12FFL-0052

Activation and Control of Autoignition in HCCI Engines Using

Volumetrically-Distributed Ignition of As-Produced Single-Walled
Carbon Nanotubes
B. Chehroudi, PhD
Advanced Technology Consultants
www.AdvTechConsultants.com
4 Hidden Crest Way
Laguna Niguel, CA 92677 USA

Corso Elvezia 31
Lugano, Ticino, 6900 Switzerland

Copyright © 2012 SAE International

ABSTRACT
The discovery that nanostructured materials exhibit properties different than their bulk materials provided many exciting
opportunities with technological applications. One such opportunity is the observed ignition of the single-walled carbon nanotubes
(SWCNTs) with an ordinary camera flash. In this paper, light-activated ignition characteristics of the as-produced SWCNTs (50 wt%
iron nanoparticle content) with a camera flash are presented. The primary objective of this work is to use nanostructured materials as
means for distributed (or volumetric) ignition and improved combustion in propulsion systems. Important examples are
homogeneous-charged compression ignition (HCCI) engines, liquid rocket fuel sprays, and enhanced flame stabilization in gas turbine
engines. The idea was originally proposed by the author in April 2003 and the first patent filed in July 2004 following a series of
initial investigations. Based on these and additional tests, this new ignition method is now considered as a potential enabling
technology for volumetric and distributed ignition of liquid fuel sprays or gaseous fuel-air mixtures with the lowest incident power
intensity possible. This means remote and spatial ignition within any desired and adjustable region defined by the shape of the light
from a pulsed light source. Average intensities in between 10 to 150 W/cm2 are required for ignition of SWCNTs. This is a factor of
80 less than cases where lasers (pulsed and continuous wave (cw)) are used in coal particles. Results acquired in a premixed gaseous
fuel-air mixture in a cylindrical combustion chamber, comparing a spark plug with the light-activated distributed ignition of SWCNTs,
confirmed the patented concept and showed a truly on-demand activation of the autoignition process for HCCI engine applications.
Faster fuel-air mixture burn rate reaching up to a factor of 3 has been demonstrated for distributed ignition under lean mixture as
compared with a conventional spark ignition system.

Keywords: HCCI, carbon, nanotube, ignition, rocket, engine, fuel, propulsion

INTRODUCTION
A gaseous mixture of fuel and oxidizer can be ignited either through an internal heat release due to exothermic chemical
reactions leading to autoignition (if temperature, pressure, and stoichiometry are appropriate), or through an external addition of
energy, for example, in spark or laser ignition. Accordingly, combustion engines (automotive engines, gas turbine, rockets, etc.) either
rely on autoignition, such as diesel engines, or on one or more electrical sparks as in gasoline-fueled automotive engines. The
combustion chambers in most of these engines are fed with gaseous or liquid fuels. Typically, in direct-injection liquid-fueled
combustors, a spray with an optimized drop size distribution is needed for best performance, efficiency, and lowest emission of
pollutants. The nature of combustion itself can also be bracketed between two extremes of being homogenous, where at ignition time
a uniform mixture of fuel vapor and oxidizer is formed in which flame kernel formation and propagation rate are critical; or
heterogeneous in which flame burning speed is controlled by fuel/oxidizer mixing rates within the combustion chamber. It is well
established that homogenous combustion is soot-free if operated lean, and not only is low in regulated emission of nitric oxides (NO x)
Page 1 of 12
and carbon monoxide (CO), but also delivers high values of engine thermal efficiencies, see for example Heywood [1] and Glassman
[2]. For this reason, design trends nowadays for both gas turbine (aircraft and ground-based) and automotive engine combustors are
towards introduction or expansion of the lean premixed operating regimes.

An important example of this trend is the homogeneously-charged compression-ignition (HCCI) piston reciprocating engine,
in which the heat-release process starts with autoignition of the lean premixed fuel and air mixture, for example see Yao et al. [3] and
Chehroudi [4]. Here, good control of the time when autoignition occurs is of paramount importance for successful engine operation.
There are a host of different approaches to partially address this control requirement, most of which, with the exception of carbon
nanotubes, are discussed in Yao et al. [3] For example, variable compression ratio, variable induction temperature, variable exhaust
gas percentage, variable valve actuation, and variable fuel ignition quality are amongst the most popular approaches. However, these
methods are overly complex, require expensive engine modifications with sophisticated/costly new sensors, have limited operating
range, and are inherently incapable to time the autoignition event in the same manner as achieved through the innovative method
advocated in this paper.

The so-called distributed ignition, where a very large number of randomly distributed ignition agents within a gaseous
premixed mixture are simultaneously ignited on demand, is an important enabling technology which the author patented and is the
focus of this publication. This has been demonstrated by the use of nanostructured materials, specifically, single-walled carbon
nanotubes (SWCNTs), triggered with a low-energy pulsed light source such as an ordinary camera flash. Another example where
distributed ignition can be useful is in liquid rocket booster engines and scramjet engines. This is because nearly 30% of the
combustion instabilities in liquid rockets, which can potentially lead to engine destruction in a fraction of a second causing loss of life
and cargo, are traced back to the character of the ignition event itself, see Harrje and Reardon [5], Chehroudi et al. [6], and Chehroudi
[7]. It is believed that such an innovative ignition system offers a new flexibility to achieve an optimum ignition strategy for the best
rocket engine startup performance. There are also potential applications for satellites because of their small size, weight and low
energy requirements.

In most engine applications cited above, a reliable ignition source is needed and, in fact, this is even more critical when it
comes to liquid rocket booster engines where one successful ignition is critical to have, or else, a catastrophic event could ensue. For
example, in gasoline-fueled automotive engines, one or at most two spark plugs are used to ensure successful ignition and flame
formation in every cycle of an engine operation, see Chehroudi [8]. In gas turbine aircraft engines, the engine relight at high altitude is
critical if the stabilized flame is blown out of the combustion chamber. In almost all applications, the number of ignition sites are fixed
by design, as a matter of compromise, and limited to a few points or at best confined to a fixed narrow region within the combustion
chamber, such as in liquid rockets, where it is achieved by the flame jet approach. Nevertheless, plurality of the ignition sources is
advantageous in many applications. For example, the late professor Oppenheim referring to novelty and importance of distributed
ignition in a gasoline-fueled two-stroke engine, which was amazingly operating normally with deactivated spark plug, stated that
“Surprisingly enough the operation of the engine is then significantly smoother, the cyclic variability becomes practically
annihilated”, and he continues by saying that “The engine system should be recognized as remarkable proof of the ultimate in
enhanced ignition, whereby a virtually infinite number of ignition sources are distributed throughout the fresh charge to initiate
combustion in bulk at proper rate of burn, yielding at the same time clean and efficient operation of the engine”, see Dale and
Oppenheim [9]. Such quotations precisely characterize the Volumetrically-distributed ignition described in this paper.

The ignition concept described in this paper is based on the use of nanostructured materials and has been shown to enable on-demand
selection of a desired and adjustable region in space where distributed ignition is called for. This non-existent and new flexibility
provides an additional engineering parameter at a designer’s disposal for optimization of the ignition process and heat release rate in
HCCI engines and other applications.

In what follows, first, a brief background on ignition of dry nanostructured materials is presented. Next, a description of an
experimental setup to measure minimum ignition energies of dry SWCNTs samples is given along with an experimental procedure.
Here the objective is to investigate effects of incident light wavelength and flash pulse duration on the ignition process. Then ignition
of fuels, specifically the distributed ignition of a gaseous mixture of fuel and air, similar to what exists in a HCCI engine, is presented
in a constant volume chamber. The paper concludes with a synopsis of the observed ignition behavior of the SWCNTs and its
applications for on-demand initiation and control of autoignition in HCCI engines.

BACKGROUND ON IGNITION OF DRY NANOSTRUCTURED MATERIALS

The use of nanostructured materials as distributed ignition agents for fuels is quite new and was first proposed by the author
on June 1, 2002 and subsequently demonstrated by his research group in July 25, 2003. Therefore, very little was understood about
the fundamental interaction of light with nanostructured materials pertaining to the ignition phenomenon. However, the ignition of dry

Page 2 of 12
and “fluffy” single-walled carbon nanotubes using a simple and benign camera flash was first reported by Ajayan et al. [10].
Interestingly, the ignition was discovered serendipitously when a graduate student intended to document results of his experiments by
an ordinary flashed camera. Ignition, however, did not occur for similar materials such as multi-walled carbon nanotubes (MWCNTs),
graphite powder, fluffy carbon soot, and C60. This initial observation attracted attention of the author of this article from the outset as
a new light-weight and low-energy ignition source. The stunning part of the finding was that the ignition was initiated by an ordinary
small camera flash unit with two AA batteries.

In this section, research results for ignition of dry (no fuel) SWCNTs conducted by others are reviewed to set the stage for
ignition of fuels discussed later. The paper will then focus attention on ignition characteristics of dry samples and presents, what is to
this author’s best knowledge, the first systematic measurements of the minimum ignition energy (MIE) for candidate nanostructured
materials. Distributed ignition of fuels and its application in HCCI engines are discussed later.

Braidy et al. [11] confirmed the flash ignition effect on SWCNTs but also reported the presence of iron oxide particles in the
combustion byproducts. Chiang et al. [12] described that the carbon shells are known to be permeable to oxygen and allow oxidation
of Fe nanoparticles. Smits et al. [13] believe that the flash ignition of SWCNTs should be attributed to the pyrophoric nature of fine Fe
particles within the nanotube bundles, rather than to any property of the SWCNTs themselves. However, the SWCNTs are believed to
provide a medium stabilizing these nanoparticles to prevent spontaneous initiation of ignition until they are exposed to an appropriate
stimulus such as energy from camera flash. What has not yet been determined is a mechanism by which the flash either damages the
SWCNTs, exposing the Fe particles to the oxygen, or somehow makes the Fe particles more reactive.

Tseng et al. [14], most recently investigated the photoacoustic and ignition of the SWCNTs and MWCNTs along with carbon
fibers, C60, graphite powder, carbon paste, and diamond nano-powder in presence of a camera flash. They confirmed many of the
observations of the previous studies. Interestingly, they measured increasingly higher values of CO2 with a sequence of light flash on
SWCNTs. This suggests that nanotubes were oxidized by the flash light exposure, even though they have not reached the ignition
point-- which by itself depends on the content of the catalyst particles dispersed in the materials and a continuous supply of oxygen.
From a practical point of view, for example in terms of applications in HCCI engines, this is a very important observation because it
implies no or minimal contributions to engine exhaust solid carbon emission as they not only react to produce CO2 during the ignition,
but what is left un-ignited, has already been heated up through light energy absorption which later would burn during the combustion
phase. Hence, no or minimal impact on engine emission of carbon particles is expected.

Other nanostructured materials such as Silicon (Si) nanowires have also been reported exhibiting the photothermal and
ignition by a pulsed flash light, see Wang et al. [15]. They indicated that light intensity as low as 20 W/cm2 was able to initiate
ignition. Since no gas was entrapped in the Si or other seminconductor nanowires, Si exhibited a distinct photoacoustic effect. Also,
because a layer of Si oxide always covers the nanowires and the fact that optical absorption coefficient of the oxide is very low (at
400 nm to 700 nm incident radiation), they concluded that the large photo-effect must be from the Si nanowire itself. But they found
no difference between the absorption spectrum of the Si nanowire and pure Si single crystals, suggesting that the large photo-effect is
another unusual phenomenon in Si nanowires. Finally, the amount of energy needed to bring about ignition increased with diameter
of the nanowire and those with larger than 40 nm diameter could not be easily ignited by conventional photographic flash.

Observation that some relatively-low-cost as-produced nano-structured materials can be ignited by a benign object such as
an ordinary camera flash (or low-energy diode lasers) in a distributed manner is a novel and new opportunity to achieve on-demand
spontaneous ignition within any desired spatial volume defined by the illuminating light source. The idea in harnessing these
encouraging findings was initially proposed by the author and he motivated a few applications. The first case is for on-demand spatial
ignition (really, autoignition in this case) of fuel/air mixture in homogenous-charge compression-ignition engines (HCCI). And the
other is in the context of the liquid rocket booster and small satellite engines. Another important application is in the lean premixed
gas turbine flame stabilization which has the potential of almost eliminating the need for recirculation zone in order to stabilize the
flame in the combustor. In all these cases, the observed phenomenon, stemming from this new technology (i.e., nanotechnology), is
addressing important technological problems/limitations currently unresolved or not satisfactorily addressed in corresponding fields
within the old/existing technologies. Examples of similar synergies between nanotechnology and other established technologies are
also discussed in Chehroudi [16]. The HCCI and gas turbine applications are high-volume, high-impact, and cost-sensitive ones,
whereas the liquid rocket engine work is a low-volume application which is not nearly as cost-sensitive and where even a small
performance improvement at relatively high cost would be of great value to the stakeholders.

The objective for the work presented in this paper is to report experimental results towards characterization of the ignition
process in nanostructured materials assisting intelligent engine applications of the ideas discussed earlier. Having commercialization
prospects of the work in mind, two patents have already been filed and granted on the distributed ignition concept. More details on
the work including discussion of the tests performed can be found in references, for example see Chehroudi et al. [17, 18]

Page 3 of 12
EXPERIMENTAL SETUP FOR MINIMUM IGNITION ENERGY
The experimental setup consisted of either a Vivitar or a Canon camera flash, model number 730AFN and 580 XE II
respectively, as ignition light sources. A pulse-energy meter from GenTec, SUN series EM-1 with ED-500 detector head, capable of
measuring from 0.19 to 11 microns with minimum measurable energy of 1.3 mJ was used. Therefore the measurements here are in
radiometric sense (with the exception of UV range filtered by fiber cable) rather than photometric. A XYZ traversing stage with a
filter wheel for introducing optical filters within the light path was arranged as shown in Figs. 1 and 2. The light source (i.e., camera
flash) was a pulsed Xe arc lamp with 0.2 and 7 ms durations at its low and high light-energy settings, respectively, and was coupled
to a designated sample area through a 3’x½” quartz fiber optic light guide from Sunoptics Technologies. A high-resolution Canon
digital camera was used to capture the images of samples before and after they were exposed to a flash of light for ignition
characterization purposes. The Z-traverse (i.e., vertical) direction of the XYZ stage provided a means for incremental change in the
amount of energy-per-pulse experienced by the sample. A high-speed camera model Phantom V7.1 from Vision System which is
capable of capturing up to 4000 frames/s, full screen, is used to record movies of the ignition process.

Pulsed Light
Source

Filter
Filter Wheel

High-Speed
Framing Fiber
Camera Cable
System
Pyrometer and/or
Pyrometer
Spectrometer
DAQ

Nanostructured
Ignition Agents Microscope
Glass Slide
Pulsed Light
Meter

Figure 1: Schematic diagram of the experimental setup for ignition studies of nanostructured materials by low-energy light sources
such an ordinary camera flash.

The data acquisition system, model Win600 16-channel digital scope/DAQ system from Hi-Techniques, was supplemented
with a photodiode detector, DET36A from Thorlabs with a rise time of 14 ns, to record the light pulse from the camera flash and also
provide a TTL event synchronization pulse through a digital delay/pulse generator. The entire experimental setup was housed inside a
fume hood and the ventilation turned on when needed.

As-produced fluffy samples of SWCNTs were purchased from Unidym Corp, Houston, Texas. Although absorbance
measurements of SWCNTs of this particular manufacturing process have been reported by others, an in-house measurement was
certainly warranted. Figure 3 shows absorbance of different samples used in this study. Comparison of the nanotube absorbance with
those reported by others is satisfactory in general trends and order of magnitude, for example see Maruyama et al. [19]. It is clear that
SWCNTs show an enhanced NIR absorption around 1300 nm and which also increases towards the 400nm boundary of the visible
range.

It is important to have an idea for the range of the light wavelengths seen by the sample once the flash light passes through
the fiber optic cable. Spectral emission of energy from the Xe arc source along with the spectral transmission of the fiber light guide
used in this study were determined and shown in Fig. 3. The results for the Xe light source are consistent with what is reported in the
literature, see for example Brauers et al. [20] It is seen that below 400 nm, waves are strongly attenuated and the amount of light
Page 4 of 12
energy in the spectral range above about 1500 nm is negligible. Note that the Xe gas itself is in a clear fused quartz enclosure which
resembles the fiber optic material in terms of spectral transmission. Also, it is worth mentioning that although there are differences
between the spectra seen when the lamp is pulsed versus when operated under cw mode for wavelengths below 400nm, they are
filtered out strongly and hence not of concern in this study. It was found that a large fraction of the incident energy upon the samples
was in between 400 to 1000 nm range.

Fiber Light-guide
Fiber Light-
from flash unit for SWCNT (black Pulse Energy High-Speed
guide from a cw
sample ignition color) sample Meter Camera
light source for
Camera imaging
Flash Pyrometer

Microphone

Filter
Wheel

XYZ Traversing
Stage

Figure 2. Shows experimental set up for study of the photo-ignition effect in nanostructured materials. The digital camera and the
fiber coupling with the spectrometer are not shown. A SWCNT sample on a 2”x3” glass slide is also seen at the end of the fiber cable.
Emission of Xenon Light Source
Internal Transmission of Fiber Optic LF5 Ti(900mm long)
Absorbance_CNT43percent_Fe
Absorbance_CNT43percent_Fe
Absorbance_CNT30percent_Fe
Absorbance_CNT30percent_Fe
5.0 4.5

4.5
Absorbance of SWCNTs (A.U.)

4.0 4.0

3.5

3.0 3.5

2.5

2.0 3.0

1.5

1.0 2.5

0.5

0.0 2.0
100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000

Wavelength in nm

Figure 3. Absorbance of SWCNTs in arbitrary unit (A.U.) for different percentage of Fe nanoparticles by weight are shown. Also,
spectral emission of the Xe-arc light source (which was enveloped inside a clear fused quartz) is shown along with spectral
transmission of the fiber optic material (both in arbitrary scales on the left axis).

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EXPERIMENTAL PROCEDURE FOR MINIMUM IGNITION ENERGY
The output end of the fiber optic cable is attached to a traversing stage so it can be accurately moved over the sensing area of
the light energy meter for measurements of the amount of energy per each flash pulse. The small gap between the pulse energy-
sensing element and the end of the fiber optic is kept the same as that between the fiber end and the SWCNTs samples in the test
section. Hence, the energy-per-pulse measured by the sensor is the same as that applied to the sample. The ignition test started with
an energy/pulse well below the energy required for the ignition. Then it was progressively increased in each small step until the onset
of ignition was detected. The test was also continued beyond this point for many steps. At each step, the energy-per-pulse was
measured and images of the samples were taken before and after the application of every flash pulse. Therefore, one has detailed
characterizations of the ignition process. The onset of the ignition in un-compacted samples was sharply and easily identifiable at a
large number of dispersed spots simultaneously and within the illuminated area of the samples.

RESULTS AND DISCUSSION

First, effects of flash pulse duration and light wavelength on ignition characteristics of dry (i.e., no fuels used) SWCNTs are
discussed. Then, minimum ignition energy as a function of flash pulse duration is shown. Finally, results for the ignition of fuels and
distributed ignition of a gaseous homogeneous fuel and air mixture similar to what is found in HCCI engines are discussed using
SWCNTs.

EFFECTS OF FLASH PULSE DURATION AND WAVELENGTH ON IGNITION PROCESS

As-produced samples of SWCNTs with 50% (by weight) Fe content were used for this study because of its lowest price,
availability, and the lowest required minimum ignition energy. Lower Fe percentage was found to demand higher required ignition
energy as reported in past publications by the author’s group cited later. In tests conducted here, the energy-per-pulse was increased
progressively from a very low value and according to the procedure explained earlier until a sudden ignition at multiple locations (i.e.,
spatially distributed) was observed on the sample. The flash pulse energy at this point was considered as the minimum ignition energy
needed for sample ignition. Table 1 shows a summary of the results. Note that in Table 1 there are pairs of results with the same filter
covering a certain range of wavelengths. Obviously, this wavelength range changes as the filter model number is varied. Comparing
pairs of results with the same filter, one sees that regardless of the filters used, the minimum energy-per-pulse needed for the onset of
ignition depends only on the pulse width of the flash unit. For the shorter pulse width of 0.2 ms, the minimum ignition energy is
mostly within 30-35 mJ/pulse and about 80-95 mJ/pulse for the much longer pulse width of 7 ms.

Data shown in Table 1 suggests that there is no sizable effect of the light wavelength within the range studied here. Instead,
the speed with which a certain amount of light energy is delivered to the sample plays an important role. Specifically, it is shown that
a lower amount of energy (~30-35 mJ) is able to initiate ignition if the sample is exposed for a shorter duration. This is intuitively
reasonable because at a shorter pulse duration, the energy transfer characteristic time is comparatively shorter than the time constant
for energy (heat) losses from the sample (especially by conduction mode). Here, the same spectral light characteristics are assumed at
different pulse durations.

MINIMUM IGNITION ENERGY AND INTENSITY

To further investigate the impact of the flash pulse width and determine the minimum ignition energy and energy flux of
nanostructured materials, as-produced samples of SWCNTs were exposed to a range of pulse durations (in Full-Width Half-
Maximum, FWHM, sense) and results are presented in Fig. 4. Note the progressive reduction in MIE as flash pulse duration is
reduced. Energy flux (i.e., J/s-cm2 or W/cm2) has also been calculated by measuring the light exposure area on the samples. Because
the light source was not perfectly uniform, the minimum ignition intensities are to be interpreted as an averaged values needed for
ignition. They are also shown in this figure which indicates a linear relationship in the log-log plot with a very good correlation.
Assuming that the spectral content of the light source is independent of the pulse width, and (consequently) energy transfer
efficiencies to samples being the same within the range of pulse widths studied, the data suggests competition between two main
processes, namely, rate of energy transfer to the sample versus the rate of energy losses to its environment.

Page 6 of 12
In this context, it is useful to compare this newly-acquired results with those published in the past. Being the first to produce such a
data set for carbon nanotubes, there is no direct comparison available in the literature. However, Ajayan et al. [10] estimated 100 and
300 mW/cm2 as the energy needed to ignite fluffy dry and compacted samples, respectively. However, no effects of other parameters
were considered. This is different than what is measured here. It appears that what they reported was the luminous energy
(photometric measurement) instead of the total energy measured in radiometric sense, which is what the author is presenting in this
paper.

FILTERS MIE Flash Pulse

USED (mJ/pulse)/ Duration
(W/cm2) (ms)

No filter 85±10 / 7
7.3 ±1.4
No filter 32±5 / 0.2
255 ±40
Long Pass 83±15 / 7
495-nm 7.5
Long Pass 36±5 / 0.2
495-nm 290
Long Pass 97±15 / 7
550-nm 8.7
Long Pass 33±5 / 0.2
550-nm 260
Short Pass 79±15 / 7
1100-nm 7.1
Short Pass 29±5 / 0.2
1100-nm 230
Long Pass 83±15 / 7
700-nm 7.5
Long Pass 32±5 / 0.2
700-nm 255
Short Pass 85±15 / 7
900-nm 7.7
Short Pass 32±5 / 0.1
900-nm 255
Many other 80±15 / 7
filters 7-8
Same as Not Applicable 0.2
above
Table 1. Measured Minimum Ignition Energy (MIE) per pulse and calculated power per unit area on the sample for different filters.
The same exposure footprints are assumed for both low and high light-energy settings. For all cases shown, ignition was observed. A
Vivitar flash was used.

Minimum Ignition Energy, [mJ/pulse]

Energy Flux on the Sample, [W/cm2]
Minimum Ignition Energy, [mJ/pulse]

Minimum Ignition Energy Flux. [W/cm2]

100 500
y = 7.95x0.27
R² = 0.95

50
y = 3972.8x-0.726
R² = 0.9923

10 5
100 1000 10000
Light Pulse Duration, [microsecond]

Figure 4. Log-log plot of the minimum ignition energy and energy flux as a function of flash pulse duration for the as-produced
samples of SWCNTs with 50% (by weight) Fe contents. The illuminated area is constant for all cases (~2 cm 2). A Canon flash unit
was used.

Page 7 of 12
 It is also constructive to review studies reported in which both high-power cw and pulsed lasers were used to ignite micron
sized coal particles. In a systematic test program in which samples of very low (petroleum coke), low (char 1 and char 2), medium
(coal 1 and coal 2), and high (coal 3) volatile matter (VM) were positioned at the end of a fiber optic connected to a cw Nd:Yag laser
at 1.064 micron, Zhang et al. [21] and Zhang [22] showed homogenous, heterogeneous and mixed mode ignition depending on the
VM content of the samples. Zhang et al. [21] results suggest that the minimum ignition light intensities decline from about 800
W/cm2 with a very low VM to 300 W/cm2 for up to 45% of VM. However, because the SWCNT samples used here were vacuum
dried with no volatile matter, comparable results indicate minimum intensities of above 800 W/cm 2, being much higher than what was
achieved in SWCNTs, (see Fig. 4). If indeed the percent VM effect for coal particles is transferable to SWCNTs, this suggests even
lower minimum ignition intensities are needed for ignition of fuel-wetted samples. Another work certainly worth mentioning is by
Phuoc et al. [23] in which a pulsed Nd:Yag laser at 1.064 micron with pulse duration of 5 ms were used to ignite coal particles. The
coal particles were grounded and screened to 400 mesh and pressed into cylindrical pellets of 3 mm diameter and 2 mm in length.
They reported that ignition was not possible for intensities smaller than 800 W/cm2 in all cases investigated. Comparing this result at
the 5 ms laser pulse duration with the corresponding one measured for SWCNTs using camera flash (broadband), one reads a value
close to about 10 W/cm2, nearly 80 time less intensities needed for SWCNTs. And, of course, at considerably lower costs.

DISTRIBUTED IGNITION OF FUELS WITH SWCNTS AND HCCI APPLICATION

To the best of this author’s knowledge, Chehroudi et al. [24, 25, 26, 27, 28, 29] were the first to demonstrate and report use
of carbon nanotubes as an ignition agent for fuels. Chehroudi’s group also discussed the first application of the nanotube ignition in
the context of the fuels of interest to propulsion systems and also HCCI engines. They were able not only to ignite a wide range of
fuels, but also reported distributed ignition of the carbon nanotubes, that is, simultaneous ignition of a large number of spatially-
distributed nanotubes exposed to the light from the flash. Distributed nature of ignition is readily seen in as-produced samples and also
observed at somewhat reduced level in compacted samples, for more details see the references by Chehroudi’s group. Figure 5 shows
progression of the ignition and burning processes when a sample of SWCNTs mixed and wetted with a few drops of a fuel spread on
the surface of a glass slide. For this particular fuel, and at initial stages, SWCNT pieces are launched into the air like projectiles while
the burning process continues. A list of fuels of interest to propulsion was investigated and details are found in references cited
earlier.

Figure 5. Shows time- resolved ignition and subsequent burning of a mixture of SWCNTs and a few drops of a liquid hydrocarbon
fuel. Sequence of images from upper left to lower right corner. Time between the frames: ~0.5 s, exposure time: ~.25 ms.

Page 8 of 12
 They also showed ignition of drops of a variety of liquid fuels. This was accomplished by placing samples of SWCNTs
within the fuel vapor and air mixing layer surrounding a liquid fuel drop and at a range of distances to the surface of the drop.
Detailed examination of images suggested an intuitive series of events where initial ignition of the nanotubes was followed by an
ignition of the fuel and air mixture surrounding the drop as the fuel being vaporized. The ignition in this gas-phase fuel-and-air
mixture created a flame which subsequently engulfed the drop and consumed the liquid fuel to the end. This test essentially showed a
great potential for the success of the distributed ignition in homogeneous gaseous fuel and air, similar to what is found in HCCI
engines. This is precisely why the author proposed the HCCI engine as an important application in the granted patent.
Simultaneously, it showed a potential for distributed ignition of liquid fueled sprays for applications in liquid rocket engines. Finally,
initial encouraging results suggested feasibility of distributed ignition in liquid sprays when SWCNTs were fluidized in air passages of
a coaxial ultrasonic injector producing a very fine liquid sprays. Recently, and in a systematic work, this author's original ideas on
distributed ignition (patent filed in 2004 and first publication available since 2005) have also been demonstrated in a homogenous
fuel/air mixture, see Berkowitz and Oehlschlaeger [30].

Figure 6 shows a schematic diagram of a cylindrical combustion chamber filled with homogeneous mixture of ethylene and
air at about 2 bar pressure and ambient temperature. A flash from a disposable camera used at the center of the chamber to initiate
distributed ignition after a batch of SWCNTs is injected into the combustion chamber. The character of the ignition and pressure
history were compared with those produced by a conventional spark plug.

Camera Flash
(Xe) Element

Pressure
Transducer

Spark
SWCNT
Plug
injection
point

Gas Fill Line

+
-
Batteries

Figure 6. Schematic diagram of the cylindrical constant volume chamber (I.D. =50.8 mm. length=76.2mm) for comparative studies
between spark ignition combustion and light-activated distributed ignition with SWCNTs. A xenon flash from a disposable Kodak
camera (model 8951428-K) operated with one AA battery was used. SWCNTs were injected into a premixed homogeneous fuel and
air gaseous mixture. Spark location was at 12 mm from the wall.

Figure 7 shows side-by-side comparison of the ignition with a conventional spark plug with that by the light-activated
distributed ignition using SWCNTs. It is seen that in conventional combustion, a flame is created which propagates inside the
combustion chamber and burns the charge, whereas in the distributed ignition case, no such a flame is detected. The many bright dots
seen in the latter case are SWCNTs which were ignited subsequent to activation of the flash unit. Figure 8 shows a comparison of
results for the two cases as a function of equivalence ratio. It is seen that time durations for both 0-to-10% pressure rise and 10-to-90%
pressure rise are reduced when light-activated distributed ignition is used. Especially important to notice, and something emphasized
here, is this difference when a lean mixture is used, being of particular interest for HCCI engines at part and low load operations. For
example, at equivalence ratio of 0.7, about 27 ms time was needed for each of the 0-to-10% and 10-to-90% peak pressure periods,
whereas about 10 ms time was required for each periods when light-activated distributed ignition was used with SWCNTs. Hence,
the total 0-to-90% time is shortened from 54 ms (in spark-initiated ignition) to 20 ms (light-activated distributed ignition of
SWCNTs). This is a noticeable and important reduction of 34 ms nearly reaching a factor of 3 faster fuel-air burn rate.

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Figure 7. High-speed images of the combustion in spark ignited premixed mixture (left three columns) and light-activated distributed
ignition with SWCNTs (right three columns). In each case, the sequence of images starts from upper left corner, goes left to right in
each row, and ends up at the lower right corner. From Reference 30.

Figure 8. Comparison between spark ignition (flame initiation and propagation) and light-activated distributed ignition (on-demand
autoignition) with SWCNTs. Left: time from the ignition to 10% of the peak pressure. Right: time from 10% to 90% peak chamber
pressure. From Reference 30.

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 Results directly and convincingly indicated volumetrically-distributed ignition at numerous locations within the fuel/air
mixture. The high-speed movies showed no flame propagation as seen by the spark plug ignition and the process was characterized as
spontaneous ignition at numerous sites. Such an observation is obviously consistent with this author’s earlier gas-phase ignition
surrounding a fuel drop and reconfirms his patented distributed ignition concept initially conceived in 2003. The work clearly
demonstrated an on-demand activation of the autoignition process in a premixed fuel and air mixture of immediate relevance to and
application in HCCI engines. It is believed that such a truly on-demand activation and control of the autoignition process is needed to
address the shortcomings of the chemistry-dominated autoignition-delay-based approaches currently being researched in HCCI
engines. Furthermore, the illumination volume by a pulsed light within the combustion chamber can readily be tailored to achieve a
more adjustable rate of heat release, considered an important additional advantage of the proposed approach here and lack thereof
being one key issue with most other technologies considered so far.

CONCLUSIONS
Results from the ignition of SWCNTs are reported. The SWCNTs can be readily ignited in a spatially distributed manner
with a low-energy-level Xenon pulsed source such as an ordinary camera flash. Minimum energies required for ignition of the un-
compacted fluffy samples were studied as a function of flash pulse duration and at different wavelength regions. Initial investigation
on the effects of the wavelength showed no noticeable change in minimum ignition energy for the wavelength range studied. On the
other hand, flash pulse duration played an important role in determining the minimum ignition energy. The shorter this duration, the
lower is the minimum energy necessary to bring about ignition of the as-produced SWCNT samples. This is explained to be due to
large differences between energy transfer and dissipation time scales. The shorter the duration, the less time is available for heat
dissipation from the sample. This means faster temperature rise for the same input energy. Depending on the flash duration, intensities
between 10 to 150 W/cm2 were needed to bring about ignition of the SWCNTs. This is a factor of 80 lower than when laser is used in
coal particles. Initial results by the author strongly suggested potential for the light-activated volumetrically-distributed ignition of
premixed gaseous fuel air mixtures, being of direct application to on-demand activation of the autoignition in HCCI engines. This
innovative and patented distributed ignition concept has also been demonstrated in a premixed fuel-air- SWCNTs mixture formed
within a constant-volume cylindrical chamber, being directly comparable with, and applicable to, HCCI engines. When compared
with electric spark ignition, both the ignition-to-10%-peak-pressure rise delay times and 10%-to-90%-peak-pressure rise periods
were much shorter (reaching nearly factor of 3 faster burn rate) when distributed ignition is used under leaner than stoichiometric
conditions.

REFERENCES
1. Heywood, J. B., Internal combustion engine fundamentals, McGraw-Hill Science/Engineering/Math; 1st edition , April 1,
1988.
2. Glassman, I., Combustion, Academic Press, 3ed edition, New York, NY, 1996.
3. Yao, M., Zheng, Z., and Liu, H. Progress and recent trends in homogeneous charge compression ignition (HCCI) engines, 35,
pp. 398-437, 2009.
4. Chehroudi, B. Homogeneous charge compression ignition engine (HCCI) engines, Powertrain International, 5 (1), pp.6-10,
2002.
5. Harrje, D. T. and Reardon, F. H. Liquid propellant rocket combustion instability, NASA SP-194, Scientific and Technical
Information Office, Washington, D. C., 1972.
6. Chehroudi, B., Tally D., and Yang, V., 2010. Liquid propellants and combustion: fundamentals and classifications, Wiley
Encyclopedia of Aerospace Engineering, John Wiley Publishing, Editors: Blockly R., and Shyy, W.
7. Chehroudi, B. Physical Hypothesis for the Combustion Instability in Cryogenic Liquid Rocket Engines, AIAA Journal of
Propulsion and Power, Vol. 26, No. 6, November–December 2010.
8. Chehroudi, B. Ignition issues and their impact on engine performance, efficiency and emission, Society of Automotive
Engineers, Seminar Notes, ID C0131, 2005.
9. Dale, J. D., and Oppenheim, A. K. Enhanced Ignition for I.C. Engines with Premixed Gases, SAE Paper 810146, 16 pp.
(highlighted in Automotive Engineering, Vol. 90, No. 1, pp. 87-93, 1982), SAE Transactions, Vol. 90, Section 1, pp. 606-
621, 1981.
10. Ajayan, P.M., Terrones, M., de la Guardia, A., Huc, V., Grobert, N., Wei, B. Q., Lezec, H., Ramanath, G., and Ebbesen, T.
W. Nanotubes in a Flash_ Ignition and Reconstruction, Science 296, pp. 705, 2002.
11. Braidy, N, Botton, G. A., and Adronov, A. Oxidation of Fe nanoparticles embedded in single-walled carbon nanotubes by
exposure to a bright flash of while light, Nanoletters 2 (11), pp. 1277-1280, 2002.
12. Chiang, I.W., Brinson, B.E., Huang, A.Y., Willis, P.A., Bronikowski, M.J., Margrave, J.L., Smalley, R.E., Hauge, R.H.
Purification and characterization of single-wall carbon nanotubes (SWNTs) obtained from the gas-phase decomposition of
CO (HiPco Process), J. Phys. Chem. B 105, 8297 – 8301, 2001.
Page 11 of 12
 13. Smits, J., Wincheski, B., Namkung, M., Crooks, R., Louise, R. Response of Fe powder, purified and as-produced HiPco
single walled carbon nanotubes to flash exposure, Material Science and Engineering A358, pp. 384 –389, 2003.
14. Tseng, S. H., Nyan, H. T., Hsu, W. K., Chen, L. J., Wang, J. H., Chiu, C. C., Lee, C. Y., Chou, L. J., Leou, K. C. Ignition of
carbon nanotubes using photoflash, Carbon, 45, pp. 958-964, 2007.
15. Wang, N., Yao, B. D., Chan, Y. F., Zhang, X. Y. Enhanced photothermal effect in Si nanowires, Nano Letters, vol. 3, no. 4,
pp. 475-477, 2003.
16. Chehroudi, B. Supercritical Fluids: Nanotechnology and Select Emerging Applications, Invited Review Paper, special
volume dedicated to Supercritical Fluids, Combustion Science and Technology, Vol. 178, No. 1-3, January 2006, pp. 555-
621(67), 2006.
17. Chehroudi, B., Vaghjiani, G. L., and Ketsdever, A. Method for distributed ignition of fuels by light sources, United States
Patent Office, US 7,517,215 B1, April 14, 2009.
18. Chehroudi, B., Vaghjiani, G. L., and Ketsdever, A. Apparatus for distributed Ignition of Fuels by Light Sources, U.S. United
States Patent 7,665,985 B, February 23, 2010.
19. Maruyama, S., Miyauchi Y., Murakami, Y., and Chiahi, S. Optical characterization of single-walled carbon nanotubes
synthesized by catalytic decomposition of alcohol, New Journal of Physics, 5, pp. 149.1-149.12, 2003.
20. Brauers, J., Helling, S., and Aach, A. Multispectral imaging with flash light sources, IS\&T's Forth European Conference on
Color in Graphics, Imaging and Vision, Terrassa, Spain, pp. 608-612, June 9-13, 2008.
21. Zhang, D-k, Wall, T. F., and Hills, P. C. The ignition of single pulverized coal particle: minimum laser power required, Fuel,
vol. 73, no. 5, pp. 647-655, 1994.
22. Zhang, D-k. Laser-induced ignition of pulverized fuel particles, Combustion and Flame, 90, pp. 134-142, 1992.
23. Phuoc, T. X., Mathur, M. P., and Kemann, J. M. High-frequency Nd-Yag laser ignition of coals: experimental observations,
Combustion and Flame, 93, pp. 19-30, 1993.
24. Chehroudi, B., Badashan, A. Danczyk, S., and Morgan, C. Ignition Characteristics of Single-Walled Carbon Nanotubes
(SWCNTs) Utilizing a Camera Flash for Distributed Ignition of Liquid Sprays. Joint Army-Navy-NASA-Air Force
(JANNAF) Propulsion Meeting (JPM) and 6th Modeling and Simulation / 4th Liquid Propulsion / 3ed Spacecraft Propulsion
Joint Sub-committee Meeting, Orlando, Florida, Dec 8-12, 2008.
25. Chehroudi, B. and Danczyk, S. A novel distributed ignition method using single-wall carbon nanotubes (SWCNTs) and a
low-power flash light. Global Powertrain Congress, World Powertrain Conference & Exposition, Novi, Michigan, September
19-21, 2006.
26. Chehroudi, B., and Danczyk, S. A., Ketsdever, and G. L. Vaghjiani. A Low Power, Novel Ignition of Fuels using Single-
Walled Carbon Nanotubes (SWCNTs) and a Camera Flash, 53ed JANNAF Interagency Propulsion Committee Meeting, 2nd
Liquid Propulsion, 1st Spacecraft Propulsion Subcommittee, Monterey, California, Dec. 5-8, 2005.
27. Chehroudi, B., and Danczyk, S. A. An Innovative Ignition Method using SWCNTs and a Camera Flash, Nano Science and
Technology Institute (NSTI), Nanotechnology Conference and Trade Show, Anaheim, California, May 8-12, 2005.
28. Biever, C., Forget Spark Plugs, Start Your Engine with Nanotube, Coverage of the nanotube ignition work by the New
Scientist Magazine, Nov 19, 2005.
29. Chehroudi, B. Nanotechnology and Applied Combustion: Use of Nanostructured Materials for Light-Activated Distributed
Ignition of Fuels with Propulsion Applications, Recent Patents on Space Technology, Vol. 1, Issue 2, pp. 107-122 (16),
2011.
30. Berkowitz AM, Oehlschlaeger MA. The photo-induced ignition of quiescent fuel/air mixtures containing suspended carbon
nanotubes, Proceedings of the Combustion Institute, 33, pp. 3359-3366, 2011.

CONTACT INFORMATION
Bruce Chehroudi, PhD
Advanced Technology Consultants
www.AdvTechConsultants.com
ChehroudiB@aol.com

4 Hidden Crest Way Corso Elvezia 31

Laguna Niguel, CA 92677 USA Lugano, Ticino 6900 Switzerland

ACKNOWLEDGEMENTS: Financial support for the work was made possible by an initial seed fund the author secured
from the Air Force Research Laboratory (AFRL), managed by Mr. Jay Lavin and continued through a proposal the author submitted to
the Nanoscience and Technology program of the Air Force Office of Scientific Research (AFOSR), managed by Dr. Mike Berman.
Additionally, support of Dr. Ingrid Wysong at AFRL is appreciated. Contributions of Drs. G. Vaghjiani and A. Ketsdever and Mr.
Collin Morgan are especially valued.
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