Paper # 070HE-0247 Topic: Heterogeneous Combustion 8th U. S. National Combustion Meeting Organized by the Western States Section of the Combustion Institute and hosted by the University of Utah May 19‐22, 2013 Experimental Investigation of Pressure Effect on Ignition Delay of Monomethylhydrazine, 1,1‐Dimethylhydrazine, Tetramethylethylenediamine and 2‐Dimethylaminoethylazide with Nitric Acid S. Q. Wang and S. T. Thynell Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, USA A drop-on-pool impingement setup, coupled with a high-speed camera, was used to investigate the ignition delay of several hydrazine-, amine- and azide-based fuels, including monomethylhydrazine (MMH), 1,1-dimethylhydrazine (UDMH), tetramethylethylenediamine (TMEDA) and 2-dimethylaminoethylazide (DMAZ), with white fuming nitric acid (WFNA) as the oxidizer. The drop-on-pool impingement experiments were conducted in an N2 purged chamber with pressures ranging from -40 kPa to 600 kPa (gauge). In general, the ignition delay of hydrazines (MMH and UDMH) decreases with increasing pressure, whereas the ignition delay of TMEDA and DMAZ increases with increasing pressure. In addition to the pressure effect, the ignition delay of MMH/WFNA is also significantly affected by the type of droplet-pool interaction. The droplet stays within the pool after impingement at sub-atmospheric pressures (type I), while the droplet is ejected from the pool at elevated pressures (type II). The critical pressure is about 0 kPa (g) at which either interaction type was observed. The ignition delay of type I interaction is much longer than that of type II at that pressure. The ignition delay of a mixture of 33.3% DMAZ and 66.7% TMEDA was also studied. This mixture has a shorter ignition delay than both pure TMEDA and DMAZ. In addition, the pressure effect on the ignition delay of this mixture is not significant. 1. Introduction Hypergolic propellants are pairs of liquid fuels and oxidizers in which ignition occurs spontaneously upon contact between the two liquids, thereby eliminating the need for a complex ignition system [1]. The reliable restart capability of these types of engines makes them ideal for spacecraft maneuvering. An important criterion to evaluate the performance of hypergolic bipropellants is the ignition delay, which is defined as the time from the physical contact of liquid fuel and oxidizer to the achievement of ignition. A long ignition delay can cause a ‘hard-start’ problem in which unburnt fuel and oxidizer in the combustion chamber accumulate, then suddenly ignite to generate damaging pressure spikes [2]. One major factor that determines the ignition delay is the pre-ignition chemical reactions of the two reactants. For example, monomethylhydrazine (MMH, CH3NHNH2) has a shorter ignition delay than tetramethylethylenediamine [TMEDA, (CH3)2NCH2CH2(CH3)2] when red fuming nitric acid (RFNA) is used as the oxidizer, because the hydrogen abstraction from an amino group by NO2 has a lower barrier than that from the methyl group [3-5]. Another major factor that can significantly affect the ignition delay is the extent of initial contact and mixing between liquid fuel and oxidizer. For the same fuel and oxidizer pair, the ignition delay in an engine test is shorter than that obtained from a drop test [6], because the engine test has a better mixing than drop test. In addition, ignition delay obtained by the same method (i.e., drop test) may also vary from one to another because it may be sensitive to many other factors such as ambient pressure and temperature, size of droplet and pool, and even the relative speed of impingement. Therefore, the measurement of ignition delay is meaningful only when the test method and conditions are clarified. In an earlier work, a drop-on-pool impingement setup was developed to study the hypergolic interaction and measure the ignition delay of various hypergolic pairs in an open environment and at ambient pressure [7, 8]. In this work, however, a modified drop test setup is developed to study the pressure effect on the ignition delay of four fuels with white fuming nitric acid (WFNA). The molecular structure of the four fuels, monomethylhydrazine (MMH), 1,1-dimethylhydrazine (UDMH), tetramethylethylenediamine (TMEDA) and 2-dimethylaminoethylazide (DMAZ), are shown in Fig. 1. The two hydrazines are well-known fuels which have been deployed for decades in rocket engines and spacecraft [1]. TMEDA and DMAZ are less toxic than hydrazines and are considered as potential alternative fuels for MMH [8-10]. In addition, a mixture of DMAZ and TMEDA, with a mass ratio of 2:1, was claimed to have both a density impulse and ignition delay that are comparable to MMH [6]. Therefore, the pressure effect on the ignition delay of this mixture is also examined in this work. H3C H3C H3C H3C NCH2 CH3 NNH2 NCH2 NH NH2 + - H3C CH2 N H3C H3C CH2 NN N CH3 (MMH) (UDMH) (TMEDA) (DMAZ) Figure 1. Molecular structures of the considered fuels 2. Experimental Setup A schematic diagram of the drop-on-pool impingement setup is shown in Fig. 2. About 100 µL WFNA is deposited in a glass vial (inner diameter is 0.5 inch). The glass vial is then placed in a bottom cylindrical chamber with an inner diameter of 2 inches piston and length of 5 inches. A syringe dispenses the fuel, and it is (driven by pneumatic actuator) placed above the glass vial and points to the center of the oxidizer syringe pool. The syringe is kept in the top cylindrical chamber, and the drop is released by the motion from the piston of a pneumatic actuator. The chamber is first purged by N2 and is then either pressurized by the same purge gas or the pressure is reduced by a purge outlet photodiode vacuum pump. In each test, about 10 µL fuel is loaded in the He-Ne laser syringe so that only one droplet (about 7 µL) is produced. The drop-on-pool impingement interaction as well as the subsequent fuel droplet purge flow gas-phase ignition and combustion processes were recorded by a distributor WFNA Phantom V710 high-speed camera, through an optical access glass window with a thickness of 1 inch. A He-Ne laser and a corresponding photodiode, placed underneath the syringe but N gas cylinder above the glass vial, triggers the camera through a reduction in 2 the photodiode signal as the drop of fuel intersects the laser beam. vacuum pump The ignition delay is defined as the time delay between the contact of two liquids and the occurrence of luminosity. The high Figure 2. Schematic diagram of strand burner speed videos were acquired at a frame rate of 5000 fps. Therefore the temporal resolution of ignition delay measurement is 0.2 ms. 3. Results and Discussion 3.1 MMH and UDMH The drop-on-pool impingement interactions and ignition delays of MMH and UDMH with WFNA were studied from sub-atmospheric to elevated pressures. For MMH/WFNA, two different types of drop-pool interactions were observed. At pressures below 0 kPa (g), the droplet stays in the nitric acid pool after the impact (type I), while at elevated pressures the droplet is ejected from the oxidizer pool and then suspended above the pool surface (type II). Typical physical observations from the two types of interaction are illustrated in Fig. 3a and 3b, which show selected images from a test at reduced pressure (-20 kPa (g)) and a test at elevated pressure (50 kPa), respectively. Type I: as shown in Fig. 3a, the droplet impinges on the nitric acid pool at t = 0. An aerosol cloud, which is believed to be MMH nitrates [7], is formed along the path of the falling droplet through the reactions between the fuel droplet and the nitric acid vapor that is confined in the glass vial. Upon impact, liquid- phase reactions will occur at the contact (a) t = 0 t = 80 ms t = 87 ms t = 300 ms surface which forms nitrates, generate abundant heat, and produce plenty of gases. It is generally believed that a gas layer (or vapor layer) will be formed between the droplet and pool surface [11]. In this case, the gas flow is not strong enough to eject the droplet from the pool. Meanwhile, the vapors of the (b) t = 0 t = 8 ms t = 20 ms t = 200 ms two reactants react above the pool to form a nitrate cloud as shown at t = 80 ms. When the temperature rises to a certain level, the accumulated nitrate cloud decomposes rapidly followed by a gas-phase ignition which occurs at t = 87 ms. A stable cone-shape diffusion flame sustained for about 350 ms. (c) t = 0 t = 4.6 ms t =10 ms t = 20 ms Type II: as shown in Fig. 3b, the reactions between the droplet and pool Figure 3. Droplet-on-pool impingement: a) MMH/WFNA at -20 kPa; b) surface generate a gas flow that is strong MMH/WFNA at 50 kPa; 3) UDMH/WFNA at 0 kPa (gauge pressure) enough to eject the fuel droplet from the nitric acid pool at t = 8 ms. Luminosity is observed at the moment of ejection, and a diffusion flame is formed between the droplet and the pool. With the establishment of a force balance between the droplet gravity and the repelling force from gas flow, the MMH droplet is floating on and rolling along the WFNA pool surface smoothly for about 200 ms followed by rapid disintegration into many smaller droplets. The relation between the gravity (G) of droplet and the repelling force (F) from the gas flow determines whether the droplet will be ejected or not. If F > G, the droplet will be ejected.