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Development of a Gas-Generator Propellant for a Rescue System for Submarines Based on the Energetic Binder GAP

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Development of a Gas-Generator Propellant for a Rescue System for Submarines Based on the Energetic Binder GAP NATO UNCLASSIFIED Development of a Gas-Generator Propellant for a Rescue System for Submarines based on the Energetic Binder GAP Dr. Peter Jacob BAYERN-CHEMIE / PROTAC P. O. Box 1131 D-84544 Aschau/Inn GERMANY SUMMARY Rescue systems for submarines currently use hydrazine which catalytically decomposes into hydrogen, nitrogen, ammoniac and water. These gases displace water out of the submarine’s bow and aft ballast tanks in order to surface the submarine by the generated buoyant force. The use of hydrazine got under criticism because of its toxic and carcinogenic properties. An additional risk is induced by the potential formation of an explosive gas-mixture due to the presence of hydrogen. Both led to the requirement for an alternative gas generating system to be installed in new submarines and eventually to replace existing hydrazine systems. The consequent objective was the development of a new solid propellant which generates a high amount of non flammable gases, being insoluble or slightly soluble in water and environmentally clean combustion products only. As a matter of principle only the gases nitrogen and carbon dioxide came into consideration. The energetic binder GAP was a candidate fuel for development because of its high amount of nitrogen (app. 42 %), oxygen and also its availability. The oxidizer strontium nitrate was selected because of its high density, good oxygen balance and the ability to form a stable slag which remains more or less in the gas generator. Additionally, because of the size of the gas generator, a castable propellant was preferred. The development of the propellant started with thermodynamic calculations in order to obtain an oxygen- balanced formulation and to determine the combustion temperature and combustion products. Based on these results, the propellant was developed on a laboratory scale in order to study the processibility and the influence of particle-size distribution of the oxidizer on the burning rate and pressure exponent. The influence of the curing agent and the equivalence ratio on the mechanical properties were studied. The propellant was also investigated in terms of compatibility and aging behavior. Today, the patented propellant and the gas generator are fully qualified by the German authorities WIWEB and WTD 91. The system passed all examinations successfully. The industrialisation took place in 2000 and 2001. The start of serial production for German customer (BWB) started in 2001. The new rescue system will be integrated into the U 212 submarines, currently built for the German and other European Navies. INTRODUCTION Rescue Systems for Submarines currently use hydrazine which catalytically decomposes into hydrogen, nitrogen, ammoniac and vaporous water. Besides the toxic properties of hydrazine, there is the theoretical possibility of an ignition of the exhaust gases due to the potential formation of oxyhydrogen gas. This resulted in the requirement to replace the existing “RESUS” system by an Inert Gas-generator Paper presented at the RTO AVT Specialists’ Meeting on “Advances in Rocket Performance Life and Disposal”, held in Aalborg, Denmark, 23-26 September 2002, and published in RTO-MP-091. RTO-MP-091 8 - 1 NATO UNCLASSIFIED NATO UNCLASSIFIED Development of a Gas-Generator Propellant for a Rescue System for Submarines based on the Energetic Binder GAP (INGA) with equivalent properties in respect of yield of gas, volume, weight, service life, operating reliability and shock resistance against water bombs. Additionally the combustion products must not be toxic or flammable. The study of an alternative system using a solid propellant started with a consideration of all possible gases which can be created chemically during gas generator burning. In order to get a high efficiency of the system, the generated gaseous products should be insoluble or only slightly soluble in water and exhibit a small molecular weight. Nitrogen, carbon monoxide, hydrogen, methane and oxygen are possible candidates. The noble gases helium, neon and argon can not produced chemically and were not considered further. Due to their small molecular weight carbon monoxide, hydrogen and methane yield in high volume even at small weight percentage. In order to avoid those combustible gases, the propellant formulation has to be oxygen-balanced. Oxygen is produced only by use of excess oxidizer. Herewith a decrease of burning temperature is achievable but oxygen also had to be avoided because of its corrosive effects on the boat structure. Each combustion of organic material unavoidably generates the components carbon dioxide and water. In fact those gases contribute only little to the displacement of water out of the ballast tanks. According to thermodynamic calculations carbon dioxide contributes due to slow rate of dissolving and diffusion into the water significantly (about 50 %). One original design goal of cool burning (1500 K) could not be fulfilled because the gas generator propellant has to be stoichiometrically balanced. In order to cool down the hot gases after the nozzle, water is mixed into the gas stream by an ejector. REQUIREMENTS FOR THE PROPELLANT Combustion Products • High amount of gases insoluble or slightly soluble in water • The amount of flammable gases must be out of the explosion limits at all time • All combustion products have to be environmentally clean and non-toxic Ballistic Properties • The rate of burning shall be between 5 and 7 mm/s at 100 bar • The operational pressure shall be between 70 and 130 bar • The pressure exponent shall be below 0.7 • The gas generator must burn stable even at high pressures Mechanical Properties • The mechanical properties between –10 °C and +40 °C should guarantee a safe burning of the gas generator even after an water-bomb attack at the submarine (400 g / < 5 msec) Service Life • The service life shall at least 10 years (without additional life extension programs) 8 - 2 RTO-MP-091 NATO UNCLASSIFIED NATO UNCLASSIFIED Development of a Gas-Generator Propellant for a Rescue System for Submarines based on the Energetic Binder GAP Environment • The gas generator should not produce any environmentally harmful or toxic combustion products. • The propellant formulation should not contain toxic components. Safety • The storage classification must not be 1.1 • The grain must not have detonative properties. Refurbishment • The refurbishment after the service life should be possible and easy to perform. ASSESSMENT OF NITROGEN RICH FUELS The following table summarizes the main properties of nitrogen rich fuels. The main focus lies on the nitrogen-content, processibility, burning temperature, burning rate, environmental properties, availability and price. Table1: Candidate Fuels (Nitrogen Rich) Formula Name N2-Content Properties Manufacturing [%] Process toxic raw material, NaN3 Sodiumazid 64,6 high burning rate, press only N2, cold burning, solid NH2 NIGU 53,8 cheap raw material, press HN C low burning rate, NHNO cold burning, solid 2 H expensive raw material, N 5-ATZ 82,3 moderate burning, press H N 2 C N moderate temperature, hygroscopic, N N solid teratogene NH NH2 TAGN 58,7 Produces much H2, expensive, press H2N N C * HNO3 NH NH not in large scale production, 2 explosive, solid N N N N C N N C N N expensive, N N − − GZT 78,8 press ⊕⊕ H H H H not in large scale production, N N C C solid H2N NH2 H2N NH2 toxic, produces much H2, – H2N-NH2 Hydrazene 87,4 liquid H expensive raw material, CH2 C O GAP 42,0 cast produces much N2, CH N 2 3 in serial production, liquid n RTO-MP-091 8 - 3 NATO UNCLASSIFIED NATO UNCLASSIFIED Development of a Gas-Generator Propellant for a Rescue System for Submarines based on the Energetic Binder GAP All the listed solid fuels (sodium azid, Nigu, 5-ATZ, TAGN and GZT) show an excellent amount of nitrogen and a relatively low burning temperature. But in order to manufacture a grain of about 150 kg the pressing technology appears inadequate. Nevertheless first tests with the systems Nigu/strontium nitrate, Nigu / strontium nitrate /ammonium nitrate, Nigu / ammonium nitrate, Nigu/ strontium nitrate / titanium dioxide and 5-ATZ/ammonium nitrate were performed. The burning behavior was tested by strands/Crawford. As a result, all those mixtures show a burning rate between 5 and 12 mm/sec at 100 bar with a pressure exponent between 0.75 and 1.15. Furthermore the ignition is very difficult. Therefore it became very quickly obvious that the energetic binder GAP was the only promising alternative. In terms of processibility, GAP allows to manufacture a castable propellant with the perspective to fulfil the requirements described above. ASSESSMENT OF OXIDIZERS In order to get an oxygen balanced propellant it is necessary to manufacture a mixture with a high content of solid oxidizer. It is also useful to select an oxidizer with a high nitrogen content and without chlorine for environmental aspects. It has further to be considered that different to HTBP-binders, GAP can not be filled with a high amount of solid oxidizer. Ammonium nitrate has both a high nitrogen and oxygen content. Drawbacks are low performance, low burning rates and phase transitions that influence the propellant properties. Furthermore this material is very hygroscopic. AP generates hydrochloride and exhibits a very high flame temperature while KPC has no nitrogen at all. Since the N2-content and the O2-content of potassium nitrate and strontium nitrate are similar, it was decided to use strontium nitrate, because of its higher density allowing to achieve a processibility during the mixing process. According to thermodynamic calculations strontium nitrate (SrO) forms a stable slag with a very high melting point which remains to a large extent in the gas generator. Table 2: Candidate Oxidizers Formula Name N2-Content O2-Content Density [%] [%] [kg/m³] NH4NO3 AN 35,0 60,0 1725 NH4ClO4 AP 11,9 54,5 1950 KClO4 KPC 0,0 46,2 2520 KNO3 Potassium nitrate 13,9 47,5 2109 Sr(NO3)2 Strontium nitrate 13,2 45,4 2986 THERMODYNAMIC ASSESSMENT With the propellant formulation according to Table 3 thermodynamic calculations have been performed.
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