Laser-Ignition of Methane-Air Mixtures at High Pressures and Temperatures M. Weinrotter*, B. Schwecherl, H. Kopecek, E.

Wintner Photonics Institute, Vienna University of Technology, Gusshausstrasse 27, 1040 Vienna, Austria Johann Klausner, Gnther Herdin GE Jenbacher, 6200 Jenbach, Austria
Abstract Laser ignition of lean methaneair mixtures was investigated in a combustion chamber with constant volume at high temperature and pressure. As an ignition source a Nd:YAG laser with maximum energy output of 25 mJ was used. Special interest was given to temperature dependence of lean ignition limits and minimum pulse energy (MPE) for successful ignition. MPE was measured at three different initial temperatures (423, 548 and 673 K), two different initial pressures (2 and 3 MPa) and different air/fuel equivalence ratios over a range from = 1.2 to 3. The main result with respect to lean ignition limits was the finding that the limits explicitly shift to leaner gas mixtures with increasing initial temperature (vessel temperature) and increasing initial pressure. Introduction Modern diode-pumped pulsed solid-state lasers represent attractive potential alternative ignition sources for many combustion applications, especially for internal combustion engines [1]. Particularly for gas engines with high load pressures leading to expensive spark plugs with a limited lifetime, laser ignition with its many advantages is of high interest. A second interesting application for a laser ignition system is an advanced version of operation of internal combustion engines called HCCI (homogeneous charge compression ignition) which represents an interesting alternative to a reduction of NOx emission. The laser plasma stabilizes the temporal jitter of the self-ignition timing normally taking place in an HCCI engine as it was shown by Kopecek et al. [2]. The main advantages of laser ignition in comparison to conventional spark plug ignition are: Ignition of leaner mixtures [3,4] feasible => lower combustion temperatures => lower NOx emissions [3,5] No erosion effects occurring like in the case of spark plugs leading to significantly longer availability of laser ignition systems Higher load/ignition pressures applicable => increase in efficiency [6,7] Choice of arbitrary positioning of the ignition plasma in the cylinder available Simplified possibility of multipoint ignition [8,9,10] Absence of quenching effects associated with spark plug electrodes Shorter ignition delay and shorter combustion time [11,12,13] Precise ignition timing possible High load/ignition pressures of highly developed gas engines for optimum efficiency require increased spark plug voltage leading to enhanced erosion of the electrodes resulting in spark plug lifetimes of approximately 2,000 4,000 h. Further on, re-adjustments of the * Corresponding author: martin.weinrotter@tuwien.ac.at Proceedings of the European Combustion Meeting 2005 electrode gap in time intervals of 1,000 1,500 h have also to be made which again means a shutdown of the engine (experience from gas engines of GE Jenbacher). Especially for ultra-lean combustion with stoichiometric pre-chamber ignition lifetimes of up to 600 h for a spark plug are standard. Therefore it became a main aim to increase the lifetime of an ignition system and minimize service efforts. A diode-pumped laser ignition system offers potential lifetimes of up to 10,000 h having an overall efficiency of about 10 %. Furthermore, with the possibility of multipoint ignition, combustion can be started by two or more simultaneous plasmas at different locations in the cylinder thereby shortening the total combustion duration. Moreover, even leaner mixtures can be ignited in this case than with one point ignition. Without quenching effects by the spark plug electrodes, shorter ignition delays and shorter combustion times are feasible.

Figure 1: Range of timescales for various processes involved in laser-induced ignition: the lengths of the double arrowed lines indicate the durations of the indicated processes. Inserts: (a) typical laser pulse duration; (b) examples for temporal development of spatially resolved OH concentrations in flame kernels; (c) typical pressure rise in the combustion chamber

Figure 1 shows an overview of the processes involved in laser-induced ignition covering several orders of magnitude in time from the nanosecond domain of the laser pulse itself to the duration of the entire combustion reaction lasting several hundreds of milliseconds. The laser energy is deposited in a few nanoseconds leading to shock-wave generation. An ignition delay of 50-100 ms, depending on the mixture composition, can be observed. The combustion can last between 100 ms up to 2000 ms again depending on gas mixture, initial pressure, pulse energy, plasma size, position of the plasma in the combustion chamber and initial temperature. Laser ignition, or laser-induced ignition, is the common expression for the initiation process of combustion via the stimulation by a laser light source. Basically, such energetic interactions of a laser (pulse) with a gas may be classified into one of the following four schemes as described in [14]: thermal breakdown, non-resonant breakdown, resonant breakdown and photochemical mechanisms. In the experiments to be presented, the laser spark was created by non-resonant breakdown. By focusing a pulsed laser to a sufficiently small spot size, the laser beam creates high intensity and hence exerts a strong electric field in the focal region. This results in a well localized plasma with temperatures in the order of 106 K and pressures in the order of 102 MPa as mentioned in [15,16]. The most dominant plasma generation process is the electron cascade scheme: existing initial electrons absorb photons out of the laser beam via the inverse bremsstrahlung process. If the electrons gain sufficient energy, they can ionize other gas molecules on impact, leading to an electron cascade and breakdown of the gas in the focal region. It is important to note that this process requires initial seed electrons. These electrons are produced from impurities in the gas mixture (dust, aerosols and soot particles) which are always present [17]. These impurities absorb the laser radiation and lead to high local temperature and, in consequence, to free electrons starting the avalanche process. In contrast to multiphoton ionization (MPI), no wavelength dependence is expected for this initiation path [7]. It is very unlikely that the first free electrons are produced by multiphoton ionization because the intensities in the focus (1010 W/mm2) are too low to ionize gas molecules via this process, which requires intensities exceeding 1012 W/mm2 [16,18]. Specific Objectives The main objectives in this work have been to investigate the temperature dependence of laser ignited methane-air mixtures under high ignition pressures. Measured was the minimum laser pulse energy necessary for a breakdown in air (Ethr), the minimum laser pulse necessary for ignition and following combustion (MPE) and the pressure history in the combustion chamber. The main aims have been to determine the temperature dependence of the MPE and

the lean limit of the combustible gas mixture at different initial temperatures and pressures. Moreover, the minimum breakdown energy (Ethr) should be determined for different initial temperatures and pressures. Beside these parameters also exhaust gas measurements should be performed to investigate the combustion performance. Experimental setup The experimental setup with emphasis on the optical scheme of the igniting beam is depicted in Figure 2. The beam of a Q-switched Nd:YAG laser (Litron NANO-T200-20) was focused into a high-pressure, constant volume combustion chamber through a sapphire window with a thickness of 5 mm. The laser pulse duration was about 5 ns (FWHMfull width at half maximum), the original beam had a diameter of 2.5 mm (1 / e2), and the beam quality described by the M2 factor was about 1. A part of the laser beam (about 4 %) was used to sample the energy of each pulse by using a pyroelectric detector (SpectroLas PEM21) and a power meter (LEM2020). Laser pulse energies between 1 and 20 mJ were used.

13 12 14 10
Plasma

11 9

15 8 16 4 6 5
Nd : YAG Laser

1 2 3

Figure 2: Experimental setup: 1 Nd:YAG-Laser; 2/2 waveplate; 3beam sampler (4%); 4high reflection mirrors (99.5%); 5pyroelectric detector; 6power meter (LEM2020); 7expanding lens (f=-50mm); 8collimating lens (f=300mm) 9 focusing lens in combination with a spherically correcting meniscus lens (f=100mm); 10 combustion chamber; 11heating (Ihne&Tesch); 12piezoelectric pressure transducer (Kistler 7061B); 13charge amplifier; 14digital storage oscilloscope; 15 personal computer;16gas supply After the beam sampler the laser beam was guided by 3 mirrors (reflectivity ~ 99.5 %) to an expanding and collimating lens which expands the beam diameter from 2.5 to 16 mm to yield a higher numerical aperture (NA). In these experiments the NA was 0.16. A special lens

minimum breakdown energy [mJ]

setup consisting of a plano-convex focusing lens (f=100mm) and a meniscus lens (f=100mm) with a final focusing length of 50 mm was used. With this special setup the laser beam had a focal waist of about 21 m with calculated intensities of about 1010 W/mm2. So the minimum laser energy necessary for ignition (MPE) was minimized to very small values. The combustion process was characterized by its pressure history measured by a piezoelectric pressure transducer (Kistler 7061B; response time 8.8 sec). The sensor signal had to be amplified in a charge amplifier and was recorded in a digital storage oscilloscope connected to a personal computer. For all experiments, compressed air (water free) and methane with a purity of < 99.9 % were used in order to yield data relevant for practical applications. For achieving the intended ratio of the gaseous mixture components according to the partial pressure method (Dalton), it was necessary to measure the partial pressures of methane and air by using a high resolution (resolution = 100 Pa) pressure meter. This method was assured by accompanying measurements of the methane content in the combustion chamber before ignition with gas chromatography. A special high temperature and pressure combustion chamber was designed and built for these experiments. It can withstand maximum explosion pressures up to 20 MPa even with initial wall temperatures up to 673 K. The interior diameter and length of the combustion chamber were 68 mm and 160 mm, respectively. The maximum filling pressure of one load was 3 MPa and the chamber was heated up to a given initial temperature between 423-673 K to investigate the effect of the temperature. After filling, about one minute waiting time was observed before each ignition attempt in order to achieve stabilized mixture conditions. To explore the minimum pulse energy needed for ignition/breakdown (MPE / Ethr), the pulse energy was gradually increased from pulse to pulse till the mixture was ignited. Results and discussion Before the combustion experiments were carried out the minimum laser pulse energy necessary for a breakdown (Ethr), employing the special lens system mentioned in the experimental setup chapter, was investigated. The breakdown could be easily determined because it was always associated with a cracking noise, the appearance of a bright flash of light in the focal region, and the abrupt absorption of the laser pulse transmitted through the focal region. Because of the stochastic behavior of the breakdown at the minimum breakdown energy, Ethr was defined as the laser energy at which the gas would break down for around 50 % of the experiments. Moreover, no mentionable difference of Ethr in combustible methane-air mixtures and pure air could be observed. Consequently, due to the easier experimental procedures the following experiments were carried out in pure air. Figure 3 shows the dependence of Ethr on pressures between 0.1 and 4 MPa and temperatures between 296

and 673 K. Every measured point in the diagram represents 10 measured values corresponding to 50 % probability for plasma generation under the given conditions. It can be clearly seen that especially between atmospheric conditions and 1 MPa Ethr is significantly decreasing which is in correlation with the existing literature. For pressures above 1 MPa no clear dependence can be noticed. Further on a clear increase of Ethr with increasing temperature (=>decreasing density) can be seen in Figure 3 leading to the conclusion that Ethr is mainly dependant on the density in the focal volume.
minimum breakdown energy Ethr [mJ] 12 10 8 6 4 2 0 0 1 2 pressure p [MPa] 3 4 296 K 373 K 473 K 573 K 673 K

Figure 3: Minimum breakdown energy (Ethr) versus pressure at different temperatures in pure air
12 10 8 6 4 2 0 0 10 20 30 40 pressure p [bar] 673 K 296 K Calculated

Figure 4: Comparison of measured and calculated minimum breakdown energy (Ethr) versus pressure at 296 and 673 K in pure air. The calculation was done using Ethr=K p-2/n with n = 4 and K = 10 To check if the present results can be compared with the electron cascade mentioned in the introduction process, we compared our experimental results with the breakdown energies predicted by the electron cascade theory, represented by the following relation [16]:

Ethr p-2/n

(1)

20 18 16 14 MPE [mJ] 12 10 8 6 4 2 0 1,2 1,6

where p is the pressure. Using for n the value 4 [18] and a proportionality constant K of 10, Eq. 1 generates results which agree well with the measured values as it can be seen in Figure 4. Measured Ethr for two temperatures 296 and 673 K were compared with the calculated values of Ethr. Figure 5 depicts one of the main results of this paper: the dependence of the minimum pulse energy necessary for ignition (MPE) on the initial temperature, air/fuel equivalence ratio () and initial pressure. Like it is known out of the literature and former experiments, MPE is increasing with leaner mixtures. However, the new finding is that with higher temperatures the lean limit can be expanded significantly. For an initial pressure of 2 MPa the lean limit can be shifted from about = 1.8 at 423 K to 2.6 at 673 K. At 3 MPa the lean limit can be expanded even up to a of 3. This is very important for ultra-lean powered, stationary, electricity producing gas engines like mentioned in the introduction because the NOx emissions are reduced significantly under this lean burning condition. Further on, slightly higher MPE can be recognized for the 2 MPa experiments in comparison to the 3 MPa combustions. At 2 MPa, mixtures could be ignited with energies up to 12 mJ in comparison to 3 MPa where it was possible to ignite with energies up to 16 mJ. This can be explained in the steeper rise of the MPE versus at lower initial pressures. A very interesting finding is also that rich mixtures (< = 1.6-2) are characterized with a constant value for the MPE with no dependence on the temperature or . Only at the lean limit for the different initial temperatures and pressures the MPE rises formidably. At low values the mixture ignites successfully in any case if there is an ignition source. Around the lean limit this is not the case. At this lean border it is not enough to have only high intensities in the focal region to produce a plasma; beside the intensity to generate the plasma it needs a specific minimum energy to create a self sustaining flame front and to feed the following combustion. This effect can be clearly seen in Figure 5 in the rising MPE with leaner mixtures. Mention worthy is also the increasing variance of the MPE with the leanness of the mixtures. This can be explained in small local inhomogeneities in the gas mixture and slight variations in the plasma size which have a large impact on the MPE at the lean limit.

423 K 548 K 673 K

2 MPa

2,0 []

2,4

2,8

3,2

20 18 16 14 MPE [mJ] 12 10 8 6 4 2 0 1,2 1,6

423 K 548 K 673 K

3 MPa

2,0 []

2,4

2,8

3,2

Figure 5: Minimum pulse energy for ignition (MPE) versus at 423, 548 and 673 K; comparison at 2 and 3 MPa initial pressure; methane-air mixtures

In Figure 6 the linear increase of the lean limit (limit) in dependence of the initial temperature and initial pressure (2/3 MPa) is depicted. It can be noticed quite well that at 3 MPa the lean limit is raised much faster with temperature than with an initial pressure of 2 MPa. This can be explained by the fact that at higher temperatures chemical reactions easier take place than at lower temperatures. Further on, especially at the beginning of the methane oxidation, normally many endothermic reactions are happening; these reactions take place more easily at high temperatures than the other way round.

limit for each different initial temperature, a separation of the combustion events in partial and complete events 2 MPa can be definitely made like in Figure 7. Partial 2,8 3 MPa combustions have a far lower peak pressure than 2,6 complete ones. Just at an initial temperature of 673 K nearly no difference in the peak pressure values for 2,4 partial and complete combustions can be seen. 2,2 As a result of these experiments, we got to know that 2,0 partial combustions only occur near the lean limit region. High speed videos showed that the combustion 1,8 is prone to starving in the constant volume combustion 1,6 400 450 500 550 600 650 700 chamber because of a lack of turbulence and insufficiently homogeneous gas-mixtures. But it can be T [K] taken for granted that in a gas engine with its turbulent Figure 6: Lean limit (limit) versus initial temperature at conditions partial combustions will turn to complete initial pressure (2 and 3 MPa); methane-air mixtures ones.
3,0 lean limit llimit [-]

3,2

During the experiments, especially near the lean limit, beside the complete combustion events partial combustion events also took place. Figure 7 shows four pressure histories of laser-ignited methane-air mixtures at an initial pressure of 2 MPa, an initial temperature of 548 K and an air/fuel equivalence ratio = 1.9 lying near the lean limit for this conditions (see Figure 5). On the ordinate the excess pressure is depicted in which the 0 value corresponds to 2 MPa initial pressure. In order to ensure the assumption of partial combustions, exhaust gas measurements of CO, CO2 and O2 were made. If partial combustions took place, on the one hand little CO2 and much CO are produced as a result of incomplete combustions. On the other hand, less O2 remains if combustion was complete. For further details on partial combustions in a combustion bomb with ultra-lean limits please see Weinrotter et al. [19].
5 complete combustion partial combustion

14

peak pressure [MPa]

12 10 8 6 4 2 0

423 K partial 423 K complete 548 K partial 548 K complete 673 K partial 673 K complete

1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0 3,2

[]

Figure 8: Peak pressure versus at 423, 548 and 673 K; Comparison of complete and partial combustions; initial pressure = 3 MPa; methane-air mixtures Figure 9 illustrates a comparison of ignition delay times (t5%) in dependence of the air/fuel equivalence ratio at different initial temperatures. In these measurements, the ignition delay was defined as the time interval between the appearance of the laser pulse and the instant when 5 % of the peak pressure was reached. Only complete combustions are depicted. Especially for engine designers, the t5% is a very important value. Shorter values are more desirable because they are better defined and more rounds per minutes (r.p.m.) are possible. It can be distinctively seen in Figure 9 that the t5% is increasing with leaner mixtures. Further on, with increasing initial temperature the t5% is decreasing which can be again explained in the easier and faster happening of chemical reactions at high temperatures.

excess pressure [MPa]

4 3 2 1 0 0 500 1000 1500 2000

time [ms]

Figure 7: Pressure history of complete and partial combustions of methaneair mixtures; = 1.9; initial pressure = 2 MPa; initial temperature = 548 K Figure 8 depicts the measured peak pressure of different methane-air equivalence ratios at an initial pressure of 3 MPa and different initial temperatures. The open symbols indicate partial combustion peak pressures the solid symbols complete combustions. It can be clearly observed the decreasing peak pressure with leaner mixtures which can be explained in the smaller energy content of leaner mixtures. At the lean

600

ignition delay t5% [ms]

500 400 300 200

423 K 548 K 673 K

Acknowledgements Financing by the company GE Jenbacher GmbH & Co OHG, Austria, by the Austrian Industrial Research Promotion Fund (FFF) project grant 803050 and Austrian Advanced Automotive Technology (A3) project number 806238/7782, is gratefully acknowledged. References

100 0 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8

1.
[]

2. 3.

Figure 9: Ignition delay time (time when 5% of peak pressure is reached) versus 423, 548 and 673 K; only complete combustions; initial pressure = 3 MPa; methane-air mixtures Conclusion Methane-air mixtures ( = 1.2-3) have been ignited in a combustion chamber at different initial pressures (0.1-4 MPa), different initial temperatures (423-673 K) and different laser pulse energies (1-20 mJ). As ignition source a Q-switched Nd:YAG laser at 1064 nm with a pulse duration of 5 ns was employed. The laser beam was focused by a special lens setup consisting of a plano-convex focusing lens and a meniscus lens with a finally focusing length of 50 mm. In dependence of the initial pressure and temperature the minimum laser pulse energy necessary for a breakdown (Ethr) was investigated. The main results are that with higher initial pressure the energy necessary for a plasma is significantly decreasing especially between 0.1-1 MPa. Further on, Ethr is increasing with increasing initial temperature which leads to the conclusion that Ethr is mainly depending on the density in the focal volume. The experimental results have been compared with the theory and good agreement was achieved. A second main result is that with increasing initial temperature the lean limit can be shifted to leaner mixtures. For an initial pressure of 2 MPa the lean limit can be shifted from about = 1.8 at 423 K to 2.6 at 673 K. At 3 MPa the lean limit can be expanded even up to a of 3 at 673 K. This is very important for ultra lean powered, stationary, electricity producing gas engines like in the introduction mentioned because with this lean burning condition the NOx emissions are reduced significantly. Especially at the lean limit the phenomenon of partial combustion was observed. Moreover, with higher initial temperatures the ignition delay (time when 5 % of the peak pressure is reached) decreased. Hence, as a final conclusion, laser ignition with its various potential advantages offers a very promising alternative to conventional ignition systems. In this study especially the influence of the temperature on the lean limit, ignition delay time and MPE was studied.

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