Combustion and Flame 159 (2012) 13141320

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Combustion and Flame

journal homepage: www.elsevier.com/locate/combustame

Deagration-to-detonation transition via the distributed photo ignition of carbon nanotubes suspended in fuel/oxidizer mixtures
Daniel J. Finigan, Brian D. Dohm, Jeffrey A. Mockelman, Matthew A. Oehlschlaeger
Department of Mechanical, Aerospace, and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY, USA

a r t i c l e

i n f o

a b s t r a c t
Here the promotion of ame acceleration and deagration-to-detonation transition (DDT) using the distributed photo ignition of photo-sensitive nanomaterials suspended in fuel/oxidizer mixtures is demonstrated for the rst time. Distributed photo ignition was carried out by suspending single-walled carbon nanotubes (SWCNTs) with Fe impurity in quiescent C2H4/O2/N2 mixtures and ashing them with an ordinary Xe camera ash. Following the ash, the distributed SWCNTs photo ignite and subsequently provide a quasi-distributed ignition of the C2H4/O2/N2 mixture. In a closed detonation tube the quasi-distributed photo ignition at one end of the tube leads to the promotion of ame acceleration and DDT and, for sensitive C2H4/O2 mixtures, appears to lead to direct detonation initiation or multiple combustion fronts. The DDT run-up distance, the distance required for the transition to detonation, was measured using ionization sensors and was found to be approximately a factor of 1.5 to 2 shorter for the distributed photo ignition process than for traditional single-point spark ignition. It is hypothesized that the increased volumetric energy release rate resulting from distributed photo-ignition enhances DDT due to the decreased ignition delay and greater early-time ame area and turbulence levels, which in turn result in accelerated formation and amplication of the leading shock and accelerated DDT. 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Article history: Received 9 June 2011 Received in revised form 18 August 2011 Accepted 27 September 2011 Available online 20 October 2011 Keywords: Deagration-to-detonation transition Detonation tube Ignition Photo ignition Nanoparticles

1. Introduction Flame acceleration and deagration-to-detonation transition (DDT) have been the subject of numerous studies, see pertinent reviews [14], motivated by the extreme danger undesired detonation can pose to industrial processes involving combustible gases and the potential for utilizing the rapid energy release and high overpressures resulting from detonation for high-efciency high-speed propulsion cycles [57] (e.g., pulse detonation engines PDEs). Due to the unsteady nature of propulsion cycles reliant on detonation, the time and length scales associated with the ignition and formation of a detonation wave in conned geometries is critical to the performance of detonation engines [8]. A detonation wave can be directly initiated using a high-energy source or by ame acceleration resulting in deagration-to-detonation transition (DDT), where the ame is initiated using a traditional low-energy ignition source (e.g., spark). Because of the very high energy requirements for the direct initiation of a detonation in gaseous fuel/air mixtures (order of kilojoules) [9], DDT is the most practical means by which to generate a detonation in a propulsion engine. Following a localized deposition of energy (e.g., spark), DDT occurs through several ame acceleration steps. First a laminar ame forms
Corresponding author. Address: 110 8th St., JEC 2049, Troy, NY 12065, USA.
E-mail address: oehlsm@rpi.edu (M.A. Oehlschlaeger).

from the ignition kernel and quickly becomes wrinkled due to the LandauDarrieus instability, intrinsic to freely expanding ames [3]. The wrinkled ame develops into a fully turbulent ame brush which accelerates with increasing levels of turbulence and corresponding growth in ame surface area [3]. As the turbulent ame brush accelerates, compression waves are generated ahead of the ame, which coalesce into a leading shock wave [3]. Finally the accelerating ame transitions into a detonation wave. The nal transition from a high-speed turbulent ame/shock front to a detonation is thought to involve a localized explosion somewhere in or ahead of the turbulent ame brush or in the boundary layer, due to the attainment of autoignition conditions, and the establishment of an induction-time gradient enabling the SWACER (shock wave amplication by coherent energy release) mechanism originally proposed by Zeldovich [3,10,11]. Many studies suggest that the localized explosion occurs within a quenched volume of reactants within the turbulent ame brush or in the boundary layer [2]. The performance of pulse detonation engines (PDEs), where DDT is the means of detonation initiation, is dependent on the requisite time and length scales for DDT run-up, due to the requirement of sufcient engine length for DDT run-up and the limitations the time required for DDT run-up place on PDE cycle frequency. Many efforts have been made to promote ame acceleration and DDT through the use of obstacles to induce turbulent uctuations in the unburned gas ahead of the accelerating ame and thereby increase the ame

0010-2180/$ - see front matter 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved. doi:10.1016/j.combustame.2011.09.017

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area and increase the rate of ame acceleration. Studies using a wide range of obstacle geometries have been reported, including helical spirals, orice plates, dimples, bafes, and swept ramps [1215]. Of course the use of obstacles to promote DDT results in a drag penalty to engine thrust. Other non-uid mechanic DDT promotion efforts include the addition of sensitive fuel/O2 mixtures at the location of ignition to start a detonation that then propagates into a fuel/air mixture [16]. Multipoint or distributed ignition sources that promote greater levels of initial volumetric heat release and/or shock wave amplication have also been investigated for DDT promotion. Frolov et al. [17] proposed a concept for promoting DDT based on triggering 11 electric sparks, spaced down the length of a detonation tube, sequentially to amplify the leading shock wave developed from the coalescence of compression waves emanating from the accelerating ame. Their system, although effective, required a high voltage source (2500 kV) and a total spark energy deposition of 1.68 MJ/m2. Ciccarelli et al. [18] used four circumferentially-spaced spark igniters to initiate multiple ignition kernels at the head end of a detonation tube and demonstrated 30% reductions in DDT run-up distance using the four-point ignition method in conjunction with orice plate obstacles. Wang et al. [19] and Zhukov and Starikovskii [20] have demonstrated ignition and DDT promotion using a highvoltage nanosecond transient plasma ignition source (corona discharge) that creates several high-energy ignition kernels around the plasma zone. Wang et al. [19] demonstrated reductions in ignition delay and rise times of a factor of two to three for the distributed transient plasma ignition when compared to single sparks in a owing PDE. The literature contains various mechanistic explanations for the inuence of ignition distribution on ame acceleration and DDT [17,18,20], it can be generalized that the increased rate of volumetric energy release due to the distribution of ignition sites results in greater early-time ame surface area, which increases the rate of turbulence generation and ame acceleration leading to amplication of the compression from the accelerating turbulent

ame brush, and, hence, results in accelerated leading shock formation and DDT. Recently, Berkowitz and Oehlschlaeger [21] investigated a distributed ignition method for the quasi-homogenous ignition of combustible gaseous mixtures using the photo ignition of single-walled carbon nanotubes (SWCNTs) containing Fe impurity suspended in fuel/air mixtures. The photo-ignition of SWCNTs containing metal impurities was rst discovered by Ajayan et al. [22]. In subsequent studies it was determined that the photo ignition phenomenon is dependent on the presence of metal nanoparticle impurities in the SWCNTs and the SWCNTs simply act to stabilize the naturally pyrophoric metal nanoparticles [2325]. It was also shown that the photo ignition of these Fe-containing nanomaterials results in peak temperatures in excess of 1500 C based on nanoscale characterization of the products [24,25]. The exposure of the photo-sensitive nanomaterials to a low-energy Xe camera ash, when suspended in combustible fuel/oxidizer mixtures, results in the rapid heating and oxidation of the nanomaterials followed by the ignition of the fuel/oxidizer mixture. Because the nanomaterials can be distributed throughout any given volume and exposed to a spatially-diffusive light source, the ignition of the fuel/oxidizer mixture can be highly distributed. Berkowitz and Oehlschlaeger demonstrated the quasihomogenous ignition of ethylene/air mixtures through high-speed camera images (see Fig. 1), which show the luminosity from the photo-igniting nanomaterials, in lm sized clumps, and from the volumetric combustion of the ethylene/air. Experiments in a closed combustion chamber also demonstrated reductions in ignition delay and rise times by up to a factor of two when compared to single-point spark ignition [21]. In other studies, the photo ignition of SWCNTs has been demonstrated for combustion applications by Chehroudi and Danczyk for the ignition of single fuel droplets in air [26] and Manaa et al. [27] for the ignition of solid explosives. Chehroudi and Danczyk also patented the concept of using the photo ignition of carbon nanotubes in distributed ignition applications [28,29]. Distributed photo ignition has potential in combustion

Fig. 1. Images of the distributed photo ignition of a stoichiometric C2H4/air mixture at 1 bar containing suspended single-walled carbon nanotubes with Fe impurity (70% by weight), from Berkowitz and Oehlschlaeger [21].

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applications where a degree of distribution and/or control over the location and timing of ignition are desired. Here we demonstrate that the distributed photo ignition of SWCNTs with Fe impurity suspended in gaseous fuel/oxidizer mixtures can be used to promote ame acceleration and DDT in a conned geometry. 2. Experimental method Experiments were performed in a closed detonation tube to comparatively study DDT resulting from the distributed photo ignition of carbon nanotubes with Fe impurity and a traditional single-point spark ignition. A schematic of the detonation tube is shown in Fig. 2. The carbon steel tube is 1 m long with a 7.62 cm (3 in.) inner diameter and closed on both ends. The tube inner diameter is constant with average tube bore roughness of Ra = 0.41.6 lm. For the measurement of combustion wave trajectories to determine DDT run-up distances, 12 ion sensors were axially spaced every tube diameter (7.62 cm, 3 in.) along the inside of the detonation tube side wall. The ion sensors were miniature spark plugs (Rimre Mini Viper Z2, 0.5 mm spark gap, 5 mm outer thread diameter) supplied with 9 V from an alkaline battery and connected in series to a computerized data acquisition system (1 MHz National Instruments system, automated LabView software interface). Upon passage of the combustion wave at each ion sensor location, the voltage monitored by the data acquisition system sharply drops from the open circuit value ($9 V) due to the completion of the circuit at the ion sensor spark gap by the partially-ionized gases present in the combustion products; typical experimental ion sensor signals are shown in Fig. 3. Although the detonation tube was outtted with 12 sensors, only 7 were connected during a given experiment, due to the channel limitation of the data acquisition system. Sensors were strategically selected for each experiment to capture the DDT run-up distance. Measurements of DDT run-up distance were carried out for both the spark and photo ignition of quiescent stoichiometric C2H4/O2/N2 mixtures with three levels of N2 dilution (0%, 20%, and 40%), at initial pressures ranging from 25 to 170 kPa, and an initial temperature of 297 2 K. Mixture compositions and initial pressures were chosen such that DDT would occur within the 1 m tube length. The C2H4/O2/N2 mixtures were made in a holding tank via partial pressures and allowed to diffusively mix for 24 h before use. Prior to experiments the detonation tube was evacuated to 5 103 Torr and lled with the C2H4/O2/N2 mixture to the desired pressure specied with a 1000 Torr Baratron MKS manometer. Combustion was initiated at the head end of the detonation tube by either an automotive spark plug located in the tube end wall (modied MSD 6A capacitive discharge ignition controller, Champion model QL82YC spark plug, 1 mm gap, single 105 mJ sparks) or by the photo ignition of suspended nanomaterials. Photo ignition was achieved by injecting 2 mg of single-wall carbon nanotubes (SWCNTs) containing 70% Fe impurity by weight through a diffusive air-blast style injector located in the tube side wall 3 cm from the

Fig. 3. Example raw ion sensor signals for the photo ignition of a 30.3 kPa stoichiometric C2H4/O2 mixture. S1S7 labels indicate the ion sensor signals for sensors located sequentially from the ignition end of the detonation tube. In this case DDT occurred prior to sensor 3.

end wall and exposing the nanomaterials to a Xe ash. The as-produced SWCNTs with Fe impurity (no purication) were synthesized by Nano-C in a pre-mixed combustion process where the introduction of a Fe catalyst precursor allows for the SWCNT growth. The resulting Fe impurity is specied by Nano-C as 70% by weight which is approximately 10% Fe by volume. The air-blast injection resulted in a distributed suspension of SWCNT-Fe clumps throughout approximately the rst 6 cm of the detonation tube. The uniformity of the suspension could not be quantied due to insufcient optical access to the ignition zone, where high pressures are achieved, but we have previously shown that quasi-homogenous photo ignition of gaseous fuel/oxidizer can be achieved within a spherical volume with a diameter of approximately 34 cm using this relatively crude particle injection method [21]. The injected nanomaterials are suspended in aggregate clumps of lm dimensions due to adhesion and entanglement of the ame synthesized SWCNTs. The C2H4/O2/N2 mixtures were used for air-blast injection to ensure homogeneity of the gas mixture. Following injection, the suspended SWCNTs were exposed to a Xe camera ash ($300 mJ of visible light, $1 ms ash duration), housed within the tube and located at the head end, resulting in a quasi-distributed ignition phenomenon, as illustrated in Fig. 1. Both the spark and photo ignition hardware and experimental procedures used in this study were identical to those previously detailed by Berkowitz and Oehlschlaeger [21]. Following the initiation of combustion at the head end of the tube by either spark or photo ignition, the acceleration of the combustion wave from high-speed ame to detonation was monitored using the ion sensors (Fig. 3). The distance versus time trajectories provided by the ion sensors can be converted into wave velocity versus time, of course the resulting wave velocity is averaged over the sensor axial spacing. Example wave trajectory and wave velocity

Fig. 2. Detonation tube experimental setup.

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Fig. 4. Example wave trajectories (top) and wave velocity proles (bottom) for the spark and photo ignition of stoichiometric C2H4/O2 mixtures at 30.5 and 30.3 kPa, respectively.

measurements are shown in Fig. 4 for both spark and photo ignition experiments. In all experiments a sharp rise in wave velocity corresponding to DDT was observed at some axial location in the tube. At the axial location of DDT the transition in measured wave velocity was typically from 5001000 m/s to greater than 2000 m/s within one sensor spacing or tube diameter (7.62 cm). The ChapmanJouguet (CJ) detonation velocities for the studied mixtures and initial conditions are 21402360 m/s, per calculations carried out using the STANJAN thermochemical equilibrium routine [30]. The DDT run-up distance was dened as the axial location, from the ignition end of the tube, where the measured combustion wave velocity equaled or surpassed the CJ detonation velocity. Because velocity measurements (e.g., Fig. 4) are reported at the mid-point between sensor locations, the DDT run-up distance is dened as the axial location of the upstream sensor for the rst sensor pair where the measured wave velocity equaled or surpassed the CJ velocity. Using the measured wave velocity proles, DDT run-up distances were measured for C2H4/O2/N2 mixtures, selected because they provided DDT within the 1 m tube length.

3. Results and discussion Wave velocity measurements and corresponding DDT run-up distances for spark and photo ignition experiments are shown in Figs. 5 and 6, respectively; the measured DDT run-up distances are also given in Tables 1 and 2 and all measured velocity proles and calculated CJ detonation velocities are given in Table 3. Measurements of both wave velocity and DDT run-up distances were highly reproducible, as illustrated by the overlapping data for repeated conditions in Fig. 6 and Tables 13. The high level of apparent reproducibility is partly due to the 7.62 cm limit in resolution of DDT run-up distance imposed by the ion sensor spacing. The measurements show a reduction of DDT run-up distance with increasing pressure and an increase in DDT run-up distance with increasing N2 dilution, consistent with trends found in the literature [31,32]. The results shown in Figs. 5 and 6 also illustrate shorter DDT run-up distances for distributed photo ignition compared to single-point spark ignition. The measured reductions in DDT run-up distance are approximately a factor of 1.5 to 2 for photo ignition, with respect to spark ignition. Greater relative reductions

Fig. 5. Velocitydistance measurements for the spark and photo ignition of three stoichiometric C2H4/O2/N2 mixtures (0%, 20%, and 40% N2) at varying initial pressure.

for photo ignition were generally observed for longer DDT distances, occurring at lower initial pressures and greater N2 dilution. The magnitude of reduction in DDT run-up distance is consistent with the factor of 2 reduction in ignition delay and ignition rise times reported by Berkowitz and Oehlschlaeger for the photo

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D.J. Finigan et al. / Combustion and Flame 159 (2012) 13141320 Table 2 Measured DDT run-up distances for the photo ignition of the three stoichiometric C2H4/O2/N2 mixtures studied. Photo, 0% N2 Photo, 20% N2 Photo, 40% N2

P (kPa) DDT distance (m) P (kPa) DDT distance (m) P (kPa) DDT distance (m) 24.9 25.1 30.1 30.3 40.1 40.1 40.3 50.2 50.2 50.3 70.0 70.1 70.1 0.4572 0.4572 0.2286 0.2286 0.1524 0.1524 0.1524 0.0762 0.0762 0.0762 0.0762 0.0762 0.0762 50.0 50.1 50.2 70.0 70.1 84.9 85.0 101.5 101.6 0.4572 0.4572 0.4572 0.3048 0.3048 0.1524 0.1524 0.0762 0.0762 129.6 148.9 150.3 169.6 0.6858 0.381 0.381 0.3048

Fig. 6. DDT run-up distance as a function of initial pressure for both the spark and photo ignition of three stoichiometric C2H4/O2/N2 mixtures (0%, 20%, and 40% N2). Calculated ChapmanJouguet (CJ) detonation velocities also illustrated.

ignition of stoichiometric C2H4/air mixtures in comparison to spark ignition [21]. We hypothesize that the promotion of DDT observed for photo ignition occurs because the early-time heat release resulting from photo ignition is distributed volumetrically and therefore is greater in magnitude than that from a single-point spark ignition [21]. This presumably results in larger early-time ame area, increased instability and wrinkling of the early ame, faster transition to turbulence, and higher rates of turbulent ame acceleration, all of which will lead to faster leading shock formation, increased shock amplication, and accelerated DDT. This hypothesis is in concert

with the experimental observations of Sinibaldi et al. [33] who showed that the location of ignition in a tube inuences the early-time ame area which correlates with ame acceleration and DDT run-up distance. In addition to the observed reduction in DDT run-up distance, the measured wave velocity proles for the highest pressure photo ignition cases for 0% and 20% N2 dilution show what appear to be extremely overdriven detonation waves at the ignition end of the detonation tube. In these cases the magnitude of the measured wave velocities are far greater than that measured for any of the DDT cases; in some experiments the measured detonation velocities at DDT were in excess of 2500 m/s but not greater than 3000 m/s. In the case of experiments performed for stoichiometric C2H4/O2 at 50 kPa and 70 kPa, the wave velocities measured at the rst sensor pair (sensors located 7.62 and 15.24 cm from the ignition end wall) were in the range of 60007000 m/s, followed by decay within one ion senor location (one tube diameter) to a velocity near that of a CJ detonation. These extremely high wave velocities might indicate that multiple combustion fronts have been formed by the distributed photo ignition and/or that a detonation wave may have been directly initiated by the distributed photo ignition. Berkowitz and Oehlschlaeger [21] showed that the photo ignition event can be quasi-homogenous, which under highly-sensitive fuel/O2 conditions could lead to quasi-volumetric explosion at the ignition end of the tube, directly following the ash, resulting in direct initiation of a detonation due to the high energy release. Matsui and Lee [9] reported a critical energy of around 100 mJ for the direct single-point initiation of a detonation

Table 1 Measured DDT run-up distances for the spark ignition of the three stoichiometric C2H4/O2/N2 mixtures studied. Spark, 0% N2 P (kPa) 25.0 25.0 29.6 30.1 30.5 39.9 39.9 40.0 49.9 50.1 50.1 70.0 70.0 70.1 DDT distance (m) 0.762 0.762 0.381 0.381 0.381 0.2286 0.2286 0.2286 0.1524 0.1524 0.1524 0.1524 0.1524 0.1524 Spark, 20% N2 P (kPa) 50.1 50.1 50.6 69.9 70.1 84.9 85.0 101.4 101.7 DDT distance (m) 0.8382 0.8382 0.8382 0.4572 0.4572 0.3048 0.3048 0.0762 0.0762 Spark, 40% N2 P (kPa) 130.2 132.4 148.9 149.6 169.6 DDT distance (m) 0.8382 0.8382 0.6858 0.6858 0.4572

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Table 3 Combustion wave velocity prole measurements and calculated ChapmanJouguet (CJ) detonation velocities. All experiments performed at an initial temperature of 297 2 K. Spark ignition (left) P (kPa) CJ vel. (m/s) Axial location (cm) (sensor mid-points) Wave velocity (m/s) 49.53 560 49.53 491 11.43 377 11.43 334 11.43 416 11.43 401 11.43 336 11.43 433 11.43 540 11.43 595 11.43 629 11.43 940 11.43 802 11.43 953 57.15 680 57.15 635 19.05 432 19.05 403 19.05 448 19.05 686 19.05 526 19.05 646 19.05 2931 19.05 2822 19.05 2822 19.05 2721 19.05 2540 19.05 2540 57.15 582 57.15 488 57.15 610 41.91 907 41.91 620 26.67 605 19.05 540 19.05 2822 19.05 2458 57.15 560 57.15 467 57.15 657 57.15 552 26.67 548 64.77 635 64.77 615 26.67 501 26.67 582 26.67 591 26.67 2241 26.67 2241 26.67 2241 26.67 2540 26.67 2458 26.67 2458 26.67 2458 26.67 2309 26.67 2381 64.77 866 64.77 615 64.77 712 49.53 2721 49.53 2540 34.29 2381 26.67 699 26.67 2458 26.67 2627 64.77 646 64.77 581 64.77 867 64.77 657 34.29 504 72.39 896 72.39 866 34.29 552 34.29 692 34.29 770 34.29 2381 34.29 2621 34.29 2381 34.29 2931 34.29 2381 34.29 2241 34.29 2458 34.29 2381 34.29 2627 72.39 726 72.39 668 72.39 762 57.15 2540 57.15 2721 41.91 2721 34.29 2628 34.29 2241 34.29 2309 72.39 699 72.39 718 72.39 2540 72.39 2117 41.91 595 80.01 2822 80.01 2309 41.91 2721 41.91 2241 41.91 2309 41.91 2309 41.91 2309 41.91 2241 41.91 2005 41.91 2241 41.91 2458 41.91 2309 41.91 2458 41.91 2117 80.01 819 80.01 693 80.01 712 64.77 2381 64.77 2458 49.53 2309 41.91 2628 41.91 2309 41.91 2309 80.01 747 80.01 645 80.01 2628 80.01 2381 49.53 2822 87.63 2822 87.63 2822 49.53 2930 49.53 2822 49.53 2540 49.53 2241 49.53 2241 49.53 2241 49.53 2309 49.53 2309 49.53 2241 49.53 2381 49.53 2381 49.53 2381 87.63 2117 87.63 2721 87.63 2822 72.39 2177 72.39 2177 57.15 2309 49.53 2458 49.53 2241 49.53 2309 87.63 2458 87.63 2381 87.63 2540 87.63 2458 57.15 2381 Flash ignition (right) P (kPa) CJ vel. (m/s) Axial location (cm) (sensor mid-points) Wave velocity (m/s) 26.67 1058 26.67 680 11.43 680 11.43 630 11.43 965 11.43 865 11.43 940 11.43 5861 11.43 5080 11.43 4233 11.43 4010 11.43 6927 11.43 4010 34.29 828 34.29 712 19.05 686 19.05 837 19.05 2721 19.05 2309 19.05 2721 19.05 2721 19.05 2540 19.05 2721 19.05 2540 19.05 2930 19.05 2628 41.91 918 41.91 662 26.67 2721 26.67 2721 26.67 2381 26.67 2381 26.67 2309 26.67 2458 26.67 2381 26.67 2540 26.67 2381 26.67 2381 26.67 2381 49.53 2628 49.53 2309 34.29 2822 34.29 2721 34.29 2381 34.29 2309 34.29 2309 34.29 2381 34.29 2309 34.29 2241 34.29 2381 34.29 2005 34.29 2381 57.15 2458 57.15 2930 41.91 2309 41.91 2309 41.91 2309 41.91 2309 41.91 2309 41.91 2381 41.91 2381 41.91 2458 41.91 2381 41.91 3048 41.91 2381 64.77 2309 64.77 2627 49.53 2309 49.53 2309 49.53 2309 49.53 2309 49.53 2309 49.53 2381 49.53 2381 49.53 2381 49.53 2309 49.53 2309 49.53 2381

/ = 1.0 C2H4/O2, 0% N2 25.0 2307 25.0 29.6 30.1 30.5 39.9 39.9 40.0 49.9 50.1 50.1 70.0 70.0 70.1 2307 2315 2316 2317 2329 2329 2330 2340 2340 2340 2356 2356 2356

/ = 1.0 C2H4/O2, 0% N2 24.9 2307 25.1 30.1 30.3 40.1 40.1 40.3 50.2 50.2 50.3 70.0 70.1 70.1 2308 2316 2316 2330 2330 2330 2340 2340 2340 2356 2356 2356

/ = 1.0 C2H4/O2/N2, 20% N2 50.1 2230 49.53 569 50.1 2230 49.53 485 50.6 2231 49.53 501 69.9 2244 34.29 640 70.1 2244 34.29 651 84.9 2252 19.05 610 85.0 2252 11.43 615 101.4 2259 11.43 3436 101.7 2260 11.43 3313

/ = 1.0 C2H4/O2/N2, 20% N2 50.0 2330 41.91 856 50.1 2230 41.91 856 50.2 2230 34.29 786 70.0 2244 11.43 907 70.1 2244 11.43 540 84.9 2252 11.43 828 85.0 2252 11.43 886 101.5 2259 11.43 3464 101.6 2260 11.43 4763

49.53 2059 49.53 2721 41.91 847 19.05 674 19.05 573 19.05 2458 19.05 2309 19.05 2540 19.05 3175 57.15 625 41.91 2241 34.29 740 19.05 600

57.15 2822 57.15 2381 49.53 2177 26.67 819 26.67 876 26.67 2540 26.67 2540 26.67 2628 26.67 2309 64.77 591 49.53 2721 41.91 2381 26.67 556

64.77 2381 64.77 2241 57.15 2721 34.29 2241 34.29 2241 34.29 2241 34.29 2540 34.29 2381 34.29 2540 72.39 2177 57.15 2381 49.53 2721 34.29 2259

72.39 2241 72.39 2309 64.77 2309 41.91 2721 41.91 2822 41.91 2241 41.91 2309 41.91 2241 41.91 2309 80.01 2721 64.77 2177 57.15 2309 41.91 2721

80.01 2309 80.01 2241 72.39 2241 49.53 2381 49.53 2381 49.53 2241 49.53 2241 49.53 2309 49.53 2241 87.63 2627 72.39 2116 64.77 2241 49.53 2628

u = 1.0 C2H4/O2/N2, 40% N2

130.2 132.4 148.9 149.6 169.6 2142 2143 2147 2147 2152 49.53 540 49.53 778 49.53 482 49.53 548 19.05 582

u = 1.0 C2H4/O2/N2, 40% N2

129.6 148.9 150.3 169.6 2141 2147 2148 2152 49.53 635 34.29 929 26.67 640 11.43 540

in stoichiometric C2H4/O2 at an initial pressure of 1 atm. While the 105 mJ spark does not provide direct initiation for stoichiometric C2H4/O2 mixtures at initial pressures of 50 kPa or 70 kPa, the exposure of the suspended nanomaterials to the Xe ash (approximately 300 mJ of visible optical energy with a 1 ms ash duration) results in unique initial velocity proles, perhaps indicative of direct detonation initiation resulting from a volumetric explosion. Further investigation of the dynamics of the photo ignition and

detonation formation phenomena, through high-speed optical imaging and multiple dynamic pressure measurements, is needed to determine if direct detonation initiation is possible and further understand ame acceleration and DDT from distributed photo ignition for cases where it is not. The two-fold reduction in DDT run-up distances demonstrated here using the distributed photo ignition of suspended nanomaterials in gaseous fuel/oxidizer mixtures are similar in magnitude to

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those realized using distributed transient plasma ignition [19]. The photo ignition method has advantages for detonation engines, in that it provides DDT promotion with a very low optical power ([22] reported photo ignition with as little as 100 mW/cm2 ash power, here we used a Xe ash with 300 mJ of visible energy and a duration of 1 ms) and therefore could be implemented with simple light sources (e.g., ash lamp, light-emitting diode, diode laser) requiring low-mass low-voltage power supplies. However, complicating its application to detonation engines, the photo ignition method utilizes photo-sensitive nanomaterials that would have to be distributed into either the oxidizer or fuel stream. Further research is needed to evaluate the photo ignition method demonstrated here for DDT promotion and ignition in general. For this study, exposing SWCNTs with Fe impurity with to the ash from a Xe camera ash was implemented simply because it was known to produce the photo ignition phenomenon. However, other metal and carbon-based nanomaterials are also known to exhibit photo ignition (e.g., graphene oxide [34]) and initial experimental studies performed in our laboratory suggest that nanomaterial selection is important for optimizing ignition, ame acceleration, and DDT promotion. Similarly, the optimization of the light source has yet to be considered and could provide further gains. Importantly, the photo ignition demonstrations presented here were carried out for sensitive C2H4/O2/N2 mixtures. These studies need to be extended to fuel/air conditions where the photo ignition technique may need to be combined with other uid mechanic means of promoting DDT (e.g., orice plates, helical spirals, ramps) for sufciently short DDT run-up distances for engine applications.

is needed to understand the mechanism for detonation formation for these cases. Acknowledgments We are grateful for the support of the US Ofce of Naval Research with Dr. Gabriel Roy as technical monitor and to Heesik Yoo, Aaron Ide, Stephen Kim, and Garrett Ellsworth for initial setup of the experiment. References
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4. Summary The promotion of deagration-to-detonation transition (DDT) using the distributed photo ignition of photo-sensitive nanomaterials suspended in fuel/oxidizer mixtures has been demonstrated for the rst time. Single-wall carbon nanotubes (SWCNTs) with 70% Fe impurity by weight were suspended at one end of a closed detonation tube lled with C2H4/O2/N2 mixtures. The SWCNTs were exposed to a Xe camera ash causing them to photo ignite and subsequently produce a volumetrically distributed ignition of the C2H4/O2/N2 mixture. The distributed photo ignition leads to enhanced ame acceleration and deagration-to-detonation transition (DDT). Combustion wave velocity measurements made with ion sensors show that photo ignition provides DDT run-up distances that are around a factor of 1.5 to 2 shorter than for traditional single-point spark ignition. We hypothesize that the increased volumetric energy release rate resulting from distributed photo-ignition enhances DDT due to greater early-time ame area and turbulence levels, resulting in accelerated formation and amplication of the leading shock and accelerated DDT. For the most sensitive C2H4/O2 mixtures studied, photo ignition yields extremely high combustion wave velocity measurements immediately following ignition, with velocities approximately 3 greater than the ChapmanJouguet detonation velocity, suggesting that the detonation was either directly initiated or that multiple combustion fronts are formed by the distributed ignition. Further study

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