation. However, the non-fugitive component is the composition of an aspect of this invention is present in less than an amount which prevents the composition froth thereafter fading to the first hue, i.e., the hue of the fire retardant composition components without the colourant.
According to another embodiment of a general aspect of this invention, a concentrate composition is provided for preparing the liquid composition described above by dilution thereof with the aqueous carrier. The concentrate composition of this aspect of this invention generally comprises the fire retardant components and the colourant.
In one embodiment, the concentrate is a dry composition. In another embodiment, the concentrate is a liquid which is suitable for later dilution with water to form the final mixed liquid fire retardant composition.
As used herein, the term "Errs retardant components" means all of the components of the composition except the "colourant" and the liquid carrier, if any. The fire retardant components will include a fire retardant salt and may optionally include (and usually will include) other common ingredients of fue retardant formulations, e.g., corrosion inhibitors, spoilage inhibitors, flow conditioners, anti-foaming agents, foaming agents, stability additives and thickening agents.
The term "coiourant" means a combination of at least two components, namely, a fugitive component and a non-fugitive component.
The "fugitive component" is a dye, or a dye which is dispersed in a matrix (i.e., a pigment), which fade, over time and under ambient field conditions to a colourless or less-highly-coloured hue. A number of such dyes and pigments are well-known in the art. For example, many water-soluble dyes fade rapidly and there are so-called fluorescent pigments (fluorescent dyes which are encapsulated in a resin integument) which are suspendible in the fire retardant compositions of aspects of this invention and which also fade rapidlw to provide the "fugitive" effect. Typical examples of prior art fugitive dyes and pigments include C.I. Basic Red I dye, 6BL dye, Basic Violet II dye, Basic Yellow 40 and encapsulated-dye pigments which are available commercially, e.g., the pigments known by the trade name of the AXTM series pigments, supplied by Day-Glo Color Corp., Cleveland, Ohio. At present, it is preferred to employ encapsulated-dye fugitive pigments v~rithout uv absorbers, rather than using water-soluble dyes because the encapsulated-dye pigments are less likely to stain.
The colourant is present in an amount which provides a colour ("second hue") to the composition which is different from the colour of the composition without the colourant ("first hue"). The second hue contrasts with the hue of the vegetation (normally green and/or brown). Advantageously, the second hue is red, orange or pink.
The colourant also includes a "non-fugitive" component, i.e., a component which is insoluble in the carrier liquid and which, if coloured, does not necessarily fade after aerial application of the fire retardant composition.
The non-fugitive component preferably has an index of refraction of at least 2Ø
For example, prior art: fire retardant compositions containing fugitive colourants and which also contain various clays and other insoluble materials, e.g., attapulgite clay, tricalcium phosphate, (c:omponents which have refractive indices below 2.0), did not have the improved aerial visibility which is exhibited by the compositions of aspects of the present invention unless the amounts of such lower-index materials are so large that the compositions are not "fugitive". To achieve improved aerial visibility, smaller quantities of non-fugitive compor,~ents can be employed if the refractive index is higher and larger quantities of lower-index materials are required to achieve desirable results.
g The non-fugitive component of an aspect of this invention is included in the colourant in an amount which is sufficient to provide improved aerial visibility of the composition when it is first aerially applied to the vegetation. However, the amount of the non-fugitive component in the fire retardant composition of an aspect of this invention is less than the amount which would prevent the fire retardant composition of an aspect of this invention from fading to the first hue after application.
The non-fugitive component is dispersible or suspendible in the final fire retardant composition of an aspect of this invention and in a liquid concentrate of an aspect of this invention of such composition. The dispersibility or suspendibility of such a component is primarily dependent upon particle size and particle size distribution and the nature of the other components which are present in the fire retardant composition of an aspect of this invention, e.g., thickeners, etc.
Also, the chemical structure and characteristics of the non-fugitive pigment in the fire retardant composition of an aspect of this invention must be compatible with the other components, espE:cially with the carrier liquid. It must be sufficiently chemically-inert that it does not lose its functional capability when combined with the other components of the fire: retardant composition of an aspect of this invention.
It should also be non-toxic, and, if coloured, should not undesirably affect the hue established by the fugitive component: of an aspect of this invention.
For example, in a presently preferred practice of aspects of this invention, red iron oxide pigments are employed as the non-fugitive component. Yellow iron oxide pigments and white pigments, e. g. , titanium dioxide can also be employed.
Although coloured pigments, e.g., red or yellow iron oxide do not fade appreciably, the amounts of such pigments in tree fire retardant compositions of an aspect of this invention are small enough that the overall composition of an aspect of this invention ultimately fades to a neutral colour, i.e., substantially the same colour which the composition of an aspect of this invention would have exhibited if no colourant had been added.
For example, if a red fugitive component and red iron oxide (non-fugitive component) are employed, the initial colour (second hue) of the resultant fire retardant composition of an aspect of this invention will be red. If a red fugitive component and yellow iron oxide (non-fugitive component) are employed, the second hue will be orange.
If a red fugitive component and a white non-fugitive component are employed, the second hue will be pink. Any of these second hues may provide sufficient contrast with the hue of the ground vegetation to provide acceptable aerial visibility. At present, it is preferred to employ red iron oxide in combination with a red fugitive component to form the colourant of an aspect of this invention.
The maximum quantity of non-fugitive pigment which can be employed, which will still maintain the overall fugitive (fading) characteristics of the fire retardant composition of an aspect of this invention, will vary, depending on the natural or "neutral" colour of the fire retardant composition components and the natural colours of the terrain and vegetation. For example, if a blue-coloured fire retardant composition, e.g., that disclosed in U.S. Patent No. 3,960,735 to Lacey, is employed on darkly-coloured vegetation, e.g., spruce fir, a greater quantity of a coloured non-fugitive colourant, e.g., red iron oxide, can be employed. On the other hand, less of a coloured non-fugitive component can be employed if the base composition is highly viscous, or if the composition is applied on less highly coloured vegetation or terrain, e.g., chaparral. It appears that the maximum quantity of coloured non-fugitive component is higher when using a clay thickener than when using a gum thickener in the fire retardant composition of an aspeca of this invention. In general, it appears that the coloured non-fugitive pigment can be no more than 20 % to 30 % by weight of the total colourant. The maximum amount of the total colourant which is employed will be less than the amount which would prevent the fire retardant compositions of an aspect of this invention from fading to a neutral colour. These amounts can be determined by routine tests by persons skilled in the art having; regard to this disclosure.
For example, the maximum amount of red iron oxide which can be employed, irrespective of the amount of fugitive component presently appears to be 0.5 %
by weight of the liquid concentrate: formulations and 0.10 % by weight in diluted mixed concentrate compositions. However, for any given base composition of fire retardant composition components (fire retardant salt, thickener, corrosion inhibitor, etc.), the optimum and maximum concentrations of colourant components of an aspect of this invention can be determined by those skilled in the art without undue experimentation, having regard to the disclosure hereof. :For example, suitable procedures for assessing the aerial visibility and fugitive fading characteristics of these compositions are set forth in Sections 3.8 and 4.3.7 of Specification 5100-304a, February 1986, U.S. Department of Agriculture Forest 5 Service Specification for Long Term Retardant, Forest Fire, Aircraft or Ground Application.
The use of both a dye and a pigment in the same fire retardant composition is disclosed by U.S. Pate:nt No. 3,960,735, issued June l, 1976 to Lacey. In the Lacey patent (Example III) both "red iron oxide" and "6BL dye" are included in a fire retardant 10 concentrate composition. However, the primary colouring agent, red iron oxide, was present in an amount which was far in excess of that which would permit the composition to fade to the hue which it would exhibit if the dye/iron oxide had not be added, i.e., in U.S. Patent No. 3,960,735, to Lacey, the compositions were not "fugitive". The dye was added to the composition of Example III disclosed in that patent for the purpose of supplementing the re:d colour of the iron oxide, i.e., making the composition "redder", because the iron cyanide blue corrosion inhibitor of Lacey (Col. 2, lines 5 et seq. ) and the red iron oxide otherwise provided a "purplish" composition.
A prior art composition was known and used in the United States prior to the present invention whiclh may have included a colourant consisting of a mixture of a dye and a small quantity of Ti02, which was encapsulated in a polymeric matrix.
This prior composition was manufactured and shipped as a dry powder "concentrate" which was then diluted with water for field application. The quantity of Ti02 in this product was only 40ppm to SOppm in the final diluted concentrate, which was far less than the amount which is required to provide the enhanced visibility which is achieved by the compositions of aspects of the present invention.
The determination of whether the hue of the fugitive composition (second hue) fades to the hue of the fire retardant composition of an aspect of this invention without any colourant (first hue;) can be determined by the method which is described in Section 4.3.7.2 of Specification 5100-3U4a (February 1986), "USDA Forest Service Specification for Specification for Lcrng Term Retardant, Forest Fire Aircraft or Ground Application" .
The following examples are presented to illustrate principles of the present invention further to those skilled in the art. These examples do not, however, constitute limitations on the scope of aspects of this invention.
This example illustrates the practice of an aspect of this invention in the manufacture of so-called "liquid concentrate"-type fire retardant products.
The products are prepared in accordance with the procedure described U.S. Patent No.
3,960,735 to Lacey, except that the colourant in the fire retardant composition of an aspect of the present invention is substituted for the colouring agents described therein.
A concentrate composition is manufactured using two different types of ammonium polyphosphate liquid. The ingredients of each of these compositions are set forth in Tables A and 1B. Both of these compositions have improved aerial visibility in comparison to the same compositions which do not contain the red iron oxide pigment.
However, these fire retardant compositions of aspects of this invention have acceptable fading characteristics, i.e., fade to hue which are substantially the same as the compositions would exhibit without addition of the colourant.
TABLE A
Wt. % in Wt. % in Final Concentrate Diluted (5:1) Composition FIRE RETARDANT
COMPONENTS
Ammonium Polyphosphate Liquid (11-37-0) 99.3 - 78.6 22.2 - 17.58 Attapulgite Clay (AA Special) 0 - 10.0 0 - 2.24 TABLE A (Continued) Wt. % in Wt. % in Final Concentrate Diluted (5:1) Composition COLOURANT
COMPONENTS
Corrosion, Inhibitor Reagent(s), Stabilizers, Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.0 0 - 2.24 Fugitive Pigment (DAY-GLOTM 122-9180) 0.5 - 1.0 0.22 - 0.22 Non-Fugitive Pigment (Titanium Dioxide) 0.2 - 0.4 0.04 - 0.09 LI(,~UID CARRIER
Water None Balance TOTAL 100.00 100.00 TABLE B
Wt. % in Wt. % in Final Concentrate Diluted (4.25:1) Composition FIRE RETARDANT
COMPONENTS
Ammonium Polyphosphate Liquid (10-34-0) 99.3 - 77.4 24.74 - 19.28 Attapulgite Clay (AA Special) 0 - 10.0 0 - 2.49 TABLE B (Continued) Wt. % in Wt. % in Final Concentrate Diluted (4.25:1) Composition FIRE RETARDANT
COMPONENTS
Corrosion Inhibitor Reagent(s), Stabilizers., Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.0 0 - 2.49 COLOURANT COMPO NENTS
Fugitive Pigment (DAY-GLOTM 122-91 0. 5 - 2.0 0.12 - 0. 50 &0) Non-Fugitive Pigment (Yellow Iron Oxide) 0.2 - 0.6 0.05 - 0.15 LI(,~UID CARRIER
Water none balance TOTAL 100.00 100.00 This example illustrates the practice of an aspect of this invention by the manufacture of so-called dry or powder concentrate compositions. These dry compositions are thereafter mixed with water to form a final diluted fire retardant composition which is suitable for aerial application. These compositions are manufactured in accordance with the methods disclosed in U.S. Patent No.
4,176,071 to Crouch. The ingredients in each composition are set forth in Tables C, D
and E.
Each of these fire retardant compositions of aspects of this invention has acceptable aerial visibility and fugitive fading characteristics.
TABLE C
Wt. % in Wt. % in Final Concentrate Composition FIRE RETARDANT
COMPONENTS
Ammonium Sulphate 78.20 14.5 Diammonium Phosphate 3.78 0.7 Guar Gum 4.20 0,g Xanthan Gum 0.11 0.2 Corrosion Inhibitors 1.08 0.20 Spoilage Inhibitor 0.54 0.10 Defoamer/Anti-Oxidant 10.79 2.00 COLOURANT COMPONENTS
Fugitive Pigment 1.08 0.20 Non-Fugitive Pigment (Red Iron Oxide) 0.22 0.04 LIOUID CARRIER
Water none balance TOTAL 100.00 100.00 TABLE D
Wt. % in Wt. % in Final 5 Concentrate Composition FIRE RETARDANT
COMPONENTS
10 Ammonium Sulphate 24.52 3.2 Diammonium Phosphate 65.90 8.6 Guar Gum 5.98 .8 Stabilizer/Corrosion Inhibitor 2.30 .3 COLOURANT COMPONENTS
Fugitive Pigment 1.00 0.13 Non-Fugitive Pigment 0.30 0.04 LIt,~UID CARRIER
Water None Balance TOTAL 100.00 100.00 TABLE E
Wt. % in Wt. % in Final Concentrate Composition FIRE RETARDANT
COMPONENTS
Ammonium Sulphate x,15 g.5 Diammonium Phosphate 24.15 3.2 Guar Gum ( , pp , g Spoilage Inhibitor 0, 75 .1 Stabilizer/Corrosion Inhibitor 0 - 3.77 0 - 0.5 (variable) COLOURANT COMPONENTS
Fugitive Pigment 0.98 0.13 Non-Fugitive Pigment (Red Iron Oxide) 0.20 0.03 LIOUID CARRIER
Water None Balance TOTAL 100.00 100.00 This example illustrates the practice of aspects of the invention in the manufacture of fugitive compositions of the general type which is disclosed in U.S. Patent No.
4,983,326 to Vandersa,ll. A blended dry powder concentrate is prepared in accordance with Example 4B of U'.S. Patent No. 4,983,326 to Vandersall. The dry concentrate is mixed with water to form an intermediate low-viscosity liquid concentrate, which is then further diluted to form a high-viscosity final mixed fire retardant composition of aspects of this invention having improved aerial visibility in comparison to the same fire retardant compositions. without the iron oxide pigment and has acceptable "fugitive"
fading characteristics. Table F depicts the weight percentages of the components of the dry concentrate, interir~ediate liquid or so-called "fluid" concentrate and the final diluted mixed retardant composition of aspects of this invention.
TABLE F
Dry Con- Liquid Con- Final centrate centxate Mix FIRE RETARDANT COMPONENTS
Monoammonium phosphate 52.24 24.46 5.62 Diammonium phosphate 34.81 16.30 3.74 Guar Gum 7.24 3.39 0.78 Sodium Molybdate 0.19 0.09 0.02 Tricalcium Phosphate 2.01 0.94 0.22 Sodium Silicofluoride 0.47 0.22 0.05 Mercaptobenzothiazole 0.30 0.14 0.03 Dimercaptothiadiazole 0.72 0.34 0.08 TABLE F (Continued) Dry Con- Liquid Con- Final centrate centrate Mix FIRE RETARDANT COMPONENTS
Polyalkylene Derivatives of Propylene Glycol 0.13 0.06 0.01 COLOURANT
Fugitive Component 1.61 0.75 0.17 Red Iron Oxide 0.28 0.13 0.03 LIOUID CARRIER
Water none 53.18 balance TOTAL 100.00 100.00 100.00 Example 4 illustrates the best mode presently known for practising an aspect of the present invention. Each of the products described in Examples 4 and 5 has acceptable aerial visibility and fugitive fading. If the red iron oxide is deleted from the compositions or reduced below 0.20 wt % in the concentrate, the compositions will not have acceptable aerial visibility, even if the red iron oxide which is deleted is replaced by equal amounts of the fugitive pigment. If the fugitive pigment is eliminated or reduced and the red iron oxide content is increased to provide sufficient aerial visibility, then the compositions do not have acceptable fugitive fading.
The following compositions were prepared in accordance with method described in the U.S. Patent No. :3,960,735 to Lacey, except that the colourant in the fire retardant composition of aspects of the present invention is substituted for the colouring agents described therein. The ingredients used in preparing the liquid concentrates and the final diluted mixed fire retardant are listed in Tables G, H and I.
TABLE G
Wt % in Liquid Wt % in Dih~ted Concentrate Mixed Retardarn FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (ARCADIANTN~ 11-37-0) 90.60 20.29 Attapulgite Clay (FLORIDINTM AA Special) 3.50 0.78 Sodium Ferrocyanide (WEGOTM Technical) 4.50 1.01 TABLE G (Continued) Wt % in Liquid Wt % ~
Concentrate COLOURANT
10 Fugitive Pigment (DAY-GLOTM #122-9180) 1.00 0.22 Non-Fugitive Pigment (Mobay Corp. BAYFERROXTM
15 Red Iron Oxide 130M) 0.40 0.09 LIOUID CARRIER
20 Water none balance TOTAL 100.00 100.00 TABLE H
Wt % in Liquid Wt % in Dihited Concentrate Mixed Retai~ai~
FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (SIMPLOTTM 11)-34-0) 90.70 22.98 Attapulgite Clay (FLORIDINTM AA Special) 4.00 1.01 Sodium Ferrocyanide (WEGOTM Technical) 3.90 0.99 COLOURANT
Fugitive Pigment (DAY-GLOTM #122-91!30) 1.00 0.25 Non-Fugitive Pigment (Mobay Corp. BAYFERROXTM
Red Iron Oxide 130M) 0.40 0.10 LI(~UID CARRIER
Water none balance TOTAL 100.00 100.00 TABLE I
Wt % in Liquid Wt % in Dihited Concentrate Mixed R~darn FIRE RETARDANT COMPONENTS
Ammonium Polyphosphate Liquid (MACGREGORTM 11-37-0) 90.60 21.10 Attapulgite Clay (FLORIDINTM AA Special) 3.50 0.82 Sodium Ferrocyanide (WEGOTM Technical) 4.50 1.05 COLOURANT
Fugitive Pigment (DAY-GLOTM #122-9180) 1.00 0.23 Non-Fugitive Pigment (Mobay Corp. BAYF)=;RROXTM
Red Iron Oxide 130M) 0.40 0.09 LIQUID CARRIER
Water none balance TOTAL 100.00 100.00 This example illustrates the practice of an aspect of this invention by the manufacture of liquid concentrate products from ammonium polyphosphate liquids, using non-fugitive components other than red iron oxide. These fire retardant compositions of aspects of this invention have acceptable aerial visibility and fugitive fading characteristics. The fire retardant compositions of aspects of this invention are prepared in accordance with the: procedure of Example 1, with the components listed in Table J
and Table K.
TABLE J
Wt. % in Concentrate Wt. % in Solution Ammonium Polyphosphate90.6 20.26 (11-37-0) Attapulgite Clay 3.5 0.78 Corrosion Inhibitor 4.5 1.01 Water none balance Fugitive Pigment 1.0 0.22 Titanium Dioxide 0.4 0.09 TOTAL 100.00 100.00 TABLE K
Wt. % in Concentrate Wt. % in Solution Ammonium Polyphospate 90.7 22.83 ( 10-34-0) Attapulgite Clay 4.0 1.01 Corrosion Inhibitor 3.9 0.99 Water none balance Fugitive Pigment 1.0 0.25 Yellow Iron Oxide 0.4 0.10 'TOTAL 100.00 100.00 a a , This example illustrates the practice of aspects of this invention by the manufacture of dry concentrate products from ammonium phosphate and ammonium sulphate, using non-fugitive components other than red iron oxide. These fire retardant compositions of aspects of this invention have acceptable aerial visibility and fugitive fading characteristics. The fire retardant compositions of aspects of this invention are prepared in accordance with the procedure of Example 2, with the components listed in Tables L-O.
TABLE L
Wt. % in Concentrate Wt. % in Solution Ammonium Sulphate 94.47 - 82.21 14.70 Diammonium Phosphate 4.56 - 3.97 0.71 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 8.40 0 - 1.5 Fugitive Pigment 0.84 - 0.73 0.13 Yellow Iron Oxide 0.13 - 0.22 0.02 - 0.04 Water None 84.44 - 82.14 TOTAL 100.00 100.00 c TABLE M
Wt. % in ConcentrateWt. % in Solution Ammonium Sulphate 93.90 - 83.44 10.00 - 20.00 Diammonium Phosphate 4.69 - 6.25 0.50 - 1.50 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion.
Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 6.26 0 - 1.5 Fugitive Pigment 1.22 - 0.54 0.13 Titanium Dioxide 0.19 - 0.17 0.02 - 0.04 Water None 89.35 - 76.03 'TOTAL 100.00 100.00 TABLE N
Wt. % in ConcentrateWt. % in Solution Ammonium Sulphate 71.61 - 59.98 8.5 Diammonium Phosphate 26.96 - 22.58 3.2 Guar Gum 0 - 5.65 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 10.59 0 - 1.5 Fugitive Pigment 1.09 - 0.92 0.13 Yellow Iron Oxide 0.34 - 0.28 0.04 Water None 88.13 - 85.83 TOTAL 100.00 100.00 c TABLE O
Wt. % in Concentrate Wt. % in Solution S
Ammonium Sulphate 69.47 - 53.53 14.00 - 5.00 Diammonium Phosphate 29.78 - 20.02 6.0 - 1.87 Guar Gum 0 - 4.47 0 - 0.8 Stabilizer(s)/Corrosion Inhibitor(s)/Spoilage Inhibitor(s), Defoamer(s), etc. 0 - 16.06 0 - 1.5 Fugitive Pigment 1.65 - 1.40 0.13 Titanium Dioxide 0.10 - 0.43 0.02 - 0.04 Water None 79.85 - 90.66 TOTAL 100.00 100.00
Claims (12)
1. A fugitive color liquid fire retardant composition for aerial application to ground vegetation, said composition comprising:
a) fire retardant components having a first hue, comprising a fire retardant salt;
b) a colorant which initially colors said composition to a second hue which contrasts with the hue of said vegetation, said colorant comprising:
i) a fugitive color component;
ii) a non-fugitive component which is present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application; and c) an aqueous carrier.
a) fire retardant components having a first hue, comprising a fire retardant salt;
b) a colorant which initially colors said composition to a second hue which contrasts with the hue of said vegetation, said colorant comprising:
i) a fugitive color component;
ii) a non-fugitive component which is present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application; and c) an aqueous carrier.
2. A concentrate composition for preparing a fugitive color liquid fire retardant composition for aerial application to ground vegetation, by dilution thereof with an aqueous carrier, said concentrate composition comprising:
a) fire retardant components having a first hue, comprising a fire retardant salt; and b) a colorant which initially colors said composition to a second hue which contrast with the hue of said vegetation, said colorant comprising:
i) a fugitive color component, and ii) a non-fugitive component present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application.
a) fire retardant components having a first hue, comprising a fire retardant salt; and b) a colorant which initially colors said composition to a second hue which contrast with the hue of said vegetation, said colorant comprising:
i) a fugitive color component, and ii) a non-fugitive component present in said composition in an amount which improves the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to said first hue after aerial application.
3. The concentrate composition of claim 2 which is a dry composition.
4. The concentrate composition of claim 2 which is a liquid concentrate composition.
5. The composition of any one of claims 1 to 4, wherein said non-fugitive component is red iron oxide.
6. The concentrate composition of claim 1, 2 or 4, wherein said fire retardant salt comprises a liquid ammonium polyphosphate; and wherein said non-fugitive component is red iron oxide.
7. The composition of claim 1, in which said non-fugitive component is titanium dioxide.
8. A fugitive color liquid fire retardant composition for aerial application to ground vegetation, said composition comprising:
a) fire retardant components comprising a fire retardant salt;
b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with normal vegetation or ground; and c) titanium dioxide, in an amount sufficient to improve the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to a neutral color which blends with normal vegetation or ground.
a) fire retardant components comprising a fire retardant salt;
b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with normal vegetation or ground; and c) titanium dioxide, in an amount sufficient to improve the aerial visibility of said composition, but in less than an amount which prevents said composition from fading to a neutral color which blends with normal vegetation or ground.
9. A method for fighting wildfires comprising the steps of:
applying a fire retardant composition to ground vegetation, which composition comprises:
a) fire retardant components comprising a fire retardant salt;
b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with the vegetation or ground; and c) a non-fugitive color component insoluble in an aqueous carrier which improves the aerial visibility of said composition, and said non-fugitive color component provided in less than an amount which prevents said composition from fading to a neutral color which blends with the vegetation or ground.
applying a fire retardant composition to ground vegetation, which composition comprises:
a) fire retardant components comprising a fire retardant salt;
b) a fugitive color component which improves the aerial visibility of said composition and which colors said composition to contrast with the vegetation or ground; and c) a non-fugitive color component insoluble in an aqueous carrier which improves the aerial visibility of said composition, and said non-fugitive color component provided in less than an amount which prevents said composition from fading to a neutral color which blends with the vegetation or ground.
10. The method of claim 9, wherein said non-fugitive color component comprises titanium dioxide.
11. The method of claim 9, wherein said non-fugitive color component comprises red iron oxide.
12. The method of claim 9, where said fire retardant salt comprises a liquid ammonium polyphosphate and said non-fugitive component is red iron oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/US94/08226 | 1994-07-21 | ||
| PCT/US1994/008226 WO1996003477A1 (en) | 1994-07-21 | 1994-07-21 | Fugitive color fire retardant composition for aerial application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2154122A1 CA2154122A1 (en) | 1996-01-22 |
| CA2154122C true CA2154122C (en) | 2005-02-22 |
Family
ID=22242767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002154122A Expired - Lifetime CA2154122C (en) | 1994-07-21 | 1995-07-18 | Fugitive colour fire retardant composition for aerial application |
Country Status (7)
| Country | Link |
|---|---|
| EP (2) | EP0911067B1 (en) |
| AU (1) | AU676762B2 (en) |
| CA (1) | CA2154122C (en) |
| DE (2) | DE69533524T2 (en) |
| ES (2) | ES2229560T3 (en) |
| PT (1) | PT911067E (en) |
| WO (1) | WO1996003477A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4702344A (en) * | 1986-03-20 | 1987-10-27 | Atlantic Richfield Company | Vent means for closed air system impact-type seismic source |
| US4721181A (en) * | 1986-03-31 | 1988-01-26 | Atlantic Richfield Co. | Base plate locator for seismic source |
| US6447697B1 (en) * | 1999-03-03 | 2002-09-10 | Astaris, Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
| US6676858B2 (en) * | 1999-03-03 | 2004-01-13 | Astaris Llc | Colorant liquid, method of use, and wildland fire retardant liquids containing same |
| AU2002216632B2 (en) | 2000-11-28 | 2006-01-12 | Perimeter Solutions Lp | Fire retardant compositions with reduced aluminum corrosivity |
| AU2002211757B2 (en) | 2000-11-28 | 2006-01-12 | Perimeter Solutions Lp | Biopolymer thickened fire retardant compositions |
| US6802994B1 (en) * | 2000-11-28 | 2004-10-12 | Astaris Llc | Fire retardant compositions containing ammonium polyphosphate and iron additives for corrosion inhibition |
| US6846437B2 (en) * | 2000-11-28 | 2005-01-25 | Astaris, Llc | Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors |
| WO2005014115A1 (en) * | 2003-07-23 | 2005-02-17 | Basf Aktiengesellschaft | Fire control composition and method |
| DE102009053186A1 (en) * | 2009-11-08 | 2011-05-12 | Caldic Deutschland Chemie Bv | Fire-extinguishing compositions, in particular dry powder mixtures, process for their preparation and use |
| FR3029795B1 (en) * | 2014-12-11 | 2021-01-29 | Stme | SYSTEM INCLUDING A DELAYING PRODUCT TO CONTAIN OR LIMIT THE PROGRESS OF A FIRE |
| ES2812305B2 (en) | 2020-12-31 | 2021-05-26 | Barricade Brs S L | FLAME RETARDANT COMPOSITION |
| EP4277772A1 (en) | 2021-01-18 | 2023-11-22 | Foresa Technologies, S.L.U. | Flame-retardant and smoke-suppressant formulation and cellulosic materials comprising the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB935590A (en) * | 1960-12-05 | 1963-08-28 | Berger Jensen & Nicholson Ltd | Improvements in or relating to fire-retardant protective and decorative coatings |
| US3196108A (en) * | 1962-12-06 | 1965-07-20 | Arizona Agrochemical Corp | Fire suppressing composition for aerial application |
| US3960735A (en) * | 1974-08-15 | 1976-06-01 | Early California Industries, Inc. | Corrosion-inhibited polyphosphate compositions |
| US4176071A (en) * | 1978-06-26 | 1979-11-27 | Early California Industries, Inc. | Corrosion inhibitor mixture for ammonium sulfate fire-retardant compositions and method for inhibiting corrosivity of such compositions |
| US4983326A (en) * | 1987-01-30 | 1991-01-08 | Monsanto Company | Fire retardant concentrates and methods for preparation thereof |
| US4839065A (en) * | 1987-01-30 | 1989-06-13 | Monsanto Company | Fire retardant concentrates and methods for preparation thereof |
| US4822524A (en) * | 1988-04-01 | 1989-04-18 | Chemonics Industries, Inc. | Xanthan gum enhanced fire-retardant compositions |
| US4879320A (en) * | 1989-03-15 | 1989-11-07 | Hastings Otis | Intumescent fire-retardant coating material |
-
1994
- 1994-07-21 WO PCT/US1994/008226 patent/WO1996003477A1/en active Application Filing
- 1994-07-21 AU AU74739/94A patent/AU676762B2/en not_active Expired
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1995
- 1995-07-14 ES ES99100007T patent/ES2229560T3/en not_active Expired - Lifetime
- 1995-07-14 EP EP99100007A patent/EP0911067B1/en not_active Expired - Lifetime
- 1995-07-14 ES ES95304934T patent/ES2136801T3/en not_active Expired - Lifetime
- 1995-07-14 EP EP95304934A patent/EP0693304B1/en not_active Expired - Lifetime
- 1995-07-14 PT PT99100007T patent/PT911067E/en unknown
- 1995-07-14 DE DE69533524T patent/DE69533524T2/en not_active Expired - Fee Related
- 1995-07-14 DE DE69512330T patent/DE69512330T2/en not_active Expired - Fee Related
- 1995-07-18 CA CA002154122A patent/CA2154122C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69512330T2 (en) | 2000-03-23 |
| EP0911067A3 (en) | 1999-06-02 |
| EP0911067A2 (en) | 1999-04-28 |
| WO1996003477A1 (en) | 1996-02-08 |
| PT911067E (en) | 2005-02-28 |
| EP0693304A1 (en) | 1996-01-24 |
| ES2229560T3 (en) | 2005-04-16 |
| EP0693304B1 (en) | 1999-09-22 |
| DE69533524D1 (en) | 2004-10-21 |
| DE69533524T2 (en) | 2005-08-18 |
| ES2136801T3 (en) | 1999-12-01 |
| EP0911067B1 (en) | 2004-09-15 |
| DE69512330D1 (en) | 1999-10-28 |
| AU7473994A (en) | 1996-02-22 |
| CA2154122A1 (en) | 1996-01-22 |
| AU676762B2 (en) | 1997-03-20 |
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