USOO6328831B1 (12) United States Patent (10) Patent No.: US 6,328,831 B1 Wagaman (45) Date of Patent: Dec. 11, 2001 (54) GAS-GENERATING LIQUID 6,179,937 * 1/2001 Leveritt et al. ........................ 149/45 COMPOSITIONS (PERHAN) OTHER PUBLICATIONS (75) Inventor: Kerry L. Wagaman, Bryantown, MD Anderson, W., et al. Low Cost Propulsion Using a High (US) Density, Storable, and Clean Propellant Combination. Mul, et al. Search For New Storable High Performance (73) Assignee: The United States of America as Propellants, (AIAA-88-3354, AIAA/ASME/SAE/ASEE represented by the Secretary of the 24th Joint Propulsion Conference, Boston, Jul. 1988. Navy, Washington, DC (US) Rusek, J., New Decomposition Catalysts And Characteriza (*) Notice: Subject to any disclaimer, the term of this tion Techniques For Rocket-Grade Hydrogen Peroxide J. of patent is extended or adjusted under 35 Propulsion and Power, 1996, 12,574–579. A document entitled Advanced Chemical Propulsion Sys U.S.C. 154(b) by 0 days. tems dated Nov. 21, 1995. Berezovsky, Pyrogen Fire Suppression System-Marine & (21) Appl. No.: 09/447,271 Vehicle Applications Dated Aug. 1997. (22) Filed: Nov. 23, 1999 Thomas, Martin, Fire Research News 20. (51) Int. Cl. .............................................. C06B 31/00 * cited by examiner (52) U.S. Cl. ................................................................ 149/45 Primary Examiner Michael J. Carone (58) Field of Search ..................................... 149/45-108.8 ASSistant Examiner Aileen J. Baker (56) References Cited (74) Attorney, Agent, or Firm Mark Homer U.S. PATENT DOCUMENTS (57) ABSTRACT H1768 1/1999 Mueller et al. A family of water-based, gas-generating liquid compositions 3,145,082 8/1964 Rausch et al. ....................... 423/275 is described. A composition of the present invention 3,561,533 2/1971 McKinnell. includes: hydrogen peroxide, hydroxylammonium nitrate, 3,790,415 2/1974 Tomic . and water. Compositions of the present invention may be 4,047,988 9/1977 Weill et al.. mixed with fuels to make monopropellants or used in 4,527,389 * 7/1985 Biddle et al. .......................... 60/207 bipropellant or hybrid Systems. Alternate uses of the present 5,607,181 3/1997 Richardson et al. invention include breathable gas generation or use as an 5,648,052 7/1997 Schaefer et al. ..................... 422/305 5,703,323 * 12/1997 Rothgery et al. ...................... 149/88 oxygen Source in welding. 6,013,143 * 1/2000 Thompson ............................... 149/1 6,098,516 8/2000 Gazonas .............................. 86/20.15 22 Claims, 2 Drawing Sheets Freezing Points for PERHAN Formulations H2O2= 100.0 Freezing Point -60.O -50.0 WATER=O.O -- - - - - 40.0 -50.0 -2O.O - - - - - 10.0 O.O HAN=1 OO.O WATER= 1 OO.O U.S. Patent Dec. 11, 2001 Sheet 2 of 2 US 6,328,831 B1 SUIO!QeInULIJOJINIVH?IGIAIJOS????SUI3OI 3–0IJI US 6,328,831 B1 1 2 GAS-GENERATING LIQUID Gas-generating Systems in other applications also have COMPOSITIONS (PERHAN) problems associated with them. For example, chlorate-based "chlorate candle' oxygen BACKGROUND OF THE INVENTION generators are used for emergency breathable oxygen in 1. Field of the Invention Some airplanes and in welding applications. Because of the Solid nature of the Sodium chlorate, many of these devices The present invention relates to energetic and gas cannot be turned off once triggered, and the heat production generating compositions, and in particular to oxidizing from Such a device can prove to be a fire hazard. A compositions. liquid-based oxygen generator might overcome this prob 2. Description of the Related Art lem. Moreover, chlorate-based devices typically produce There are numerous applications for gas-generating com Some byproduct chlorine, which is toxic, in the breathable positions. Energetic gas-generating compositions are com gas, and do not produce any diluent for the generated monly used, for example, in rocket propulsion Systems as OXygen. well as torpedos, Safety air bags, etc. Oxygen-generating Examples of liquid gas-generating and explosive compo compositions also have utility in breathable air generators 15 Sitions of the contemporary art are seen in the following U.S. and underwater welding. Patents. U.S. Pat. No. 3,561,533, to McKinnell, entitled Of particular interest among these compositions are those Controlled Chemical Heating OF A Well Using Aqueous which are liquids, in particular liquids which are oxidizers. Gas-In-Liquid Foams, describes a two-component hyper Liquids are necessary for many propulsion Systems since golic reaction System in which an aqueous foam of hydra they can be pumped, and liquids are in general easier to Zine or dimethylhydrazine and an aqueous foam of hydrogen handle and Store than Solids. The most commonly used peroxide are mixed. The System is used to heat oil wells. liquid oxidizers for rocket propulsion have generally been U.S. Pat. No. 3,790,415, to Tomic, entitled Chemical liquid oxygen (LOX), inhibited red fuming nitric acid Foaming And Sensitizing Of Water-Bearing Explosives (IRFNA), hydrogen peroxide (H2O), aqueous hydroxylam With Hydrogen Peroxide, describes addition of hydrogen monium perchlorate (HAP) and nitrogen tetroxide (NTO). 25 peroxide as a foaming agent/Sensitizer to water-bearing Each of these liquid oxidizers has problems associated with explosives having ammonium nitrate and fuel. Here, the use. For example, LOX requires cryogenic Storage and is hydrogen peroxide is added to the thickened or emulsified dangerous when spilled. IRFNA, NTO and HO also have explosive mixture, and decomposes in the formulation to handling and toxicity problems. HAP offers some provide oxygen bubbles for foaming before the mixture is advantages, but Suffers from the presence of hydrochloric detonated. acid in the generated gas. Most of the liquid oxidizers in U.S. Pat. No. 4,047,988, to Weill et al., entitled Liquid current use present a vapor toxicity or contact hazard, and Monopropellant Compositions, describes a monopropellant are hypergolic, that is, spontaneously combusting, in the which is an aqueous Solution of a secondary or tertiary presence of fuels. amine, and an oxidizer Such as perchloric or nitric acid. Thus, there are in fact a limited number of available 35 Hydrogen peroxide is also mentioned as a possible oxidizer. choices of liquid oxidizers. That there is a need to fill the Here, the amine apparently Serves as the fuel in the mono technology "gap' in liquid oxidizers of the contemporary art propellant. Properties of the compositions including low is Seen, for example, in the following articles. In Mul, et al., freezing temperature, and use as a torpedo propellant, are described. Search For New Storable High Performance Propellants, 40 (AIAA-88-3354, AIAA/ASME/SAE/ASEE 24 Joint Pro U.S. Pat. No. 5,607,181, to Richardson et al., entitled pulsion Conference, Boston, July 1988), the authors discuss Liquid-Fueled Inflator With A Porous Containment Device, the need for Storable, non-cryogenic propellants with better describes an automotive airbag inflator using a liquid mono performance properties. They discuss nitric acid, NTO and propellant composed of a hydroxylamine nitrate (HAN)/ hydrazinium perchlorate as Storable oxidizers. 45 triethanolamine nitrate (TEAN)/water system. A system Another problem with the available liquid oxidizers is that with hydrazine and hydrogen peroxide as liquid fuel com they are mostly limited to a single composition, and thus a ponents is also mentioned. HAN is a relatively expensive Single Set of performance and physical properties. That is, component, however. Moreover, TEAN serves as a fuel in they are not formulated to achieve different values of per this mixture, So the mixture probably cannot Serve as a formance and physical parameters. Thus, variation of per 50 general oxidant for other fuels. formance properties of propellant Systems using these oxi In addition to the above patents, U.S. Statutory Invention dizers can only be achieved by varying the composition of Registration No. H1,768, to the fuel, thus limiting design options. Mueller et al., entitled Oxidizing Agent, describes liquid Anderson, W., et al., Low Cost Propulsion Using A oxidizers comprising water, hydroxylammonium nitrate, High-Density, Storable, and Clean Propellant Combination, 55 and ammonium nitrate or hydrazine mononitrate. Two oxi discuss the need for nontoxic, Storable, restartable, throttle dizing agents designated OXSOL 1 and OXSOL 2 are able and high density impluse Systems for rocket motorS. described. Discussed applications include use in gas gen They Suggest the use of high concentration hydrogen per erators for air bags, rocket propellants and torpedo propel oxide as a propellant. Although the authors describe hydro lants. gen peroxide as nontoxic, direct human contact with hydro 60 A document entitled Advanced Chemical Propulsion Sys gen peroxide is extremely dangerous. tems discusses the need to replace hydrazine as a fuel, and Rusek, J., New Decomposition Catalysts And Character suggests use of HAN/TEAN in a catalytic thruster. As noted ization Techniques For Rocket-Grade Hydrogen Peroxide, J. above, HAN is relatively expensive, and HAN/TEAN sys of Propulsion and Power, 1996, 12, 574-579, discusses the tem probably cannot be used as a general oxidant with other use of hydrogen peroxide as a rocket propellant, both as a 65 fuels. monopropellant and as an oxidizer with hydrazine hydrate/ An additional examples of a possible utility of a gas methyl alcohol fuel. generating System is seen