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Development of a High-Performance HAN/HN-Based Low-Toxicity Monopropellant

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Development of a High-Performance HAN/HN-Based Low-Toxicity Monopropellant Trans. JSASS Aerospace Tech. Japan Vol. 14, No. ists30, pp. Pa_101-Pa_105, 2016 Development of a High-Performance HAN/HN-Based Low-Toxicity Monopropellant 1) 1) 2) 2) By Shinji IGARASHI, Apollo B. FUKUCHI, Nobuyuki AZUMA, Keigo HATAI, 2) 2) Hideshi KAGAWA and Hirohide IKEDA 1)IHI Aerospace Co., Ltd., Japan 2)Japan Aerospace Exploration Agency, Japan (Received July 31st, 2015) We have developed a hydroxylammonium nitrate (HAN)/hydrazinium nitrate (HN)-based low-toxicity monopropellant [high-performance, no-detonation propellant (HNP)] that has safety characteristics such as no autocatalytic reaction (no autocatalytic reaction: Combustion cannot continue without a source of heat) and no detonation. However, its specific impulse (Isp), a rocket engine performance indicator, was lower than that of hydrazine. Therefore, we investigated many types of compositions and found methanol to be suitable as a fuel ingredient for increasing the Isp of the developed propellant and reducing its viscosity. We produced the developed monopropellant consisting of HAN/HN/methanol/water and having a low viscosity and an Isp of 260 s at the laboratory scale. Key Words: HAN, HN, Methanol, Green Propellant Nomenclature calculated using NASA’s CEA computer program for chemical propellant performance prediction, and the HAN : Hydroxylammonium nitrate calculation conditions were as follows: vacuum, HN : Hydrazinium nitrate combustion pressure Pc = 1 MPaA, and nozzle expansion TEAN : Tri-ethanol-ammonium nitrate ratio 100. HNP : High-performance, no-detonation propellant We developed a hydroxylammonium Isp : Specific impulse nitrate/hydrazinium nitrate (HAN/HN)-based low-toxicity Tad : Adiabatic flame temperature monopropellant characterized by safety features such as tr : Reaction time of propellant with no autocatalytic reaction and no detonation but with a catalyst lower Isp value than that of hydrazine. 1,2) P : Combustion pressure c : Nozzle expansion ratio 2. Previous Work on HAN/HN-based Monopropellant : Density Isp : Density-specific impulse We developed an HAN/HN-based low-toxicity JISHA : Japan Industrial Safety & Health monopropellant that has safety characteristics such as no Association autocatalytic reaction and no detonation. In addition, we selected a low-viscosity composition to be able to employ 1. Introduction a conventional thruster. The details of the previous composition (hereinafter called HNP115) are listed in Several countries are working on the development of a Table 1. HNP115 has safety characteristics such as no low-toxicity monopropellant. Regulations pertaining to autocatalytic reaction and no detonation, but its Isp of 203 chemical substances, such as REACH in Europe, are s is lower than that of hydrazine (237 s). However, other becoming stringent in line with the trend of environmental works have achieved Isp values higher than that of protection, and hydrazine is affected by such regulations. hydrazine. Accordingly, there would be demand for a low-toxicity monopropellant in the future. In the USA, Green Table 1. Components and characteristics of HNP115. 3) Propellant Infusion Mission (GPIM) is planning to Composition HAN/HN/TEAN/Water = 46/23/6/25 (wt%) ※1 demonstrate a green propellant thruster system in-orbit in Theoretical specific impulse (s) 203 4) Theoretical adiabatic flame 1325 the near future. In Europe, the satellite PRISMA carried temperature※1 (K) Characteristics out an orbital flight in 2010. 5) The theoretical specific Density (g/cm3) 1.4 10 impulse (Isp) value achieved in these works is 260–270 s, Viscosity (mPa·s) Autocatalytic reaction No which is higher than that of hydrazine. The Isp value was ※1 Calculation conditions are Pc = 1.0 MPaA, = 100. Copyright© 2016 by the Japan Society for Aeronautical and Space Sciences and ISTS. All rights reserved. Pa_101 Trans. JSASS Aerospace Tech. Japan Vol. 14, No. ists30 (2016) Isp = 280 s 0 Isp = 270 s 3. Design of HNP Compositions 100 260 s 20 We tried to increase the Isp of HNP115. Furthermore, Detonation area 80 250 s HNP115 Increasing Isp we attempted to maintain the advantages of HNP115 240 s N 40 W H 60 a t such as no autocatalytic reaction and no detonation. + e N r A 200 s Figure 1 shows the components of the previous H 60 40 compositions in a ternary plot. The figure also shows the Detonation No Detonation 80 20 plots of Isp and the detonation area. Target area The TEAN component in the fuel was increased to （no detonation、, high Isp） 100 increase Isp in order to avoid the detonation area shown 0 100 80 60 40 20 0 in Fig. 2. As the amount of TEAN increases, the TEAN ※ Original data of this ternary map is taken from 8). viscosity of the composition increases because TEAN is Fig. 1. Contour map of Isp and detonation area of a solid ingredient soluble in water. The high-Isp area HAN/HN/TEAN/Water. that avoids the detonation area is indicated by a broken Table 2. Results of composition design. line in Fig. 1. This area represents high-viscosity HAN Propellant compositions that influence a thruster design. Therefore, Hydrazine9,10) we investigated measures to achieve high Isp and low (Conventional Improved Propellant) HNP115 (HNP202, HNP206 viscosity by replacing TEAN with a liquid ingredient. HNP207) We compared the toxicity, physical properties, Isp, and HAN/HN/ HAN/HN/ Composition N H 2 4 TEAN/Water Methanol/Water adiabatic flame temperature (Tad) of many fuel *1 *3 ingredients. Based on the results of this comparison, we Isp (s) 239 203 250–270 *1 *3 adopted methanol as the liquid fuel ingredient. Methanol Tad (K) 1170 1325 1508–2055 is readily available, and it has some actual use as a ρIsp *3 3 239 290 309–369 6,7) (g/cm ·s) low-toxicity monopropellant. Viscosity 7 We designed a few low-viscosity compositions with 0.9 <15*2 (Target) (mPa·s) at 15°C an Isp higher than that of hydrazine using methanol as a ※1 Theoretical Specific Impulse. Calculation conditions are Pc = fuel ingredient. Table 2 summarizes the results of our 1.0 MPaA, = 100. ※2 Viscosity of improved composition is an estimate. composition design exercise. ※3 Calculated based on 60% ammonia dissociation. We estimated the viscosity of the fuel compositions using methanol as a component, as shown in Fig. 2. The 0 100 Isp = 270 s figure shows that we can obtain a high Isp and low Isp = 280 s 260 s Isp = 270 s viscosity (10–15 mPa·s), similar to HNP115. In addition, 20 250 s viscosity = 10–15 mPa·s 80 for an Isp of 240 s (the same as hydrazine), the viscosity 240 s of the composition is less than 10 mPa·s, and we can N 40 W H 60 a Estimated Viscosity + te N r obtain compositions with much lower viscosity. A (mPa s) H 1 60 Figure 3 shows the Tad versus Isp of a few 40 5 monopropellants, namely the HAN/HN low-toxicity 10 15 80 monopropellant designed by us, conventional hydrazine 20 Isp = 240 s 20 viscosity = 5–10 mPas 25 monopropellant, and other low-toxicity propellants (Tad 100 30 0 and Isp are estimated). As can be seen from the figure, 100 80 60 40 20 0 there seems to be a similarity in the trends of our Methanol low-toxicity monopropellants and other low-toxicity Fig. 2. Isp and estimated viscosity of HAN/HN/methanol/water. monopropellants, i.e., Isp increases as the adiabatic flame temperature increases. Pa_102 S. IGARASHI et al.: Development of a High-Performance HAN/HN-Based Low-Toxicity Monopropellant 300 absence of a source of heat (heated wire in this case). 290 HNP203 280 Therefore, methanol is a candidate material for a 270 HNP202 composition that has a high Isp and the desired safety 260 characteristics. 250 Isp [s] Isp 240 IA's high Isp compositions 230 LMP-103S(estimated) ※ 220 AF-315E(estimated) Table 3. Results of lab-scale production and evaluation of SHP163(estimated) improved compositions. 210 Hydrazine(60% Ammonia Dissosiation) 200 HAN Propellant 1000 1200 1400 1600 1800 2000 2200 2400 2600 Hydrazine6) Properties HNP202, Tad [K] (Conventional) HNP115 HNP206, ※ Isp and Tad of these compositions were calculated by IA HNP207 from the following sources: 11, 12, 7). Fig. 3. Relationship between Isp and Tad of low-toxicity 7 7–13 Viscosity (mPa·s) 0.9 monopropellants. at 15°C at 15°C Density (g/cm3) 1.0 1.4 1.2–1.4 4. Results of Lab-scale Production and Evaluation of Improved Compositions pH (-) 10.1–10.7 1.3 1.3–1.4 Onset temperature 100–120 >170 140–170 4.1. Results of lab-scale production and data (°C) @ 1 atm collection No Autocatalytic reaction No No We produced a few compositions (including HNP202, (over 5 MPa) HNP206, and HNP207) in quantities of up to 1 kg for Detonable No No No analysis on the basis of composition design.3) We (Φ10-mm steel pipe) (Isp 260 s) obtained various characteristics of the compositions, 0 such as their physical properties (viscosity, density, and 100 Isp = 270s Isp = 280 s 260s pH) and safety properties (exothermic onset temperature, 20 250s 80 burning rate, and detonation). If the propellant has the 240s Calculated by CEA, and the calculation conditions autocatalytic reaction characteristic, it can decompose are Pc = 1 MPaA, 40 Wa N 60 H te when passing through a feed tube to a fuel tank, which + r N A ▲ could cause the tank to burst. Table 3 summarizes the H 60 Partial Reaction 40 gathered data. The viscosities employed herein were Water 6 % × No Detonation Water 12 % useful for achieving the target value below the 80 20 composition design point. The densities and pH 100 employed herein were useful for achieving the same 0 values as those of HNP115.
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