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Investigation of CO 2 infrared chemiluminescence emission and LIF detection

for combustion diagnostics applications

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Zhongshan Li Johan Zetterberg

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 Investigation of CO2 infrared chemiluminescence emission and LIF
detection for combustion diagnostics applications
Z. S. Li*, J. Zetterberg, P. Malm and M. Aldén

Division of Combustion Physics, LTH, P.O. Box 118

Lund University, S-221 00 Lund, Sweden

Abstract
Infrared chemiluminescence emission from flames was firstly investigated, where the emission from CO2 at ~4.3 µm
was found to be the major contribution. Infrared laser-induced fluorescence (IRLIF) has been applied for the
detection of carbon dioxide by probing its ro-vibrational levels. Infrared laser beams at 2.7 µm were utilized to
excite the overtone and combination band (1001). The 2.7 µm laser beam was produced through different frequency
mixing in a LiNbO3 crystal pumped by a Nd:YAG and dye laser system. Fluorescence was observed at 4.3 µm due
to radiative relaxation of the asymmetric stretching mode ν3. With an infrared camera, single-shot two-dimensional
IRLIF images of CO2 were obtained. Possible influence from stimulated emission e.g. amplified spontaneous
emission and resonance enhanced stimulated Raman scattering was studied. IRLIF of CO2 at elevated pressure and
the potential for engine diagnostics have also been performed in order to investigate the applicability of this
technique for EGR (exhaust gas recirculation) detection.

Introduction the ro-vibrational transition in the IR part of the

During the last decades different laser diagnostic spectrum for spatially resolved detection of some of
techniques have been developed and applied for the species mentioned above, e.g. polarization
achieving a deepened understanding of combustion spectroscopy detection of carbon dioxide [8, 9],
processes. Outstanding features like non- methane and ethane [10, 11], laser-induced
intrusiveness in combination with high temporal, fluorescence (LIF) detection of CO [12], CO2 [12,
spatial and species resolution have contributed to 13] and water [15].
these applications, see [1-3] for background With the advances of infrared laser sources and
references. Most of the laser diagnostic applications the improved performance of infrared CCD cameras,
for studies of combustion processes have been made two dimensional species-specified diagnostics with
in the UV/visible region of the spectrum by exciting IRLIF become possible. In this paper we demonstrate
electronic transitions. There are, however, several the use of infrared laser-induced fluorescence
difficulties associated with the limitation to this (IRLIF) for the detection of CO2 molecules.
spectral region. First of all, there are a number of
species that for various reasons can not easily be Excitation schemes
measured in this spectral region, e.g. CO2, which Shown in Figure 1 is a partial energy level
however has been identified as yielding a potential diagram of the low-lying vibration levels of CO2.
background emission at high pressure [4], and CO, Different excitation schemes are indicated in the
NH3, H2O, where two-photon excitation schemes figure. Infrared fluorescence from the radiative de-
have to be used for flame detection using LIF, see excitation of the ν3 mode at 4.26 µm are observed for
e.g. [5-7]. Probing molecular ro-vibrational all the cases. The excitation of the (1000)→(0001)
transitions by IR excitation schemes has always been transition with 10.6 µm CO2 laser was adopted by
attractive to the combustion diagnostic community. Kirby et al. [13]. This excitation scheme is good only
Many important combustion species such as CO2, for hot CO2 detection as substantial thermal
CO, H2O and hydrocarbons, which have no populations of the (1000) level are required. The
conveniently accessible electronic transitions, do excitation of the (0000)→(1201) transition with a 2
have strong absorption in the mid-IR spectral range. µm laser beam has also been performed [13, 14] and
However, spatially resolved laser-based combustion two dimensional LIF was obtained. However, due to
diagnostic experiments in the mid-IR spectral region the weakness of this transition, achievable detection
via ro-vibrational transitions have been limited by the sensitivities are limited. The transition (0000)→(1001)
poor availability of proper IR laser sources, low is about 45 times stronger. In this paper the excitation
sensitivity of infrared detectors and the relatively low of (0000)→(1001) with 2.7 µm infrared laser beam
IR fluorescence quantum yields. There has, however, was investigated.
during the last years been promising reports on using

* Corresponding author: [Link]@[Link]

Associated Web site: [Link]
Proceedings of the European Combustion Meeting 2005
 (2001)
0
(12 1)
0
(04 1)

(1001)
wavenumber (cm-1)

0
(02 1)

(0111)
0 2
(20 0) 4
(04 0) (12 0)
(04020) (1200)
(04 0)
(0001)
1
3
(03 0) (11 0)
1
(03 0)

2
(1000) (02 0)
(0200)

(0110)

n 1 n 2 n 3

Figure 1. Partial vibrational energy level diagram of CO2 molecules. The thick arrows indicate the three possible laser
excitation transitions, and the swing lines indicate the fluorescence transitions.

Flame emission measurements infrared radiative background of the flame

As a common knowledge, flames emit heat, chemiluminescence is also of great concern regarding
thermal radiation. This is mostly due to the the planar LIF detection of CO2. The flame infrared
blackbody radiation of the heated soot particles. It radiation was investigated in this work with high
would be very interesting to know the spectral spectral resolution.
structure of infrared emission of the lean flames. The

Figure 2. IR emission from the burned region of a methane/air premixed flame on a McKenna burner at atmospheric
pressure.

Spectral-resolved flame infrared emission of was focused with a CaF2 lens onto the entrance slit of
different lean flat flames on top of a McKenna burner a 320 mm spectrometer (TRIAX320, 300g/mm or
was investigated. The burned region of the flat flame 100g/mm grating). The dispersed light was imaged at

2
the output slip with an infrared camera (Santa infrared LIF, so this may block infrared LIF detection
Barbara Focal-plane, SBF L134). Shown in figure 2 in combustion environments. Looking carefully on
is an example of the flame emission [16] from a figure 2, one may find that the CO2 flame emission
premixed methane/air flame. No efforts were put in band is centre on 4.5µm, which is slightly shifted
purging to remove the water vapor and CO2 in the from the band center 4.26 µm. This is due to the cold
ambient air, so the absorptions of this two species ambient air CO2 absorption, which is distributed
were included in the recorded flame emission mostly in the low angular momentum levels and the
spectrum. hot rotational line emissions in the P-branch direction
The major infrared emitters in the burned region experience less absorption.
of a lean methane/air flame are water and carbon
dioxide molecules, which has a 2:1 ratio in molecular Infrared LIF Experiments
number density. One can see from figure 2 that the The experiments employed an injection-seeded
water emission line at ~ 3 µm and ~ 5.5 µm, and the single-longitudinal-mode Nd:YAG laser (Spectra
carbon dioxide emission line at ~ 4.5 µm are shown Physics, PRO 290-10) operating at a repetition rate of
in the flame emission spectrum. Similar structures 10 Hz and pulse length of 8 ns. The second harmonic
have been seen in flame infrared absorption spectrum at 532 nm from the Nd:YAG laser was used to pump
[17], but with the CO2 line at 4.3 µm more dominant a tunable dye laser (Sirah, PRSC-D-18) operating
in the emission spectrum. This is because that the de- with LDS 765 dye. The residual fundamental beam
excitation of the carbon dioxide (0001) → (0000) after frequency doubling at 1.064 µm was difference
band and hot bands e.g. (1001) → (1000) provide the frequency mixed in a LiNbO3 crystal with the dye
strongest fluorescence emission channel. Besides, the laser output centered at 765 nm, and a tunable IR
thermally excited N2 molecules in the hot flame laser beam was generated at 2.7 µm with a pulse
environment are infrared un-active and form a energy of approximately 5 mJ. The bandwidth of the
vibrational energy reservoir for CO2. From the flame IR laser beam was measured to be 0.025 cm-1 by an
chemiluminescence measurements, one can notice excitation scan of an IR LIF spectrum of CO2 P (24)
that the nascent CO2 emission form a strong infrared at 10 mbar.
background, which overlap very much with the

Measured LIF Intensity

Intensity (arb. Units)

HITRAN calculated spectrum

Absorption (arb. Units)

-1
Wavenumber (cm )

Figure 3. LIF excitation-scan with 2.7 micrometer IR laser excitation. The spectrum was taken in an atmospheric pressure gas
jet with 5% carbon dioxide diluted in Ar.

3
 The CO2 (AGA, 99.99%), N2 (AGA, 99.99%) and environments based on the Hitran database [18], is
Ar (AGA, 99.99%) gases used in the present also shown in figure 3. The missed lines in the
experiment were controlled separately by mass flow measurement spectrum are due to the strong
controllers (Bronkhorst HIGH-TECH). The complete absorption of the excitation laser by ambient water
mixing of the two gases was ensured by sending the vapour.
gases through a more than 10 m long 6 mm diameter In the acquisition of the IRLIF images, a
plastic tube from the flow meters to the optical vertically polarized infrared laser sheet of 10 mm
interrogating region. The gas inlet of the mixed CO2 height was formed with about 1 mJ per pulse through
with N2 or Ar flow was connected to a 5 mm jet. an optical system made of CaF2 optics. The laser
In the acquisition of the IRLIF spectra, the mixed sheet was sent through the middle of an atmospheric
CO2 gas jet was crossed by the 2.7 µm infrared beam. pressure gas jet with CO2 diluted in Ar from a 5 mm
The IRLIF was collected perpendicular to the diameter nozzle. A planar laser–induced fluorescence
excitation beam with two CaF2 spherical lenses (f = (PLIF) image was obtained by imaging
250 mm) and filtered with a narrow band interference perpendicularly to the laser sheet from the
filter (centred at 4.26 µm) before being detected by a intersection region with the infrared camera. Shown
77 K InSb infrared photovoltaic detector (Judson, in figure 4 are two single-shot CO2 PLIF images
J10D). The LIF signal from the InSb was first taken with different CO2 concentrations. The good
amplified in a preamplifier (Judson, PA-9) and then signal-to-noise ratio with as low as 0.26% CO2
integrated in a boxcar integrator. The data were concentration indicates the feasibility of the PLIF
transferred and stored in a PC for further analysis. An imaging with this method. By comparing with the
excitation scan LIF spectrum, as shown in figure 3, previous published PLIF images obtained the 2 µm
was obtained by scanning the laser across the (0000) infrared laser beams [14], one can find that the
→ (1001) band. A stimulated absorption spectrum of detection sensitivity with the 2.7 µm are much more
the CO2, calculated at room temperature and ambient improved.

a b
Figure 4. Single shot LIF images of carbon dioxide in free gas jets with about 1 mJ per pulse the 2.7 µm
infrared laser in the excitation laser sheet. a: 0.26% CO2 in Ar, Signal-background = 69 counts; b: 4.50% CO2
in Ar, Signal-background = 810 counts.

Following the preparation of the CO2 to the (1001) function of CO2 concentration, an investigation of the
state, several inter and intra energy transfer processes dependence of the IRLIF signal intensity on different
may take place due to collisions with buffer gases. CO2 mole fractions was performed. Time-resolved
Furthermore the small fraction of the excited CO2 at IRLIF was also recorded at ~ 2349 cm-1. The decay
(1001) will also suffer collision with the majority of plots showed complex profile with fast and slow
the unexcited CO2 at (0000) states. The important decays. This indicated also the substantial
vibrational energy transfer processes are those which contributions of the cascading to the IR fluorescence
involve minimum quantum number change in the measured. Unless the rate constants for all the
deactivation of (1001) vibrational state. In our IRLIF processes above are available, it is difficult to obtain
experiment, we collected the total emission at ~ 2349 quantitative IRLIF. A thorough investigation of the
cm-1 and therefore the collected emission may result CO2 line will be reported in another paper, which
from CO2 (1001), CO2 (0201) and CO2 (0001) states includes collision-induced line broadening and shifts,
[19]. In order to study the behaviour of IRLIF as a

4
LIF depolarization ratio, radiative lifetimes, technique [22]. However, the aim of the investigation
saturation effects and stimulated emissions [20]. of stimulated emission from CO2 infrared transitions
Stimulated emission from CO2 by pumping the was to explore the potential interference to the IRLIF
(0000) → (1001) transition with 2.7 µm laser beam measurements. In our investigation, stimulated
was observed in our IRLIF measurements. Super emission being observed only at a pressure lower
radiant or stimulated emission in the mid-infrared than 500 mbar. This indicates that stimulated
from molecular ro-vibration transitions, which was emission from (1001) will not be a problem in case of
produced by pumping some overtone or combination a pressure higher than 500 mbar, which is mostly the
band of infrared active molecules e.g. C2H2, CO2, case where this technique is being applied. As the
N2O, has been proposed as a method in obtaining pressure increase, the LIF signal starts to decrease.
mid-infrared laser radiation [21]. The stimulated The IRLIF signal was detectable with our IR camera
emission from pumping the molecular electronic until the pressure increased to ~10 bar.
transitions has also been used as a diagnostic

a b

c d

Figure 5. IR emission from engine. The hot exhaust valve is clearly visible.

Engine experiments view through the top window, where the intake valve
Inside a combustion engine, applicability of (left) and the exhaust valve (right) are visualized.
IRLIF and the properties of the infrared emission Shown in figure 5(b) is the IR emission from the top
from the nascent CO2 were investigated. A single- window at a crank angle of 160 degree before the
cylinder, side-valve engine modified with optical top-dead-centre (TDC), where the exhaust valve
accesses [23] was adopted in this measurement. looks brighter due to its high temperature. The image
Isooctane was used as fuel. The sapphire windows in figure 5(c) is taken at the TDC, where the CO2 in
were utilized to enable the transmission of both the the exhaust gas emits due to the thermal population
2.7 µm laser beam and the 4.3 µm fluorescence light. of its vibrational excited states. The image in figure
The predicted IRLIF was not observed in the present 5(d) is taken at 20 degree after TDC, where the
setup due to the strong infrared emission both from strong infrared chemiluminescence from nascent CO2
the wall thermal radiation and CO2 chemi- dominates the illustration. The preliminary
luminescence. Shown in figure 5 are infrared images investigation shows the possibility of direct
taken from the top window at different crank angles visualization into the combustion engine in the mid-
with a narrow filter centred at 4.3 µm placed in front infrared spectral region, which indicates subsequently
of the infrared camera. Figure 5(a) shows the normal the possibility of inner surface temperature

5
 measurements, the possibility of nascent CO2 9. Z. T. Alwahabi, Z. S. Li, J. Zetterberg and M.
chemiluminescence measurements etc.. Besides, hot Aldén, Opt. Commun. 233, 373-381 (2004).
surface as background has to be avoided in IRLIF 10. Z.S. Li, M. Rupinski, J. Zetterberg, Z.T.
measurements. Alwahabi and M. Aldén, Appl. Phys. B 79, 135-
138 (2004).
Conclusions
The IRLIF technique was presented for the 11. Z.S. Li, M. Rupinski, J. Zetterberg and M.
detection of CO2 by probing the combination band Aldén, Proc. Combust. Inst. 30, in press (2004).
(1001) → (0000). The feasibility of planar imaging of 12. B. J. Kirby, R. K. Hanson, Planar laser-induced
CO2 with IRLIF was demonstrated. Although the fluorescence imaging of carbon monoxide using
results indicate the challenge in quantifying IRLIF vibrational (infrared) transitions, Appl. Phys. B
images, this excitation scheme holds great potential 69 (1999), 505-507.
for sensitive instantaneous gas diagnostics in general.
This is especially important for molecules that do not 13. B. J. Kirby, R. K. Hanson, Linear excitation
posses an accessible optical transition such as CO, schemes for IR planar-induced fluorescence
CO2 and N2O. Spectral resolved infrared imaging of CO and CO2, Appl. Opt. 41 (2002),
chemiluminescence emission from flames was 1190-1201.
studied and the emission from CO2 at 4.3 µm was 14. Z.S. Li, J. Zetterberg, Z. Alwahabi and M.
found dominated. IR emission from a combustion Aldén, Infrared LIF and Polarization
engine was successfully observed through sapphire Spectroscopy Detection of CO2 by Probing Ro-
windows, which opens the possibility of direct Vibration, European Combustion Meeting 2003.
surface temperature measurements, CO2
15. H. Li, R. K. Hanson and J. B. Jeffries, Diode
chemiluminescence studied etc..
laser-induced infrared fluorescence of water
vapor, Meas. Sci. Technol. 15 (2004) 1285.
Acknowledgements
This work is supported by the Swedish Science 16. Andreas Pettersson, science master thesis, Lund
Council (VR) and the Swedish Energy report on Combustion physics, LRP 100,
Administration (STEM). Division of Combustion physics, Lund Institute
of Technology.
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