Neidert, Jamie B. (3175 Southampton Drive Jeffersonton, VA, 22724, US)
Black III, Robert E. (14603 Farm Pond Court Centreville, VA, 20120-1649, US)
Lynch, Robert D. (7312 Stuart Circle Warrenton, VA, 20187, US)
Martin, James D. (11113 Luxbury Court Manassas, VA, 20109-7426, US)
| 1. | An ammonium nitratefree fire suppressant composition comprising potassium nitrate in an amount sufficient to yield at least about 10 wt. °o of potassium carbonate when the composition is combusted. |
| 2. | The fire suppressant composition as in claim 1, further comprising a guanidine salt. |
| 3. | The fire suppressant composition as in claim 2, wherein the guanidine salt is selected from aminoguanidine nitrate, guanidine nitrate, triaminoguanidine nitrate, diaminoguanidine nitrate, and ethylenebis (aminoguanidinium) dinitrate. |
| 4. | The fire suppressant composition of claim 1, further comprising copper phthalocyanine. |
| 5. | The fire suppressant composition of claim 1 or 4, further comprising particles of iron or iron oxide. |
| 6. | The fire suppressant composition of claim 1. further comprising a water soluble binder. |
| 7. | The fire suppressant composition of claim 1, wherein the potassium nitrate is present in an amount between about 30 wt. °o to about 75 wt.. based on total composition weight. |
| 8. | The fire suppressant composition of claim 7. wherein the potassium nitrate is present in an amount between about 40 wt. % to about 60 wt. %. |
| 9. | The fire suppressant composition of claim 7 or 8, further comprising guanidine nitrate in an amount between about 30 wt. % to about 65 wt. °o. based on the total composition weight. |
| 10. | The fire suppressant composition of claim 9. wherein the guanidine nitrate is present in an amount between about 40 to about 55 wt. %. |
| 11. | A fire suppressant composition comprising. based on total composition weight. between about 40 wt. % to about 60 wt. °o potassium nitrate ; between about 40 to about 55 wt. °o guanidine nitrate : less than about 1. 5 wt. °o iron oxide powder : and less than about 5 wt. °ó copper phthalocyanine. |
| 12. | The fire suppressant composition of claim 11, wherein the iron oxide powder is present in an amount of about 0. 5 wt. %. |
| 13. | The fire suppressant composition of claim 11, wherein the copper phthalocyanine is present in an amount less than about 2 wt. %. |
| 14. | A method of suppressing a fire, which comprises applying to a fire a reaction product of the fire suppressant composition of claim 1, 10 or 11. |
BACKGROUND AND SUMMARY OF THE INVENTION The most effective conventional gaseous fire extinguishing systems available comprise the HALON-class of flame retardants and fire extinguishers. which enjoy wide usage and acceptance within the civilian and military communities. For example, HALON 104 containing carbon tetrachloride (CC14) is conventionally used to fight electrical fires. The most effective and widely used fire extinguishing agents contain bromine compounds which thermally decompose in a fire or flame to produce the bromide anion (Br) which disrupts the chain reactions involved in the burning process.
However, the HALON-class of fire extinguishers are environmentally unacceptable and are believed to cause depletion of the upper atmosphere ozone layer. Accordingly, the manufacture of HALONS was banned on December 31. 1994 and the manufacture of chlorofluorocarbons (CFCs) was banned the following year on December 31. 1995.
There is, therefore. an urgent need for effective alternate fire extinguishing systems that do not involve HALONS. It is toward providing such a need that the present invention is directed.
Broadly, the present invention is embodied in fire suppressant compositions which are substantially free of ammonium nitrate and which comprise potassium nitrate in an amount sufficient to generate at least about 10 wt. % potassium carbonate when combusted. Most preferably, a guanidine salt, such as guanidine nitrate. is used in combination with the potassium nitrate.
These, as well as other, aspects and advantages of the present invention will become more clear from the following detailed description of the preferred exempiary embodiments thereof which follows.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING FIGURE 1 is a graphical plot of burning rate (in/sec) versus pressure (psi) for formulations S1-S2 identified in the Examples below ; and FIGURE 2 is a graphical plot of ballistic gas generator tests using composition S1 in the Examples below and generators conditioned to 80°C and 21 °C. respectively.
DETAILED DESCRIPTION OF THE INVENTION The compositions of this invention are free of ammonium nitrate (AN).
Instead, as a necessary component, the compositions of this invention will include potassium nitrate (KN) in an amount sufficient to yield at least about 10 wt. % potassium carbonate (K2CO3) in the combustion gases when the composition is combusted. Most preferably, the KN component will be used in amounts ranging between about 30 wt. % to about 75 wt. %, and more preferably between about 40 wt. °ó to about 60 wt. %.
Guanidine salts or derivatives may also be employed in combination with the KN component. Suitable guanidine salts for use in the present invention include aminoguanidine nitrate (AGN), guanidine nitrate (GN), triaminoguanidine nitrate (TAGN), diaminoguanidine nitrate (DAGN), and ethylenebis- (aminoguanidinium) dinitrate (EBAGN). GN is particularly preferred. The guanidine salt is employed in the compositions of this invention in an amount between about 30 wt. °h to about 65 wt. °s. and more preferably between about 40 to about 55 wt. °O. based on the total composition weight.
The compositions of this invention may also further comprise a minor amount of a water-soluble organic binder. The water-soluble organic binder may comprise guar gums. polyvinylpyrrolidone (PVP), polyacrylonitrile (PCN), polyvinyl alcohol (PVA) and water-soluble cellulosics such as hydroxyethylcellulose (HEC) and
carboxymethyl cellulose (CMC). The water-soluble organic binder may be present in the range of about 1 wt. % to about 15 wt. %, and more preferably between about 1 to about 5 wt. °o.. based on total composition weight.
A burning rate modifier in the form of a powdered metal or its corresponding metal oxide, salt or complex may also be present in the compositions of the present invention. The burning rate modifier that may be employed in accordance with the present invention inclues for example, iron, copper, magnesium, aluminum. tungsten, titanium, zirconium, hafnium. calcium strontium, bismuth. tin and zinc and their respective metal oxides. salts and complexes. One particularly preferred burning rate modifier is superfine iron oxide powder marketed as NANOCAT material commercial available from Mach I Corporation of King of Prussia, PA.
This preferred iron oxide powder has an average particle size of about 3 nm, a specific surface area of about 250 mgm, and bulk density of about 0. 05 gm/ml. The iron oxide powder may be employed in the compositions of this invention in an amount less than about 1. 5 wt. % and typically about 0. 5 wt. %.
Copper compounds, such as copper phthalocyanine, may also be employed as burning rate modifiers in the compositions of the present invention. Such copper compounds may be used in an amount less than about 5 wt.%, and typically about 2 wt.%.
The burning rate modifiers noted above may be used singly. or in admixture with one or more other burning rate modifiers and/or augmentors as may be desired.
The compositions of this invention may be uncatalyzed (i. e., the composition is void of a combustion catalyst), or may be catalyzed. That is. the composition may include a combustion catalyzing effective amount of a combustion catalyst.
Additives conventionally employed in gas generant compositions may also be employed in the compositions of the present invention, provided they are compatible with all other components and with the general objectives of the present invention.
Non-energetic flame retardant chemicals can also be used to supplement the formulations of the present invention. In addition, flame inhibition chemicals, such as sodium bicarbonate. potassium bicarbonate. potassium carbonate. potassium
chloride and monoammonium phosphate compounds can be employed as additives to the compositions of the present invention.
When it is indicated that a fire is present or imminent in. for example. a cargo bay of an airplane or ship, or in vehicles or buildings, the compositions of the present invention may be actuated to produce and release a mixture of water vapor and inert gases in which potassium carbonate with, or without combustion species of the metal and/or metal oxide are entrained. The fire is effectively suppressed by chemical action of the generated potassium carbonate and by action of generated inert gases in reducing the oxygen content to a level that will not sustain combustion. Moreover, since the compositions of the present invention generate significant amounts of potassium carbonate, fire regeneration is substantially prevented.
The compositions employed in the present invention have low pressure exponents, high burning rates and low flame temperatures. The reaction times to produce the water vapor and inter gaseous products are typically on the order of milliseconds, thereby providing rapid and efficient fire suppression.
The present invention will be further understood from the following non-limiting Examples.
Examples Example 1 Table 1 below exemplifies fire suppression compositions, identified as samples S1-S5, according to the present invention, in comparison to a sample, designated CS1, in accordance with commonly owned U. S. Patent Application Serial No. 09/109. 156 filed on July 2, 1998 (the entire content of which is expressly incorporated hereinto by reference). All theoretical calculations in Table 1 below are at 2000 psi operating pressure.
Table 1 Propellant C1 S1 S2 S3 S4 S5 AN, % -- -- -- -- -- -- KN, % 40 44.9 52.1 56.8 47.3 48.5 GN, % 60 52.6 42.4 35.7 49.2 47.5 PVA, % -- -- 3 5 1 1.5 Copper Phthalocyanine 2 2 2 2 2 Fe3O4 -- 0.5 0.5 0.5 0.5 0.5 Tc, K 1962 1985 2080 2096 2065 2068 Te, K 1261 1308 1269 1309 1226 1237 Moles of gas 3.0 2.7 2.7 2.6 2.9 2.8 K2CO3, % 27.3 30.7 35.6 38.8 32.3 33.1 H2O, % 26.6 23.8 21.7 20.4 23.1 22.8 N2, % 33.1 30.7 27.1 24.6 29.5 28.9 CO2, % 13.0 14.1 14.8 15.4 14.3 14.5 Fe3O4, % -- 0.5 -- -- -- -- Fe2O3, % -- 0.5 0.5 0.5 0.5 Cu, % 0.2 -- -- 0.2 0.1 Cu Oxides, % -- -- 0.3 0.3 0.1 0.1 *All theoretical calculations run at 2000 psi operating pressure.
Example 2 The compositions S1-S5 were subjected to aging/cycling tests, with the results thereof being shown in Table 2 below.
TABLE 2 Propellant: S1 S2 S3 D4 S5 Pellet crush stress, psi 58766823672858446604 Baseline Strain. to 9. 07. 36. 97. 27. 2 Pellet diameter. in. 0. 523 0. 524 0. 524 0. 523 0. 523 Pellet crush stress, psi 5173 7059---6073 6320 (-40OC Strain, % 8. 410-9. 39. 3 Diameter. in. 0. 527 0. 526---0. 526 0. 526 50 cycles Pellet crush stress, psi 5853 7039 7738 6262 6468 (-40°C to 107°C) Strain, % 11. 9 11. 3 10. 9 8. 4 9.0 Diameter, in. 0. 526 0. 527 0. 526 0. 529 0. 526 100 cycles Pellet crush stress, psi 5806 7270 6973 6581 6855 (-40°C to 107°C) Strain, % 12. 3 11. 6 9. 7 10. 8 10. 7 Diameter, in. 0. 528 0. 529 0. 530 0. 526 0. 526 200 cycles Pellet crush stress, psi 5511 7272 6989 6289 6409 (-40°C to 107°C) Strain, % 14. 6 12. 7 11. 9 12. 6 11. 3 Diameter, in. 0. 532 0. 530 0. 533 0. 529 0. 529 107°C Aging Pellet crush stress, psi 6265 7709 8297 6865 7003 17 days Strain, % 11. 0 11. 0 10. 5 10. 1 10. 0 Diameter, in. 0. 525 0. 525 0. 524 0. 525 0. 525 Example 3 Compositions S1-S5 were subjected to burning rate tests. with the results thereof being graphically depicted in accompanying FIGURE 1. As can be seen, all compositions advantageously exhibited increased burning rates with an increase in pressure.
Example 4 Composition S1 was further characterized in ballistic gas generator configurations tested at ambient (21°C) and hot (80°C) conditions. As shown in accompanying FIGURE 2, the composition exhibited low temperature sensitivity to burning rate. This allows operation across a wide range of temperatures and enables use of the composition in wider range of applications.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment. it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.