Fuel 225 (2018) 370–380

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

A shock tube study of ignition delay times in diluted methane, ethylene, T

propene and their blends at elevated pressures
⁎
Jiankun Shao, David F. Davidson , Ronald K. Hanson
Mechanical Engineering Department, Stanford University, Stanford, CA 94305, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Ignition delay times (IDT) of small hydrocarbons at elevated pressures provide a valuable constraint for the
Ignition delay time refinement of the core small-hydrocarbon sub-mechanisms used in all combustion kinetics. Current knowledge of
Methane these core mechanisms is based largely on low-pressure data, with only limited high-pressure data available. To
Ethylene remedy this, the present study focuses on ignition delay times in methane, ethylene, propene and their blends at
Propene
elevated pressures. IDT measurements were performed in 4% O2, balance Ar mixtures, over the temperature
Shock tube
range of 950–1800 K, at pressures of 14–60 atm and equivalence ratios of 1 and 2. IDT was determined from
High pressure
recorded sidewall pressure, OH∗ emission measurements and fuel time-histories measured using laser absorption
at 3.39 μm. These measurements extend the test conditions of earlier studies, with the advantage that they have
all been performed at similar conditions and with the same facility and should provide a uniform set of kinetics
targets for the evaluation of core small-hydrocarbon mechanisms. This dataset also allowed the temperature
variation of the pressure and equivalence ratio scaling for methane and ethylene IDT to be investigated.

1. Introduction surrogate (36% methane/64% ethylene) to simulate the behavior of

There is increasing interest in refining detailed kinetics mechanisms
for combustion at elevated pressures. This interest extends to both
distillate fuels [1,2] and simpler hydrocarbons, such as methane,
ethylene, and propene [3]. Efforts to simplify the detailed mechanisms
for distillate fuels have led to the HyChem model that describe the ig-
nition processes of these fuels in two stages: pyrolysis and oxidation
[4,5]. In the pyrolysis stage of the model, the large hydrocarbon com-
ponents of distillation fuels are cracked into smaller hydrocarbons [6],
which are subsequently oxidized in the second stage. Because of this
change in molecular structure, these models rely on accurate descrip-
tions of the ignition of smaller hydrocarbons such as methane, ethylene,
propene and their blends. That is, the models require precise core small-
hydrocarbon sub-mechanisms. To refine and validate these core sub-
mechanisms, however, accurate ignition delay time (IDT) data are
needed for methane, ethylene, propene and their blends, particularly at
high pressures where current data are limited. Accurate IDT predictions
of methane and alkenes have also become a critical issue in the nu-
merical studies of reacting flows. For example, Wang et al. [7] con-
ducted a systematic high-resolution numerical study of deflagration-to-
detonation (DDT) of methane/air mixtures in a detonation tube; Shao
et al. [8] studied methane addition effects in a small spark ignition
engine; and Pellett et al. [9,10] proposed a simple two-component
partially-cracked JP-7. Because of the continuing need to improve
modeling of the combustion of small molecule kinetics, further IDT
studies, particularly at elevated pressures, are of value.
A significant amount of literature exists for ignition delay times for
methane, ethylene, and propene at low pressures. For methane, earlier
measurements were mainly conducted at low pressures of 0.5–15 atm
[11–17]. A few studies conducted in the last decade, however, probed
higher pressures. Huang et al. [18] conducted a series of shock tube
experiments to measure the ignition delay of homogeneous methane/
air mixtures at moderate temperatures (1000–1350 K) and elevated
pressures (16–40 atm). Petersen et al. [19] measured IDT of methane/
O2/dilute mixtures at pressures ranging from 35 atm to 260 atm. Pe-
tersen et al. also investigated the pressure and equivalence ratio de-
pendencies of methane/O2/Ar mixtures at 14–52 atm. For ethylene,
previous IDT studies were mostly focused on fuel-lean to stoichiometric
mixtures close to ambient pressures [20–33]. More recent investiga-
tions [34,35] highlight that the predictive capabilities of existing re-
action models of ethylene combustion remain unverified and uncertain
for fuel-rich mixtures and at elevated pressures, conditions that are
important for soot and PAHs formation. Most recently, Davidson et al.
[36] measured the ethylene IDT in diluted 4% O2/Ar mixtures from 15
to 35 atm. In this study, we measured methane IDT at 14 and 52 atm,
and extended the measurement range of ethylene IDT to 60 atm with an

⁎
Corresponding author at: Department of Mechanical Engineering, Stanford University, 418 Panama Mall, Room 104, Stanford, CA 94305-3032, United States.
E-mail address: dfd@stanford.edu (D.F. Davidson).

https://doi.org/10.1016/j.fuel.2018.03.146
Received 8 January 2018; Received in revised form 15 March 2018; Accepted 21 March 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
J. Shao et al. Fuel 225 (2018) 370–380

emphasis on pressure and equivalence ratio dependencies. driven vane assembly for 15 min prior to the experiments.
For propene, there are only a limited number of earlier investiga-
tions. Burcat et al. [37] and Qin et al. [38] conducted their early in-
2.2. Shock tube diagnostics
vestigations at pressures below 7 atm. Recently however, Burke et al.
[39] conducted a much more detailed study in six different shock tubes
Three diagnostics were employed: laser absorption at 3.39 μm, ex-
and two rapid compression machines (RCMs) over a wide range of
cited OH radical (OH∗) emission near 306 nm, and sidewall pressure.
conditions. The combination of shock tube and RCM data greatly ex-
This experiment setup gives detailed information of the reaction pro-
panded the data available for validation of propene oxidation models to
gress, and under these operating conditions the ignition delay times
higher pressures (2–40 atm) and lower temperatures (750–1750 K). In
defined by the three signals are self-consistent. The differences between
this study, we include a series of propene IDT measurements at 16 atm
the three signals is typically within ± 3% at most operating conditions,
to provide an overlapping dataset with those performed for CH4 and
but can increase to ± 15% for IDT values below 100 μs. Fuel con-
C2H4.
centration was monitored using an IR HeNe laser passing through fo-
In this study we have also addressed the need for IDT data for
cusing optics, filters, and sapphire windows and with common-mode
mixture blends, as fuel blends may not follow simple linear mixing
rejection using reference and transmission LN2-cooled InSb detectors.
correlations due to synergistic interactions between different compo-
The emission near 306 nm from the A2Σ+ − X2Π ((0,0) band) of OH∗
nents. We investigated methane/ethylene and ethylene/propene blends
was detected using a modified PDA36A Si detector, and a Schott UG5
at 16 atm.
filter with an optical setup that provided a temporal resolution of 7 μs.
Finally, the acquisition of an IDT dataset performed at similar
Pressure time-histories in the test section were monitored using a
conditions and in the same facility enables a more detailed investiga-
Kistler™ piezoelectric pressure transducer model 603B1. The measure-
tion of the subtle variations in temperature dependences of the pressure
ment location of all diagnostics was 1.1 cm away from the end wall.
and equivalence ratio scaling. Here we have also investigated, within
Representative data traces for an example ignition experiment are
the confines of recent detailed kinetics models, the reactions that con-
shown in Fig. 1. These data include pressure traces for the reactive
trol the pressure and equivalence ratio scaling for methane and ethy-
(fuel/oxidizer) and non-reactive cases together with OH∗ emission re-
lene IDT.
cords and 3.39 μm laser absorption measurements. Note that the early
The compositions and test conditions for the nine test mixtures
time rise of the 3.39 μm signal from 0 to 40 μs is an absorbance artifact
studied are given in Table 1.
related to the convolution of the spatial variation of laser beam and the
transition of the reflected shock past the observation port. In this study,
IDT was defined as the time interval between the arrival of the reflected
2. Experimental method
shock and the onset of ignition determined by extrapolating the max-
imum slope of signals back to the baseline. In all cases, this approach
2.1. High-pressure shock tube
provided consistent IDT among the three records. For consistency, all
ignition delay data discussed in the following sections use the OH∗
All IDT experiments were performed using the Stanford high-purity,
emission definition unless stated otherwise. The uncertainty in ignition
high-pressure shock tube (HPST). Helium was used as the driver gas
delay data is typically ± 10% at high temperatures, increasing slightly
and typical test times with uniform conditions were 2 ms; incident
(to ± 15%) for IDT values below 100 s. this uncertainty is estimated by
shock attenuation rates were monitored and ranged from 1.0 to 3.0%/
the theory of propagation of uncertainty with the primary contribution
m. The test time for the high-pressure shock tube was further extended
from the ± 1% uncertainty in the initial reflected-shock temperature.
to 8 ms when needed, by tailoring the driver gas with nitrogen. The
One of the main concerns in the acquisition of small hydrocarbon IDT
stainless steel driven section has an internal diameter of 5 cm and was
data is the influence of impurities. To minimize the impact of impurities
heated to 90 °C. Diaphragms were made of aluminum of 0.5–3.0 mm
on the IDT measurements, a three-step cleaning procedure was used:
thickness (with cross-scribing) to allow measurements over a broad
physical cleaning with acetone, chemical cleaning with tertbutylhy-
range of pressures (2–60 atm). Before introducing the test gas mixture,
droperoxide (30% TBHP in H2O), and pure oxygen shock cleaning (with
ultimate pressures in the driven section of less than 10−5 Torr and leak
T5 = 2000–4000 K). Following this procedure, highly repeatable IDT
and outgassing rates of less than 10−4 Torr/min were regularly
data was generated. General estimates of the impurity levels found in
achieved. The dP5∗/dt (where dP5∗ = dP5/P5) values were controlled,
Stanford shock tube experiments can be found in Urzay et al. [41].
and limited to a maximum value of 0.02/ms, by using a driver insert
[40]; the effect of this residual dP5∗/dt on simulations of the current
data was effectively negligible. 3. Results and discussion
Research grade test gases, methane, ethylene, propene, and oxidizer
(4% O2/Ar) were provided by Praxair. When producing test gas mix- IDT test conditions and values for all experiments are given in the
tures, the fuel was first introduced into a heated 12.8-liter stainless- Appendix A. Simulations of the CH4 IDT measurements were calculated
steel mixing tank at 110 °C. A test gas mixture of fuel/4% O2/Ar was using the FFCM-1 [3] and the ARAMCO Ver. 1.3 mechanisms [42].
then prepared manometrically and was stirred using a magnetically Simulation for the neat alkene IDT measurements were calculated using

Table 1
Gas mixture compositions in mole fraction.
Mixture # Components % CH4 % C2H4 % C3H6 % O2 Phi P (atm) T (K)

1 CH4/O2/Ar 1.96 0 0 3.92 1 14/52 1420–1752

2 CH4/O2/Ar 3.85 0 0 3.85 2 14 1464–1782
3 C2H4/O2/Ar 0 1.32 0 3.95 1 16/60 1095–1317
4 C2H4/O2/Ar 0 2.66 0 3.95 2 16 1122–1268
5 C3H6/O2/Ar 0 0 0.88 3.96 1 16 1255–1488
6 CH4/C2H4/O2/Ar 0.54 0.96 0 3.94 1 16 1133–1340
7 C2H4/C3H6/O2/Ar 0 0.24 0.72 3.96 1 15 1324
8 C2H4/C3H6/O2/Ar 0 0.53 0.53 3.96 1 15 1211–1329
9 C2H4/C3H6/O2/Ar 0 0.88 0.29 3.95 1 15 1206–1326

371
J. Shao et al. Fuel 225 (2018) 370–380

2.0 0.4 3.0 0.05

OH* Emission and 3.39 m Absorbance

CH4/4% O2/Ar Mixture C2H4/4% O2/Ar Mixture
2.5
= 1.0 = 1.0 0.04

Relative Pressure Signal

Relative Pressure Signal

1.5 0.3
1164 K, 16.4 atm

OH* Emission Signal

1576 K, 14.9 atm OH* Emission
2.0
0.03
3.39 m absorbance
1.0 0.2 1.5

Pressure 0.02
Non-Reactive Pressure 1.0

0.5 Pressure 0.1

0.01
0.5 Non-Reactive Pressure
OH* Emission
0.0 0.0 0.0 0.00
0 100 200 300 400 500 0 200 400 600 800

Time ( s) Time ( s)

10 1.5 10 0.4

OH* Emission and 3.39 m Absorbance

CH4/4% O2/Ar Mixture
C2H4/4%O2/Ar Mixture
8 = 1.0 8
= 1.0
Relative Pressure Signal

Relative Pressure Signal

1437 K, 58.3 atm OH* Emission
0.3

OH* Emission Signal

OH* Emission 1.0 1095 K, 63.3 atm
6 6
3.39 m absorbance
0.2

4 4
Non-Reactive Pressure 0.5 Pressure
0.1
2 Pressure 2 Non-Reactive Pressure

0 0.0 0 0.0
0 200 400 600 0 200 400 600 800 1000
Time ( s) Time ( s)
Fig. 1. Example IDT measurements: Methane/4% O2/Ar ϕ = 1, 1576 K, 14.9 atm; Methane/4% O2/Ar ϕ = 1, 1437 K, 58.3 atm; Ethylene/4% O2/Ar ϕ = 1, 1164 K,
16.4 atm; Ethylene/4% O2/Ar ϕ = 1, 1095 K, 63.3 atm. The non-reactive pressure profile for neat argon at similar conditions is also shown.

the USC Mech2 [43] and the ARAMCO mechanisms; the blend data was Temperature (K)
compared with the ARAMCO mechanism. IDT in the simulations was 2000 1818 1667 1538 1429 1333
10000
defined based on OH∗ emission values, except for USC Mech2, where,
Methane/4%O2/Argon 14 atm,
because OH∗ is not included in the mechanism, extrapolation of max-
imum pressure rise point back to the baseline was used for the IDT
definition.
Ignition Delay Time ( s)

1000

3.1. Ignition delay times for methane/4% O2/Ar mixtures 14 atm,

The IDT measurements for the methane/4% O2/Ar mixtures were 55 atm,
conducted at temperatures of 1420–1780 K, pressures of 13.3–58.3 atm 100
and equivalence ratios of 1 and 2, mixtures 1 and 2 in Table 1. Sum-
mary plots of the ignition delay data are given in Fig. 2. For the me- Simulation:
thane/4% O2/Ar mixture, IDT data from our measurements were con- Solid: ARAMCO
sistent with simulations at low temperatures. At high temperatures the Dash: FFCM-1
10
14 atm ϕ = 2 data and the 55 atm data are slightly longer than the si-
0.50 0.55 0.60 0.65 0.70 0.75
mulations. However, simulations of both mechanisms, in general, agree
1000/T (1/K)
reasonably well with the experimental data.
In a number of previous studies, methane-oxygen ignition times Fig. 2. Current IDT measurements of methane/4% O2/argon, and constant UV
were correlated using an expression of the form [44]: simulations using the ARAMCO and FFCM-1 mechanisms.

τign = A[O2]x [CH 4]y exp(Ea /RT) (1)

temperature in K.
where τign is the ignition delay time in seconds, A is a constant, [X] is the The fitting parameters from different resources are compared in
initial concentration in mol/cm3, Ea is analogous to an activation en- Table 2. Our values correlate favorably with the parameters from other
ergy in kcal/mol, R is the universal gas constant, and T is the

372
J. Shao et al. Fuel 225 (2018) 370–380

Table 2 Temperature (K)

IDT parameters from different sources. 1333 1250 1176 1111
10000
Source A x y Ea Ethylene/4%O2/Argon
FFCM-1 [3] 9.74E−16 −1.25 0.46 53.54 16 atm, =1
Spadaccini and Colket (1994) [30] 2.21E−14 −1.05 0.33 45.0

Ignition Delay Time ( s)

Tsuboi and Wagner (1975) [11] 4.00E−15 −1.02 0.32 53.0
Petersen et. al. (1999) [19] 4.05E−15 −1.05 0.33 51.8 1000
This study 3.53E−14 −1.06 0.36 46.6
16 atm,

researchers. The current high-pressure data are well-correlated but 60 atm,

have an activation energy (46.6 kcal/mol) that is slightly lower than the
value for Ea used by Petersen et al. [19] and Tsuboi and Wagner [11],
though very similar to that reported by Spadaccini and Colket [30]. Of
note is that the pressure dependence, P(x+y), of the experimental cor-
relations all cluster near P−0.71.
The current methane-oxygen-argon mixture measurements were
directly compared with previous data from selected literature using the
correlation derived from the current data; see Fig. 3. Our experiments
were in line with most previous results in a wide range of operating
conditions. One set of data at low temperatures from Skinner et al.
(1959) [45] fell away from the correlation but was also a significantly
different mixture (40% methane/60% oxygen) than used by the other
sets. The current measurements are consistent with these past studies,
but a smaller scatter was achieved through tight control of impurity
effects and the use of multiple diagnostics.
3.2. Ignition delay times for ethylene/4% O2/Ar mixtures
IDT values for mixtures 3 and 4 are shown in Fig. 4. For the ethylene
measurements, both the ARAMCO and the USC Mech2 mechanisms
underpredict the current results at high temperatures, near 1300 K, by a
factor of two. While the USC Mech2 does show the same trends in ig-
nition delay time variation with equivalence ratio and pressure, it does
not capture the magnitude of these variations. In the case of the
equivalence ratio, the current measurements show a very weak varia-
tion of ignition delay times with equivalence ratio, while the USC
Mech2 model shows a stronger sensitivity to equivalence ratios, espe-
cially at low temperatures. In the case of pressure, the current data
again showed a relatively weak dependence on pressure, whereas the
USC Mech2 model showed a much stronger dependence. On the other
hand, we found much higher IDT values for ethylene mixtures at 16 atm
than from the ARAMCO simulations, but the ARAMCO mechanism did
100
Simulation:
Solid: ARAMCO
Dash: USC Mech2
10
0.75 0.80 0.85 0.90
1000/T (1/K)
Fig. 4. Current IDT measurements of ethylene mixtures and the comparisons
with constant UV simulations using the ARAMCO and USC Mech2 mechanisms.
show a very low equivalence ratio dependence, in good agreement with
current measurements. The ARAMCO mechanism also predicted the
high pressure, 60 atm, IDT very well.
In Fig. 5, the present measurements are compared to selected lit-
erature studies under similar operating conditions. Our current results
agree with the earlier investigations within the combined uncertainty
limits. The agreement between current measurement and a recent sys-
tematic study, Saxena et al., was very good, except the scatter in the
current dataset was much smaller [34]. There was also another dataset
reported by Davidson et al. that was conducted in our lab using the
same facility [36]. The agreement was good in the low temperature
range, which shows the good repeatability of our facility.
3.3. Ignition delay times for propene/4% O2/Ar mixtures
Propene IDT was recently investigated by Burke et al. [39]. As
shown in Fig. 6, the current propene IDT data (15 atm) fall between the
shock tube measurements (at 10 and 40 atm for 4% O2/argon) of the
Burke et al. study [39]. The current data is also completely consistent
with the Burke et al. 4 and 40 atm data when their suggested pressure
dependence P−0.77 is used to normalize all the data. The current

Temperature (K) Fig. 3. Shock tube ignition data of methane–oxygen

mixtures from present work and earlier studies.
20 0 0 16 67 1429 1 2 50 Skinner and Ruehrwein (1959) [45]: 5–10 atm,
-1.06 0.36 ϕ = 3–8; CH4 = 6–23%. Seery and Bowman (1970)
ign = A[O2] [CH4] exp(Ea/RT) [16]: 1.5–4.0 atm, ϕ = 0.2–5; CH4 = 2–33%. Lif-
-14 A = 3.53E
-14
s shitz et al. (1971) [14]: 2–10 atm, ϕ = 0.5–2;
CH4 = 1–6.7%. Tsuboi and Wagner (1975) [11]:
Ea = 46.6 kcal/mol
3–300 atm, ϕ = 0.2–2; CH4 = 0.025–2%. Cheng and
[CH4]-0.36[O2]1.06)

Oppenheim (1984) [12]: 1–3 atm, ϕ = 0.5–1.5;

CH4 = 2–3.3%. Brabbs and Robertson (1986) [46]:
-16 2.5–4 atm, ϕ = 0.5–2; CH4 = 2–4%. Spadaccini and
Colket (1994) [30]: 3–15 atm, ϕ = 0.45–1.25;
Skinner and Ruehrwein (1959) CH4 = 3.5–6%.
Seery and Bowman (1970)
Lifshitz et al. (1971)
ign

-18 Tsuboi and Wagner (1975)

Cheng and Oppenheim (1984)
ln(

Brabbs and Robertson (1986)

Spadaccini and Colket (1994)
Current: 14atm, =1
14atm, =2 55atm,
-20
0.5 0.6 0.7 0.8
1000/T (1/K)

373
J. Shao et al. Fuel 225 (2018) 370–380

Temperature (K) Fig. 5. Shock-tube ignition data of ethylene–oxygen

mixtures from present work and previous studies.
1429 1250 1 1 11 1000
Baker and Skinner (1972) [24]: 3–12 atm,
-11
ϕ = 0.12–2; CH4 = 0.25–2%. Brown and Thomas

ign
= A[C2H4]0.07[O2]-0.92[Ar]0.41exp(-Ea/RT) (1999) [29]: 1.3–5.0 atm, ϕ = 1; CH4 = 1–6.3%.
-12 Saxena et al. (2011) [34]: 2–18 atm, ϕ = 1–3;
CH4 = 0.5–3.5%. Davidson et al. (2012) [36]:
[C2H4]-0.07[O2]0.92[Ar]-0.41

15 atm, ϕ = 0.5–2; CH4 = 1.33%.

-13

-14

-15 Baker and Skinner (1972)

Brown and Thomas (1999)
-16 Saxena et al. (2011)
Davidson et al. (2012)
ign

Current: 16atm,
-17
60atm, 16atm,
0.7 0.8 0.9 1.0
1000/T (1/K)

Temperature (K) than the blended mixture, while the IDT for ethylene diluted in 4% O2/
1515 1471 1429 1389 1351 1316 1282 1250 Ar is only slightly shorter than the blended mixture. This may be ex-
10000
plained by recognizing that ethylene provides a prompt radical pool
Propene/4%O2/Argon
Simulation: that accelerates the overall ignition process, thereby providing a shorter
Solid: ARAMCO IDT than that predicted if an average IDT of the two fuels was used. An
15 atm,
Ignition Delay Time ( s)

implication of the current results is that the seemingly self-evident

Dash: USC Mech 2
traditional assumptions that methane addition can be used to suppress
end-gas ignition and suppress engine knock [6] should not be taken for
granted in all cases. The single most conspicuous observation emerging
1000 4 atm, from the data comparison was that the ARAMCO mechanism under-
predicted IDT for the blend over the entire temperature range tested
and it also underpredicted the effect of methane at low temperatures.
40 atm, This finding of the blend IDT data reinforces the usefulness of current
IDT data as kinetics targets for the improvement of the core small-hy-
drocarbon sub-mechanisms.

100
0.66 0.68 0.70
Fig. 6. Propene IDT measurements and constant UV simulations using the
ARAMCO and USC Mech2 mechanisms at 15 atm. Solid Squares: Current study,
15 atm; Open squares: Burke et al. [39], 40 atm; open triangles: Burke et al.
[39], 4 atm.
measurements are in agreement with the higher temperature USC
Mech2 simulations, though they are significantly lower than the
ARAMCO simulations.
3.4. Methane/ethylene blend IDT measurement
Accurate CFD modeling of the HiFiRE (Hypersonic International
Flight Research Experimentation) scramjet engine requires the devel-
opment of a high-fidelity reaction mechanism that can simulate the
performance of a methane/ethylene surrogate (for JP-7 fuel) under
various combustion conditions. Pellett et. al. [9,10] proposed a simple
two-component surrogate (36% methane/64% ethylene) to simulate
the behavior of partially-cracked JP-7 in ignition, extinction and flame
strength experimental tests. IDT values for 36% methane/64% ethylene
blend diluted in 4% O2/Ar were measured, and are included in the
Appendix A.
In Fig. 7, the IDT for the 36% methane/ 64% ethylene blend diluted
in 4% O2/Ar are shown for two different pressures, 16 atm and 40 atm.
In each case, the IDT for methane diluted in 4% O2/Ar is much longer
0.72 0.74 0.76 0.78 0.80 3.5. Ethylene/propene blend IDT measurement
1000/T
Some aspects of the simulation capabilities of small hydrocarbon
core sub-mechanisms for C1–C3 species can be tested by comparing
with ethylene/propene blend IDT measurements. In this section, results
for three different fuel mixtures with 25% ethylene/75% propene, 50%
ethylene/50% propene, and 75% ethylene/ 25% propene, numbered as
mixture 7–9 in Table 1 are reported and compared with simulations.
In Fig. 8, the tested ethylene/propene blends are compared with the
simulations at two temperatures, 1210 K and 1330 K. The high-pressure
shock tube experimental data were obtained at 1210 K and 1330 K for
stoichiometric mixtures with 4% O2 in Ar at 15 atm. These experi-
mental results provide kinetic modeling constraint targets for binary
mixtures of C2H4 and C3H6. Experimental measurements of ignition
delay times at 1330 K for mixtures of C2H4 and C3H6 show only a weak
increase in IDT with C3H6 proportion while a stronger activation energy
is seen at 1210 K. The ARAMCO simulation captures the IDT trend at
1210 K, but does not accurately capture the IDT trend at 1330 K.
3.6. Pressure and equivalencies ratio dependence for methane and ethylene
The important result emerging from the comparison of the current
data with current models is that further improvements to small-hy-
drocarbon core sub-mechanisms can and should be made, most notably
in the sub-mechanisms describing alkene oxidation. With a consistent,
low-scatter IDT dataset in hand (i.e., data acquired with the same shock
tube facility and measurement protocols), it is possible to investigate,

374
J. Shao et al. Fuel 225 (2018) 370–380

2000K 1333 K 1000 K 2000K 1333 K 1000 K

10000
Fuel/ 4%/Ar Points: experiment Fuel/ 4%/Ar Points: experiment
scaled to 16 atm Lines: ARAMCO simulation scaled to 40 atm Lines: ARAMCO simulation
= 1.0 36% CH4/64% C2H4 = 1.0 36% CH4/64% C2H4
diluted in 4% O2/Ar diluted in 4% O2/Ar
1000
Ignition Delay ( s)

Ignition Delay ( s)
1000 CH4/4% O2/Ar
CH4/4% O2/Ar

C2H4/4% O2/Ar C2H4/4% O2/Ar

100

100 is defined by OH* emission

0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
1000/T (1/K) 1000/T (1/K)

Fig. 7. Current IDT measurements of methane, ethylene and 36% methane/64% ethylene blend mixtures and ARAMCO simulations.

10000 fuels). The equivalence ratio scaling was calculated for equivalence
ratios of 1 and 2 (using 14 atm IDT data for CH4 and 16 atm IDT data for
C2H4.)
Aramco Both the experiment and the simulations show similar variation of
the scaling dimension with temperature. The experimental pressure
ignition delay ( s)

1210 K Aramco scaling, n, for the diluted methane and ethylene mixtures are:

n = 0.67–2070/T for methane, T in K, ϕ = 1.

1000
n = 0.92–1672/T for ethylene, ϕ = 1

And, the equivalence ratio scaling, m, for the diluted methane and
1330 K ethylene mixtures are:

m = 0.66–430/T for methane, P = 14 atm

100
0.0 0.2
Fig. 8. Current IDT measurements and ARAMCO simulations for varying
ethylene/propene ratio blend mixtures at two temperatures: 1210 and 1330 K.
Test conditions: 15 atm, C2H4/C3H6 blend/4% O2/Argon, ϕ = 1.
for example, the subtle behavior of the temperature dependence of the
pressure and equivalence ratio scaling for IDT.
P and ϕ power-law scaling dimensions (i.e., τ ∝ P nϕm ) for methane/
4% O2/Ar mixture and ethylene/4% O2/Ar mixture were determined
for the current data. The pressure and equivalence ratio scaling di-
mensions are defined as the following:
m = 5.08–6112/T for ethylene, P = 16 atm
0.4 0.6 0.8 1.0 Both pressure and equivalence ratio dependencies are well behaved
C3H6 proportion and should provide reliable targets to validate detailed reaction models.
In Fig. 9, the pressure and equivalence ratio scalings for methane and
the equivalence ratio scaling for ethylene have been captured by the
mechanisms reasonably well. However, there are comparatively larger
discrepancies in the predictions of pressure scaling for ethylene. Sen-
sitivity analysis provides one pathway to identify potential reactions
responsible for this behavior.
To identify the dominant reactions responsible for the scaling be-
havior, a brute-force sensitivity analyses for IDT and pressure and
equivalence ratio scalings were conducted for the ethylene/4% O2/Ar
mixture. The definitions for the sensitivities are given in Eqs. (1)–(3):
τ2k−τk
Sensitivityτ =
τk (4)

Pressure scaling dimension: n=

ln ( )
τ P1
τP 2 τ15atm,2k1
−
τ15atm,k1

ln ( )
P1
P2 (2) SensitivityP =
τ50atm,2k1 τ50atm,k1
τ 15atm,k1
τ50atm,k1 (5)

Equivalence ratio scaling dimension: m=

ln ( )
τϕ1
τϕ2
τ∅ 2,2k1
−
τ∅ 2,k1
τ∅ 1,2k1 τ∅ 1,k1
Sensitivity∅ =
ln ( )
ϕ1
ϕ2 (3)
τ∅ 2,k1
τ∅ 1,k1 (6)
These dimensions based on the current experimental measurements A conventional sensitivity analysis for IDT, Eq. (4), for the ethylene/
are shown in Fig. 9, along with similar values from simulations. For the 4% O2/Ar mixture is shown in Fig. 10. Brute force sensitivity analyses
methane simulations, the ARAMCO and FFCM-1 mechanisms were were conducted at two temperatures, 1175 K and 1300 K, both at
used; for ethylene, ARAMCO and the USC Mech2 mechanisms were 16 atm. At these two temperatures, IDT was well predicted by the
used. (Similar results to the FFCM-1 simulations were seen for methane ARAMCO mechanism at 1175 K but underpredicted at 1300 K, as seen
scaling using the USC Mech2 mechanisms.) For methane, the pressure in Fig. 4.
scaling was calculated using 14 atm and 55 atm; for ethylene, pressures Several reactions have noticeably different sensitivities for IDT at
of 16 atm and 60 atm were used (for equivalence ratios of 1 for both the two different temperatures, as well as having significant sensitivity

375
J. Shao et al. Fuel 225 (2018) 370–380

Temperature (K)
1000/T (1/K)
1667 1429 1250 1111 1000
0.0 2000 1667 1429 1250 1111 1000
1.2
Fuel/ 4%O2/ Argon

Equivalence Ratio Dependence, m

Fuel/ 4%O2/ Argon
= (P1/P2)n Ethylene
Pressure Dependence, n

-0.2
P1
/ P2 / 2 = ( 1/ 2)m
0.8 1

-0.4 Methane
0.4

-0.6 Methane Ethylene

0.0
-0.8

-0.4
-1.0
0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
1000/T (1/K) 1000/T (1/K)
Fig. 9. Pressure and Equivalence Ratio Scaling Dimensions for CH4 and C2H4 IDT measurements in 4% O2/Argon. Solid Lines: Current Study; Dash Lines: ARAMCO;
Dot Lines: FFCM-1/USC Mech2.

C2H4+O<=>CH3+HCO channels of C2H3 + O2. Improved estimates or measurements of these

CH2CHO(+M)<=>CH3+CO(+M) rate constants would allow a better estimate of the contribution of these
2C2H3<=>C2H2+C2H4
C2H3+O2<=>CH2O+HCO
reactions to the IDT temperature scaling for C2H4.
O+H2<=>H+OH Sensitivity analyses at 1300 K for pressure (Eq. (5)) and equivalence
CH3+H(+M)<=>CH4(+M) ratio scaling (Eq. (6)) are shown in Fig. 11a and b. Differences in the
C2H5+O2<=>C2H4+HO2 sensitive reactions for the two mechanisms are evident and thus would
C2H4(+M)<=>H2+H2CC(+M)
be predicted to influence the pressure and equivalence ratio scaling
HCO+O2<=>CO+HO2
H2+O2<=>H+HO2 differently. Perhaps more importantly, many of these reactions that do
C2H4+O<=>C2H3+OH have an influence on the equivalence ratio or pressure scaling do not
HCO+M<=>H+CO+M appear in the Eq. (4) sensitivity analysis shown in Fig. 10, i.e. do not
CH3+HO2<=>CH3O+OH strongly affect IDT. This is possible as the definitions of Sensitivity for
C2H4+CH3<=>C2H3+CH4
C2H4+OH<=>C2H3+H2O
IDT (Eq. (4)) and P scaling (Eq. (5)) are not simply related mathema-
C2H4+O<=>CH2CHO+H USC Mech2 tically. A comparison of Figs. 10a and 11a shows that there are 7 re-
C2H3+O2<=>CH2CHO+O actions. in Figs. 10a and 11 reactions in Fig. 11a that are not included in
ARAMCO
H+O2<=>O+OH the other Sensitivity figure.
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 Still taking the ARAMCO mechanism as the example, of particular
Percent Sensitivity interest are the two product channels of C2H4 + O reactions that oc-
a) Sensitivity analysis of IDT (Eqn. 4) at 1300K curred in all three sensitivity analyses (Eqs. (1)–(3)). An increase in the
reaction rate of C2H4 + O]CH2CHO + H would enhance the equiva-
and 16 atm for ethylene/4% O2 /Ar mixture.
lence ratio dependence, indicating IDT was more sensitive to equiva-
lence ratio change, and an increase in the reaction rate of
C2H4+H(+M)<=>C2H5(+M)
HCO+O2<=>CO+HO2
C2H4 + O]CH3 + HCO would suppress the equivalence ratio depen-
CH3+HO2<=>O2+CH4 dence (without a significant effect on IDT), while the opposite effect
C2H4+O<=>CH3+HCO was seen in the pressure sensitivity. Furthermore, the competition be-
C2H4+HO2<=>CH2OCH2+OH tween the two product channels of C2H3 + O2,
C2H4+O<=>C2H3+OH
C2H3 + O2]CH2CHO + O and C2H3 + O2]CH2O + HCO, affected the
C2H4(+M)<=>H2+H2CC(+M)
2HO2<=>H2O2+O2
pressure dependence. Significant changes in the published branching
H2O2(+M)<=>2OH(+M) ratios and rate constants for these reactions could reconcile the model
CH3+HO2<=>CH3O+OH with the IDT, experimental pressure and equivalence ratio de-
HCO+M<=>H+CO+M pendencies seen in this data, but further theoretical and experimental
C2H4+OH<=>C2H3+H2O
studies on these rate constants are needed before such changes appear
C2H4+H<=>C2H3+H2
C2H4+CH3<=>C2H3+CH4 appropriate.
USC Mech2
C2H3+O2<=>CH2CHO+O Evident in the above sensitivity analyses of the pressure and
ARAMCO
H+O2<=>O+OH equivalence ratio scaling, is the fact that the two mechanisms should
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 respond differently to changes in individual reaction rate constants. The
Percent Sensitivity reactions with HCO showed larger sensitivities in sensitivity analyses
b) Sensitivity analysis of IDT (Eqn. 4) at using the USC Mech2 mechanism compared to the ARAMCO me-
1175K and 16 atm for ethylene/4% O2/Ar mixture. chanism. In addition, some reactions with larger molecules, such as
C3H6, showed different sensitivities in the two mechanisms. The current
Fig. 10. IDT sensitivity analysis for ethylene/4% O2/Ar mixture. sensitivity analyses highlight the difficulty in converging on a con-
sistent and unique mechanism for alkene oxidation and the large
magnitudes. In the case of the ARAMCO model, these include two re- variability that is still seen in these mechanisms and the importance of
action product channels of C2H4 + O, and two reaction product accurate elementary rate constant measurements. Efforts are currently

376
J. Shao et al. Fuel 225 (2018) 370–380

2C2H3<=>C2H2+C2H4 USC Mech2 4. Summary

O+H2<=>H+OH
C2H3+O2<=>CH2CHO+O ARAMCO
C2H4+O<=>CH3+HCO Gas-phase ignition delay times of methane/O2/Ar mixtures, ethy-
C2H4+CH3<=>C2H3+CH4
lene/O2/Ar mixtures, propene/O2/Ar mixtures and their blends were
H+O2<=>O+OH
C2H4+O2<=>C2H3+HO2 evaluated in the Stanford high-pressure shock tube. Simple power-law
CH3+H(+M)<=>CH4(+M) pressure and equivalence ratio scalings were investigated based on the
HCO+O2<=>CO+HO2
C2H4+HO2<=>CH2OCH2+OH current data for methane and ethylene. A sensitivity analysis for pres-
C3H6+CH3<=>CH3CCH2+CH4 sure and equivalence ratio scaling of ethylene ignition delay provides a
C3H6+H<=>C2H4+CH3 list of reactions that merits further investigation to improve alkene si-
CH2OH+H<=>CH3+OH
OH+HO2<=>H2O+O2 mulations in small-hydrocarbon core sub-mechanisms. The current
2HO2<=>H2O2+O2 measurements should provide targets needed for the further develop-
HCO+M<=>H+CO+M
C2H3+O2=>H+CO+CH2O ment and evaluation of these core sub-mechanisms.
C2H4+O<=>CH2CHO+H
H+O2(+AR)<=>HO2(+AR)
CH2CHO(+M)<=>CH2CO+H(+M)
C2H3+O2<=>CH2O+HCO Acknowledgements
-0.2 -0.1 0.0 0.1 0.2
This work was supported by the Air Force Office of Scientific
Percent Sensitivity
Research through AFOSR Grant No. FA9550-16-1-0195, with Dr.
a) Sensitivity analysis of the pressure scaling (Eqn. 5). Chiping Li as contract monitor, and SBIR Contract No. FA8650-25-C-
2531 With Dr. Barry Kiel as contract monitor. Some of the methane
Reflected shock conditions: 1300 K, 16 atm
measurements were based upon work supported by the U.S.
and 60 atm, =1. Department of Energy under Award Number DE-FE0025260. The au-
thors thank Prof. Ming Jia from the Dalian University of Technology for
O+H2<=>H+OH
C2H4(+M)<=>H2+H2CC(+M) USC Mech2 help with sensitivity analyses.
H+O2(+AR)<=>HO2(+AR)
2C2H3<=>C2H2+C2H4 ARAMCO
C2H3+O2<=>CH2CHO+O
C2H4+O<=>CH3+HCO
CH2CHO(+M)<=>CH3+CO(+M)
HCCO+OH<=>C2O+H2O
CH3+C<=>C2H2+H
C2H3+H<=>H2CC+H2
H2CC+O2<=>2HCO
C3H6+CH3<=>CH3CCH2+CH4
C3H6+H<=>C2H4+CH3
CH3CO+O<=>CH2CO+OH
HCO+M<=>H+CO+M
C2H4+O<=>CH2CHO+H
HCCO+O=>H+2CO
CH3+OH<=>CH2OH+H
C3H6+O<=>C3H5-S+OH
C3H6<=>C3H5-T+H
C2H6+O<=>C2H5+OH
2CH3(+M)<=>C2H6(+M)
CO+OH<=>CO2+H
-0.15 -0.10 -0.05 0.00 0.05 0.10 0.15
Percent Sensitivity

b) Sensitivity analysis of the equivalence ratio

scaling (Eqn. 6).Reflected shock conditions: 1300 K,
16 atm, = 1 and 2.
Fig. 11. Sensitivity analysis of the pressure and equivalence ratio scalings.

in progress in this laboratory to address some of these issues.

Appendix A

Test conditions and IDT values for mixtures 1–9 of Table 1.

Mixture # T5 (K) P5 (atm) Ign_P (µs) Ign_OH∗ (µs) Ign_3.39um (µs)

Mixture 1, CH4, phi = 1

1 1752 13.5 128 108 119
1 1746 13.8 122 110 121
1 1731 13.8 144 134 147
1 1730 13.5 159 140 144
1 1730 13.7 168 143 158
1 1651 13.9 265 254 264
1 1634 14.6 298 286 295
1 1613 14.4 319 307 315
1 1616 14.6 318 309 316
1 1617 14.2 342 332 340

377
J. Shao et al. Fuel 225 (2018) 370–380

1 1576 14.9 416 413 436

1 1461 14.9 1494 1454 1463
1 1420 15.5 2241 2260 2310
1 1663 54.2 107 93 96
1 1587 51.7 213 191 205
1 1537 57.5 286 268 277
1 1534 51.1 309 293 297
1 1507 52.9 372 347 365
1 1488 51.5 417 399 405
1 1453 53.8 565 547 563
1 1437 58.3 602 597 610
Mixture 2, CH4, phi = 2
2 1782 13.3 134 117 126
2 1782 13.3 134 117 126
2 1769 13.3 145 128 143
2 1749 13.3 180 163 170
2 1739 13.3 193 172 187
2 1728 13.4 206 189 195
2 1704 13.5 229 215 222
2 1657 13.6 307 309 316
2 1630 13.8 359 385 393
2 1627 13.8 393 392 402
2 1600 13.9 461 469 487
2 1504 14.3 1259 1205 1276
2 1481 14.4 1471 1526 1660
2 1464 14.8 1717 1731 1895
Mixture 3, C2H4, phi = 1
3 1317 15.7 91
3 1303 15.8 116
3 1295 15.8 127
3 1275 15.5 182
3 1271 15.8 216 184
3 1269 15.8 212 193
3 1267 15.8 223 185
3 1231 16.1 332 322
3 1195 16.3 510 499
3 1186 15.9 550 540
3 1164 16.4 704 699
3 1137 16.6 1080 1056
3 1132 16.7 1141 1120
3 1311 59.7 69 61
3 1281 59.6 107 92
3 1261 60.1 123 121
3 1263 60.3 135 125
3 1230 61.7 184 177
3 1188 61.8 319 317
3 1156 62.7 452 454
3 1117 61.9 705 698
3 1109 63.0 762 755
3 1095 63.3 913 921
Mixture 4, C2H4, phi = 2
4 1268 15.7 214 211
4 1232 15.7 302 321
4 1213 16.0 380 390
4 1206 16.0 395 416
4 1191 16.0 470 496
4 1185 16.0 480 528
4 1180 16.1 532 548
4 1159 16.4 669 689
4 1135 16.2 881 912
4 1122 16.4 994 1070
Mixture 5, C3H6, phi = 1
5 1327 14.9 860 822
5 1305 15.6 1195 1341

378
J. Shao et al. Fuel 225 (2018) 370–380

5 1255 15.7 2917 3022

5 1273 15.5 2196 2190
5 1375 15.1 555 533
5 1395 14.9 452 452
5 1431 14.7 349 336
5 1488 14.5 236 207
Mixture 6, 36% CH4/64% C2H4, phi = 1
6 1340 15.3 108
6 1276 15.2 258
6 1212 15.7 600
6 1165 16.1 1073
6 1133 16.3 1669
6 1238 15.4 425
Mixture 7, 25% C2H4/75% C3H6, phi = 1
7 1324 14.8 748 737
Mixture 8, 50% C2H4/50% C3H6, phi = 1
8 1329 14.9 543 537
8 1212 15.6 2439 2408
Mixture 9, 75% C2H4/25% C3H6, phi = 1
9 1326 14.8 335 327
9 1206 15.5 1042 1035

References with O2. Proc Combust Inst 1967;11(1):147–54. Elsevier.

[1] Davidson DF, Zhu Y, Shao J, Hanson RK. Ignition delay time correlations for dis-
tillate fuels. Fuel 2017;187:26–32.
[2] Davidson DF, Shao J, Choudhary R, Mehl M, Obrecht N, Hanson RK. Ignition delay
time measurements and modeling for gasoline at very high pressures. Proc Combust
Inst 2018. [submitted for publication].
[3] Smith GP, Tao Y, Wang H. Foundational fuel chemistry model version 1.0 (FFCM-1).
http://nanoenergy.stanford.edu/ffcm1; 2016.
[4] Wang H, Xu R, Wang K, Bowman CT, Hanson RK, Davidson DF, et al. A Physics-
based approach to modeling real-fuel combustion chemistry – 1 Evidence from
experiments, and thermodynamic, chemical kinetic and statistical considerations.
Combust Flame 2018. [in press].
[5] Xu R, Wang K, Banerjee S, Shao J, Parise T, Zhu Y, et al. A Physics-based approach
to modeling real-fuel combustion chemistry – 2 Reaction kinetic models of jet and
rocket fuels. Combust Flame 2018. [submitted for publication November 2017].
[6] Shao J, Zhu Y, Wang S, Davidson D, Hanson R. Shock tube study of jet fuel pyrolysis
and ignition at elevated pressures and temperatures. Fuel 2018. [submitted for
publication January 2018].
[7] Wang C, Shu CW, Han W, Ning J. High-resolution WENO simulation of 3D deto-
nation waves. Combust Flame 2013;160(2):447–62.
[8] Shao J, Rutland CJ. Modeling investigation of different methods to suppress engine
knock on a small spark ignition engine. J Eng Gas Turbines Power
2015;137(6):061506.
[9] Pellett GL, Vaden SN, Wilson LG. Opposed jet burner extinction limits: simple mixed
hydrocarbon scramjet fuels vs. air AIAA paper, 5664 2007.
[10] Pellett GL, Vaden SN, Wilson LG. Gaseous surrogate hydrocarbons for a HIFiRE
scramjet that mimic opposed jet extinction limits for cracked JP fuels. In Presented
at 55th JANNAF propulsion meeting, 12–16 May, 2008, Boston, MA; 2008. JANNAF
Paper-847, 38 pp.
[11] Tsuboi T, Wagner HG. Homogeneous thermal oxidation of methane in reflected
shock waves. Proc Combust Inst 1975;15(1):883–90. Elsevier.
[12] Cheng RK, Oppenheim AK. Autoignition in methane-hydrogen mixtures. Combust
Flame 1984;58(2):125–39.
[13] Burcat A, Scheller K, Lifshitz A. Shock-tube investigation of comparative ignition
delay times for C1–C5 alkanes. Combust Flame 1971;16(1):29–33.
[14] Lifshitz A, Scheller K, Burcat A, Skinner GB. Shock-tube investigation of ignition in
methane-oxygen-argon mixtures. Combust Flame 1971;16(3):311–21.
[15] Grillo A, Slack MW. Shock tube study of ignition delay times in methane-oxygen-
nitrogen- argon mixtures. Combust Flame 1976;27:377–81.
[16] Seery DJ, Bowman CT. An experimental and analytical study of methane oxidation
behind shock waves. Combust Flame 1970;14(1):37–47.
[17] Walker DW, Diehl LA, Strauss WA, Edse R. Investigation of the ignition properties of
flowing combustible gas mixtures. Ohio State University, Columbus Aeronautical
and Astronautical Research Laboratory; 1969.
[18] Huang J, Hill PG, Bushe WK, Munshi SR. Shock-tube study of methane ignition
under engine-relevant conditions: experiments and modeling. Combust Flame
2004;136(1):25–42.
[19] Petersen EL, Davidson DF, Hanson RK. Ignition delay times of ram accelerator CH4/
O2/diluent mixtures. J Propul Power 1999;15(1):82–91.
[20] White DR. Density induction times in very lean mixtures of D2, H2, C2H2 and C2H4,
[21] Gay ID, Glass GP, Kern RD, Kistiakowsky GB. Ethylene—oxygen reaction in shock
waves. J Chem Phys 1967;47(1):313–20.
[22] Homer JB, Kistiakowsky GB. Oxidation and pyrolysis of ethylene in shock waves. J
Chem Phys 1967;47(12):5290–5.
[23] Drummond LJ. Shock-initiated exothermic reactions. V. The oxidation of ethylene.
Aust J Chem 1968;21(11):2641–8.
[24] Baker JA, Skinner GB. Shock-tube studies on the ignition of ethylene-oxygen-argon
mixtures. Combust Flame 1972;19(3):347–50.
[25] Suzuki M, Moriwaki T, Okazaki S, Okuda T, Tanzawa T. Oxidation of ethylene in
shock tube. Astronautica Acta 1973;18:359–65.
[26] Jachimowski CJ. An experimental and analytical study of acetylene and ethylene
oxidation behind shock waves. Combust Flame 1977;29:55–66.
[27] Hidaka Y, Kataoka T, Suga M. A shock-tube investigation of ignition in ethyle-
ne–oxygen–argon mixtures. Bull Chem Soc Jpn 1974;47(9):2166–70.
[28] Hidaka Y, Nishimori T, Sato K, Henmi Y, Okuda R, Inami K, et al. Shock-tube and
modeling study of ethylene pyrolysis and oxidation. Combust Flame
1999;117(4):755–76.
[29] Brown CJ, Thomas GO. Experimental studies of shock-induced ignition and tran-
sition to detonation in ethylene and propane mixtures. Combust Flame
1999;117(4):861–70.
[30] Spadaccini LJ, Colket MB. Ignition delay characteristics of methane fuels. Prog
Energy Combust Sci 1994;20(5):431–60.
[31] Cadman P, Bambrey RJ, Box SK, Thomas GO. Ethylene combustion studied over a
wide temperature range in high-temperature shock waves. Combust Sci Technol
2002;174(11–12):111–27.
[32] Horning DC., Ph.D. Thesis Stanford, CA: Department of Mechanical Engineering,
Stanford University; 2001.
[33] Kalitan DM, Hall JM, Petersen EL. Ignition and oxidation of ethylene-oxygen-di-
luent mixtures with and without silane. J Propul Power 2005;21(6):1045–56.
[34] Saxena S, Kahandawala MSP, Sidhu SS. A shock tube study of ignition delay in the
combustion of ethylene. Combust Flame 2011;158(6):1019–31.
[35] Penyazkov OG, Sevrouk KL, Tangirala V, Joshi N. High-pressure ethylene oxidation
behind reflected shock waves. Proc Combust Inst 2009;32(2):2421–8.
[36] Davidson DF, Ren W, Kanson RK. Experimental database for development of a
HiFiRE JP-7 surrogate fuel mechanism. 50th AIAA aerospace sciences meeting in-
cluding the new horizons forum and aerospace exposition. Reston, VA: AIAA; 2012.
p. 1–6.
[37] Burcat A, Radhakrishnan K. High-temperature oxidation of propene. Combust
Flame 1985;60(2):157–69.
[38] Qin Z, Yang H, Gardiner WC. Measurement and modeling of shock tube ignition
delay for propene. Combust Flame 2001;124(1):246–54.
[39] Burke SM, Burke U, Mc Donagh R, Mathieu O, Osorio I, Keesee C, et al. An ex-
perimental and modeling study of propene oxidation. Part 2: Ignition delay time
and flame speed measurements. Combust Flame 2015;162(2):296–314.
[40] Hong Z, Pang GA, Vasu SS, Davidson DF, Hanson RK. The use of driver inserts to
reduce non-ideal pressure variations behind reflected shock waves. Shock Waves
2009;19(2):113–23.
[41] Urzay J, Kseib N, Davidson DF, Iaccarino G, Hanson RK. Uncertainty-quantification
analysis of the effects of residual impurities on hydrogen–oxygen ignition in shock
tubes. Combust Flame 2014;161(1):1–15.
[42] Metcalfe WK, Burke SM, Ahmed SS, Curran HJ. A hierarchical and comparative

379
J. Shao et al. Fuel 225 (2018) 370–380

kinetic modeling study of C1–C2 hydrocarbon and oxygenated fuels. Int J Chem
Kinet 2013;45(10):638–75.
[43] Wang H, You X, Joshi AV, Davis SG, Laskin A, Egolfopoulos F, et al. USC mech
version II; 2007.
[44] Krishnan S, Ravikumar R. Ignition delay of methane in reflected shock waves.
Combust Sci Technol 1980;24(5–6):239–45.
[45] Skinner GB, Ruehrwein RA. Shock tube studies on the pyrolysis and oxidation of
methane. J Phys Chem 1959;63(10):1736–42.
[46] Brabbs TA, Robertson TF. Methane oxidation behind reflected shock waves: ignition
delay times measured by pressure and flame band emission. NAS
1986;1(15):87268.

380