Fuel 287 (2021) 119486

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Full Length Article

Ignition delay times of iso-butane activated by DME under various

equivalence ratios in the shock tube
Xue Jiang *, Wenlin Huang , Hao Zhao
State Key Laboratory of Multiphase Flows in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Keywords: The ignition delay time of the high cetane number dimethyl ether (DME), high octane number i-butane, and their
Ignition delay time binary blends were investigated in a shock tube over the temperature range of 1091–1797 K, pressures of 2–10
Shock tube atm, and equivalence ratios of 0.5–2.0. The LLNL iso-Octane Model and the DME sub-set of the Aramco3.0 Model
Iso-butane
were assembled together to reproduce the ignition delay behavior of the binary blends. Chemical kinetic analyses
DME
were conducted to understand the interplay between DME and i-butane at high temperatures. The ignition delay
Chemical kinetic
of DME and i-butane show the opposite equivalence ratio dependence under the current conditions. The pro­
moting effect of DME addition on the ignition delay of i-butane becomes more significant as the equivalence ratio
increases. The research result shows that there is no significant fuel to fuel interactions between DME and i-
butane in the present conditions. The high reactivity of DME and its rapid accumulation of the free radicals lead
to the promoted auto-ignition of i-butane.

1. Introduction
Rising environmental issues and increasingly stringent emissions
regulations have directed people towards alternative fuels and advanced
combustion technologies. Dual-fuel combustion has attracted wide­
spread attention as a new concept strategy for engines. The dual-fuel
combustion can be realized on compression ignition engines using the
globally lean and homogeneous mixtures, such as the homogeneous
charge compression ignition (HCCI) [1]. This dual-fuel operational
mode can achieve high thermal efficiency and low emission at low to
intermediate loads but is restricted by the extensive energy release and
dramatically increased pressure rise rate under heavy load [2]. Alter­
natively, the ϕ- stratified charge strategy, such as the partial fuel strat­
ification (PFS) and reactivity controlled compression ignition (RCCI),
can be used on dual-fuel engines to achieve the sequential auto-ignition
[3] and reduce the pressure rise rates [4] since the ignition delay time of
the ϕ-sensitive fuel varied with the equivalence ratio. Obviously, the
control of dual-fuel combustion is closely related to the fuel chemical
kinetics [5]. The co-applications of the high octane number (low reac­
tivity) and high cetane number (high reactivity) fuel blends were found
to be able to adjust the ignition timing, extend the operating range,
decrease heat release rate, and reduce the emissions [6].
DME (dimethyl ether) is well known as an oxygen-containing
alternative fuel of petroleum which has a high cetane number of 55–60.
It can be produced from a variety of sources with affordable price,
especially, the Bio-DME has been widely concerned worldwide in recent
decades [7]. Being the smallest ether without a C–C bond, DME can
decrease the particulate, CO, and HC emissions when used as a drop-in
substitute for transportation fuels [8]. DME is also been employed as the
high activity additive blended with high octane number fuels, such as
methane [9–11], ethane [12,13], propane [14,15], and gasoline
[16–18], to demonstrate dual-fuel combustion strategies. Likewise,
mixing DME with butane, the common ingredient in liquid petroleum
gas (LPG) and liquefied natural gas (LNG), is also an ideal scheme in the
implementation of dual-fuel engines considering the differences in
reactivity [19,20]. Butane it is the simplest alkane showing structural
isomerism, particularly, i-butane has a high octane number of RON102
which is characterized with good resistance to engine knock [20]. It is
noted that i-butane is also the smallest alkane include the tertiary carbon
bonds, thus it is recognized as the prototype fuel for understanding the
oxidation and chemical kinetic of large branched alkanes [21].
Fundamentally, the combustion characteristics of both pure DME
and pure i-butane have been widely studied, involving the ignition delay
times [22–28], laminar and turbulent flames [29–39], and pyrolysis
characteristics [21,40–43], etc. Furthermore, to guide the engineering
practice of dual-fuel combustion, fundamental researches on the

* Corresponding author.
E-mail address: xuejiang1128@xjtu.edu.cn (X. Jiang).

https://doi.org/10.1016/j.fuel.2020.119486
Received 5 September 2020; Received in revised form 25 September 2020; Accepted 27 September 2020
Available online 1 November 2020
0016-2361/© 2020 Elsevier Ltd. All rights reserved.
X. Jiang et al. Fuel 287 (2021) 119486

ignition delay of the DME/alkane blends have been performed in liter­ 2. Experimental procedures
ature. The influences of DME blending on the ignition of methane have
been studied in some detail from low to high temperatures [28,44–45], The ignition delay time can be measured by several types of equip­
note that a small amount of DME blending can strongly reduce the ment, among which shock tube is widely used for high temperature
ignition delay of methane. Burke and co-workers [28] suggested that the measurement. In this research, a stainless steel shock tube comprises a
significant effect of DME addition is because of the weaker carbon- double polyester terephthalate (PET) diaphragm structure was used, as
hydrogen bonds of DME relative to methane. Although DME addition shown in Fig. 1. The inner diameter of the shock tube is 11.5 cm, and the
results in the nonlinear promotion on the ignition delay, in the laminar driver section and driven section are 2 m and 7.3 m, respectively. He­
flames which reflects both the influences of fuel transport property and lium and nitrogen were used as driven gas to generate shock waves. The
chemical kinetic, DME blending was found to enhance the laminar flame test mixtures were prepared in a mix-tank and stand for more than 12 h
velocity of methane linearly [44]. The effects of DME blending on the before the experiment. Vacuum pump sets were used to evacuate the
high temperature ignition delays of C3 - C5 straight alkanes were pressure of the mix-tank and driven section under 1.0 Pa.
revealed to be quasi-linear [46–48]. However, the nonlinear trends of The CH* chemiluminescence was detected by a photomultiplier at
DME addition on both the first-stage and total ignition delays of propane the shock tube endwall during the test to determine the onset of ignition.
and n-butane were observed in the low to intermediate temperature The reflected shock pressure was also recorded by the PCB 113B03
rapid compression machine measurement measurements [15,49]. The pressure transducer at the endwall. The typical CH* chemiluminescence
effects of DME addition on the auto-ignition of high octane number fuel trace and pressure trace evolution histories during the experiment were
are especially important for the combustion control of dual-fuel engines, given in Fig. 2. The onset of ignition in this study is determined as the
besides, fundamental combustion and chemical kinetics studies of the time interval between the moment that the shock wave reached the
binary fuel mixtures are very useful for engine optimization and dual- endwall and the time of peak CH* chemiluminescence rise rate. The
fuel modeling. However, to the authors’ knowledge, available studies pressure rise dP/dt of this shock tube was 4.2%/ms [52], which was
are mainly focused on the effect of DME blending to the straight-chain taken into account in the numerical modeling by adopting the SENKIN/
alkanes, the ignition delay study of DME enriched i-butane have not VTIM method [53]. The typical uncertainty of the ignition delay time is
been conducted. The branched alkanes are the important constituent of
considerable concentration in conventional fuels [50], different chemi­
cal structures of the branched and straight isomers will lead to the
diverse combustion and emission characteristics [51]. Besides, i-butane
is the smallest branched alkane showing the combustion properties, such
as the negative temperature coefficient (NTC), similar to large molecular
fuels [26].
Therefore, in the absence of the investigations of the DME/i-butane
mixture, we have chosen to analyze the ignition delay times under
various equivalence ratios using a shock tube in the present work. The
predictions of literature kinetic models are compared with the ignition
delay times measured herein, literature i-butane model was assembled
with the available DME sub-set to reproduce the ignition delay behavior
of the binary mixtures. Finally, chemical kinetic analyses are performed
to understand the reaction chemistry of i-butane activated by DME at
high temperatures. This work will help provide the foundation for un­
derstanding the reactivity control of the binary mixtures containing
DME and their possible applications in the dual-fuel engines.

Fig. 2. Typical CH* chemiluminescence and pressure trace at the endwall and
the definition of ignition delay time.

Fig. 1. Schematic of the shock tube.

2
X. Jiang et al. Fuel 287 (2021) 119486

± 20% determined by the standard root-sum-squares approach [54,55]. Fig. 3 (e) - (g) presents the comparison between the measured and
More detailed information on this experimental bench is available in the calculated ignition delay times of pure DME at pressures of 2 and 10 atm,
literature [52]. equivalence ratios from 0.5 to 2.0. The computed ignition delay times by
The purity of the DME, i-butane, oxygen, argon, helium, and nitrogen both the Aramco3.0 Model and Reuter Model yield good agreement with
used in this study was 99.999%. The synthetic “air” (79% Ar and 21% all the experimental data of pure DME. However, the LLNL iso-Octane
O2) was used in this study. For each mixture, Ar was used as the buffer Model is significantly faster than the measurements, especially at 10
gas with a fixed mole fraction of 80%. The compositions of test fuel atm.
mixtures are listed in Table. 1. The Aramco Model was published by the Combustion Chemistry
Centre in NUI Galway and has been continuously updated since 2013,
3. Chemical kinetic mechanism the latest version of the Aramco3.0 Model is a comprehensive kinetic
mechanism for C1 - C4 hydrocarbon and oxygenated fuels with the
Numerical simulation of the ignition delay time was performed using updated sub-set of 1,3-butadiene by Zhou et al [58]. Although the
the zero dimensional closed homogeneous reactor model in the Aramco series models were found to well reproduce the ignition delay
Chemkin-Pro program [56] rests on the adiabatic and constant-volume times of n-butane in both shock tubes [61,62] and RCMs [49,63], this
assumption. The onset of ignition is defined by the simulated tempera­ model generally over-predicted the ignition delay for i-butane at 10 atm
ture inflection point of the maximum dT/dt. in this study. This is not surprising, as observed in the study of Li et al.
It is believed that an appropriate kinetic model for i-butane/DME [21], the Aramco model fails to reproduce the fuel mole fraction profile
binary mixture can well reproduce the ignition delay times of i-butane of i-butane pyrolysis in the flow reactor over the temperatures of
and DME individually. Three available kinetic models namely, the LLNL 900–1400 K, indicating that the existing C1 - C4 core mechanism in this
iso-Octane Model, Aramco3.0 Model, and Jetsurf2.0 Model were used to model cannot accurately describe the high temperature combustion
simulate the ignition delay properties of the pure i-butane mixtures: behavior of the branched alkane despite their ability to capture the
experiments of the normal alkanes.
• LLNL iso-Octane Model [57], which was published in 2009 by the JetSurf2.0 Model was a high temperature mechanism developed
Lawrence Livermore Nation Laboratory and consists of 874 species upon the base model of USC-Mech II [64], it includes the pyrolysis and
and 3796 elementary reactions. oxidation chemistry of alkanes up to C12 and mono-alkylated cyclo­
• Aramco3.0 Model [58], which was published in 2018 by the Com­ hexanes. However, the predicted ignition delays of this model for pure i-
bustion Chemistry Centre at NUI Galway and consists of 581 species butane are longer than the experimental results at 10 atm, ostensibly
and 3037 element reactions. because the USC-Mech II model fail to well capture the macroscopic and
• Jetsurf2.0 Model [59], which was published in 2010 funded by the microscopic combustion behaviors of both butane isomers [21,65,37].
US Air Force and consists of 348 species and 2163 element reactions. The LLNL iso-Octane Model was developed according to the rate
rules of branched alkanes proposed by Curran et al. [66] in NUI Galway,
Both the LLNL iso-Octane Model and Aramco3.0 Model contain the by comparing with the experimental data herein, it is found that this
DME sub-mechanisms thus were again used along with the Reuter Model model can reproduce the ignition delays of the i-butane/oxygen/Ar
for numerical simulations of pure DME mixtures. mixtures at all investigated equivalence ratios and pressures in this
study. Unfortunately, the LLNL iso-Octane model fails to reproduce the
• Reuter Model [60], which was published in 2018 by Ju and co- experimental results of pure DME ignition delays. Note that the DME
workers in Princeton University and consists of 130 species and sub-model in the LLNL iso-Octane model is similar to that in the Ethers
893 elementary reactions. Model [67] published by NUI Galway early on.
Nevertheless, the DME sub-set in the Aramco3.0 Model was updated
Fig. 3 indicates the comparison among the experimental results of according to the more recent studies of NUI Galway [28,68], the
pure i-butane and pure DME and the numerical simulations using the pressure-dependent rate constant for the decomposition of CH3OCH2
above-mentioned models. Fig. 3 (a) - (c) gives the experimental mea­ radical were updated according to theory calculations, besides, the rate
surements and numerical simulations of the ignition delay times for pure constants for some H-abstraction reactions of DME were also re-
i-butane at pressures of 2 and 10 atm, equivalence ratios of 0.5, 1.0, and evaluated. The simulations of the Aramco3.0 Model for DME ignition
2.0. i-Butane is the simplest branched alkane and its kinetic model is the delay showed good agreements with the experimental data of this study.
basis of the mechanism of higher-order branched alkanes, however, Again, the Reuter Model was developed based on the Princeton HP-
computations from both the Aramco3.0 Model and JetSurf2.0 Model Mech model [69], by validating against the ozone-assisted DME cool
slightly over-predicted the measured i-butane ignition delay time at 10 flames in the counterflow combustor, the low-temperature chemistry
atm from the lean (ϕ = 0.5) to rich(ϕ = 2.0) conditions. The predictions coupling with low-temperature transport of DME was updated. The
of the LLNL iso-Octane Model show good agreement with the measure­ consistency between the Aramco3.0 Model and the Reuter Model for
ments under all the pressures and equivalence ratios in this study. predicting the ignition delay times indicate that those two models show
agreement on the main reaction networks in the high temperature
oxidation chemistry of DME.
Table 1 Considering the approaching base mechanisms and consanguineous
Composition of fuel mixtures. rate rules, the DME sub-set in the LLNL iso-Octane Model was replaced
Mixtures ϕ XDME/ XC4H10/ XO2/ XAr/% by that in the Aramco3.0 Model to well predict the ignition behaviors of
% % % both i-butane and DME. It is found that the merged LLNL-ARA Model can
0.5 0.676 0.000 4.056 95.268 well capture the ignition delay times of i-butane, DME, and their
D100: 100% DME 1 1.308 0.000 3.924 94.768 mixture, as shown in Fig. 4. This proposed hybrid model is thereby used
2 2.456 0.000 3.684 93.860 to simulate the ignition delays and analyze the chemistry effect of DME
0.5 0.216 0.216 4.105 95.463 on i-butane reactivity in the following discussion.
IB50D50: 50% DME/50% i- 1 0.423 0.423 4.019 95.135
C4H10
2 0.812 0.812 3.857 94.519
0.5 0.000 0.318 4.134 95.548
IB100: 100% i-C4H10 1 0.000 0.626 4.069 95.305
2 0.000 1.214 3.945 94.841

3
X. Jiang et al.
Fig. 3. Comparison between current measurements and simulation results of available kinetic models at 2 and 10 atm, equivalence ratios of 0.5, 1.0, and 2.0.
4. Results and discussion
4.1. Effect of equivalence ratio
Fig. 4 presents the effect of equivalence ratio on the ignition delay
times of pure i-butane, pure DME, and their binary mixtures at 2 and 10
atm from the experimental and simulated results. It is apparent that for
pure i-butane, the reactivity decreases with increasing equivalence ratio,
as an increase in ignition delay time is noticed when the equivalence
ratio gradually increases from 0.5 to 2.0. Furthermore, similar effects of
equivalent ratio on the ignition delay time were obtained at both 2 and
10 atm, as shown in Fig. 4 (a) and (b). This reveals that the oxygen
concentration has a significant effect on the oxidation reactivity of i-
butane in the current condition. Due to the inherent nature of the shock
4
Fuel 287 (2021) 119486
tube facility, the ignition data of i-butane were recorded in the tem­
perature range of 1175–1820 K approximately in this study. At these
high temperature conditions, the reactive threshold step H + O2 <=> H
+ OH is the dominating chain-branching reaction for most alkane fuels
[27,45] whose rate increases with the increased oxygen concentration,
this has caused the fuel-lean mixtures to be most reactive. Rather, the
dependence on equivalence ratio is reversed for the ignition delays of i-
butane at low to intermediate temperatures in RCMs [25,26] since the
low temperature chain-branching of i-butane is depended upon the
molecular oxygen addition or internal hydrogen isomerization of the
butyl radicals emanating from the fuel, but these reaction pathways are
not proceeded during the high temperature oxidation.
Fig. 4 (c) and (d) illustrates the influence of equivalence ratio on the
ignition delays of pure DME at the pressures 2 and 10 atm, respectively.
X. Jiang et al.
Fig. 4. Effect of equivalence ratio on the ignition delay times of DME, i-butane and their mixtures at 2 and 10 atm. (symbol, experiment; line, simulation using the
LLNL-ARA Model).
Generally, the effect of equivalence ratio on the ignition delay time for
pure DME is much weaker relative to that of the pure i-butane. Again,
the reversed impact of equivalence ratio was observed for DME ignition,
that is the lean DME mixture is the slowest to ignite and the rich DME
mixture is the fastest in the current experimental conditions.
Fig. 5 and Fig. 6 give the Brute-force sensitivity analyses [25] and
normalized CH3 ROP for the ignition of pure DME mixtures at 10 atm,
1300 K, and various equivalence ratios, respectively. An interesting note
is that the ignition of DME under all equivalence ratios is strongly driven
by the fuel decomposition reaction CH3OCH3 (+M) <=> CH3 + CH3O
(+M) instead of H + O2 <=> H + OH. Besides, CH2O + CH3 <=> HCO
+ CH4 and CH3OCH3 + CH3 <=> CH3OCH2 + CH4 also give the high
negative sensitivity coefficient, emphasizing the importance of CH3
associated kinetic in the high temperature ignition of DME. With the
increase of equivalence ratio, CH3OCH3 + H <=> CH3OCH2 + H2
5
Fuel 287 (2021) 119486
becomes less sensitive, indicating a reduced ignition inhibiting effect.
Besides, the sensitivity index and the normalized ROP of the reactions
CH3 + HO2 <=> CH4 + O2 and CH3 + CH3 (+M) <=> C2H6 (+M) all
decreased with equivalence ratio, indicating the less pronounced
inhibiting channels of the CH3-relevant reactions. Meanwhile, sensi­
tivity coefficient and the normalized ROP for the ignition-promoting
reactions of CH3OCH3 + CH3 <=> CH3OCH2 + CH4 and CH2O + CH3
<=> HCO + CH4 all increase with equivalence ratio, corresponding to
the enhanced ignition promoting effect.
Generally speaking, as the equivalence ratio increases, although the
reduced oxygen concentration leads to the slightly less pronounced
chain-branching channel of H + O2 <=> H + OH. However, the reduced
chemical reactivity due to the above reason was compensated by the
enhanced decomposition channel of the DME and the derived CH3
relevant chain-branching reactions, eventually promote the reactivity of
X. Jiang et al.
Fig. 5. Brute-force sensitivity analysis for the ignition delay times of D100
mixture at the equivalence ratio of 0.5, 1.0, and 2.0, pressure of 10 atm, and
temperature of 1300 K (negative coefficient, ignition-promoting reaction; pos­
itive coefficient, ignition-inhibiting reaction).
DME with the increase of equivalent ratio in the current conditions.
We note that the equivalence ratio dependence for DME ignition
observed in this study is inconsistent with the observation by Burke et al.
[28]. Burke and co-workers measured the ignition delay time of pure
DME/“air” in both shock tube and RCM, they found that the ignition
delay times of DME slightly decrease with increasing equivalence ratios
in the shock tube measurements. We noticed that in the current study,
the test mixtures were diluted by inert with the fixed concentration of
80%, thus the mole fraction of oxygen only decreases by 0.372% when
the equivalent ratio increases from 0.5 to 2.0. Hence, the sensitivity
coefficient of H + O2 <=> H + OH did not change significantly with the
equivalent ratio. Nevertheless, the DME/ “air” mixture without dilution
was studied by Burke et al. [28] where the oxygen concentration de­
creases more obviously thus expressively inhibits the chain-branching of
H + O2 <=> H + OH under the fuel-rich condition and leads to the
reduced overall reactivity.
For the IB50D50 blends, straightforwardly, the combined equiva­
lence ratio dependence of i-butane and DME was observed, that is the
increasing equivalence ratio can inhibit the reactivity of the IB50D50
mixtures but less significant as that for the pure i-butane, as shown in
Fig. 4 (e) and (f).
Fig. 6. Normalized CH3 ROP in the ignition of D100 mixtures at 10 atm, 1300 K, and f = 0.5, 1.0, and 2.0 (a) ignition-inhibiting channel (b) ignition-promoting
channel (the ROP of each reaction was normalized by the total CH3 ROP, the time was normalized by the ignition delay time of individual mixture).
6
Fuel 287 (2021) 119486
4.2. Effect of DME addition
Fig. 7 (a) - (f) gives the effect of DME addition on the ignition delays
of i-butane at 2 and 10 atm. The ignition delay time of DME and i-butane
are approaching under the fuel-lean condition, while the divergence
between the ignition delays became apparent with the increasing
equivalence ratio. It is noted that adding DME into i-butane can shorten
the ignition delay times of the mixtures from the lean to rich conditions.
To interpret the influence of DME addition on the ignition kinetic of
i-butane, the LLNL-ARA Model was used to compute the fuel consump­
tion profile during the ignition of both neat fuels and their binary
mixture. The initial fuel percentage was 100% for all the mixtures, note
that the consumption rate of i-butane becomes apparently slower in the
IB50D50 mixture relative to that in the IB100 mixture during the igni­
tion, which indicates that i-butane consumption was inhibited by DME
addition. Meanwhile, the fuel percentage of DME drops apparently
faster in the IB50D50 mixture, suggesting that DME is more rapidly
consumed through the high temperature ignition of the dual mixture.
This makes sense since the ignition of the binary mixture hinges on the
ignitibility of the more active component with lower octane value [70].
DME with higher reactivity ignites first to produce free radicals and
releases heat results in the increases in the radical pool concentration,
temperature, and pressure thereby accelerates the auto-ignition of i-
butane.
Reaction pathway analyses were performed using the LLNL-ARA
model to clarify the kinetic effect of DME addition on the ignition de­
lays of i-butane. The simulated reaction pathway in both the pure and
binary mixtures for i-butane and DME are shown in Fig. 9 (a) and (b),
respectively.
For the consumption of i-butane, 29.1% of the fuel undergoes
unimolecular decomposition, the dissociation occurs on the primary-
tertiary C–C bond and produces CH3 and IC3H7. Meanwhile, as for n-
butane, the high temperature decomposition of fuel happens on both the
primary-secondary and secondary-secondary C–C bonds site [27],
indicating the obvious influence of isomeric structure on butane unim­
olecular decomposition at high temperature. The reaction pathway in
Fig. 9 (a) also reveals that the H-abstraction reactions are making
important contributions to the consumption of i-butane, the iC4H9 and
tC4H9 radicals are produced via the H-abstractions from the primary and
tertiary C–H bond, respectively. Besides, the t-butyl radical is entirely
expended by the beta-scission reaction to produce IC4H8 which again
generates the IC4H7 via H-abstraction fluxes. Note that the C3H6 was
abundantly produced in the oxidation of i-butane via the reaction
channels of IC3H7 <=> H + C3H6, IC4H9 <=> C3H6 + CH3, and IC4H8 +
H <=> C3H6 + CH3. After that, C3H5-A and C2H4 were produced
attributed to the H-abstractions and the decomposition of propene,
respectively. The produced C3H5-A radical is chemically unreactive due
to the resonant stabilization, which is considered as one of the factors
X. Jiang et al.
Fig. 7. Effect of DME addition on the ignition delay times i-butane at 2 and 10 atm, equivalence ratios of 0.5, 1.0, and 2.0. (symbol, experiment; line, simulation
using the LLNL-ARA Model).
that led to the longer ignition delays of i-butane rather than n-butane
[27].
Fig. 9 (b) gives the reaction pathway of stoichiometric DME at 1300
K, 10 atm. For pure DME, it can be seen from the scheme that the H-
abstraction is the primary channel (74.1%) in the ignition to produce the
CH3OCH2 radical under the current condition. After that, 100% of the
CH3OCH2 decomposed to produce CH2O and CH3 at 1300 K. Never­
theless, the H-abstraction is also the primary pathway of the low tem­
perature oxidation of DME, the produced CH3OCH2 radical can react
with molecule oxygen to produce the CH3OCH2O2 radical at the inter­
mediate to low temperatures, again to produce the CH3OCH2O2H.
Competition on the branch consumption path of CH3OCH2O2H between
CH2OCH2O2H <=greater than 2CH2O + OH and CH2OCH2O2H + O2
<=> O2CH2OCH2O2H resulted in the negative temperature coefficient
phenomenon (NTC) of DME oxidation [28]. As illustrated in Fig. 9 (b),
the favored reaction path of CH3OCH2 radical is varied from O2 addition
7
Fuel 287 (2021) 119486
to decomposition in high temperatures. Note that at 1300 K, 25.6% of
the DME also decomposed to produce CH3O and CH3, then the CH3O can
readily produce CH2O.
As shown in Fig. 9, fuel to fuel interactions between DME and i-
butane were not observed in the current conditions. This view is also
supported by the fact that the kinetic model for predicting the ignition
delays of the DME/i-butane binary mixture can be obtained by directly
combining the corresponding sub-models in this study. Dames et al. [15]
did an experimental and theoretical study on the oxidation of DME/
propane blends under engine-relevant conditions and have come to
similar conclusions. They also suggest that the dual-fuel model for DME
and low-reactivity mixtures can be obtained simply by combining the
individual sub-mechanisms together.
Nevertheless, DME addition leads to the slightly enlarged H-
abstraction channel and the correspondingly reduced decomposition of
i-butane at 20% fuel consumption. Accordingly, the decomposition
X. Jiang et al. Fuel 287 (2021) 119486

pathway of DME was promoted while the H-abstractions were inhibited

slightly when blended with i-butane. This is reasonable, as shown in
Fig. 8, DME was more reactive which consumed earlier than i-butane
and lead to increased production of free radicals. Obviously, the pro­
duced free radical by DME oxidation promotes the H-abstraction of i-
butane. In the meantime, since the radical pool was consumed by the
competition of i-butane oxidation, the decomposition pathway of DME
was enlarged at high temperatures after blending.
Small radicals such as H, O, and OH, are important chain carriers for
the high temperature oxidation of both DME and i-butane, the concen­
tration of which are closely related to the ignition chemical. Besides, the
CH3 radical is of importance for the high temperature oxidation of DME.
Fig. 10 (a) shows the simulated mole fraction profiles for the sum of
H, O, and OH radicals for the stoichiometric D100, IB50D50, and IB100
mixtures at 1300 K. It is note that the radical pool mole fractions for H,
O, and OH remained essentially flat during the early induction time
while dramatically peaked near the moment of ignition. The formation
of the radical pool gradually accelerated while the peak concentrations
slightly increased successively in the mixtures of IB100, IB50D50, and
D100. Similarly, DME addition was found to promote the radical pool
during the high temperature ignition of small straight alkanes [45–47].
This indicate that the addition of the fast-reacting DME into the slow-
reacting alkanes can lead to the more pronounced accumulation of
free radicals thus enhance the overall chemical reactivity and reduce the
ignition delay time.
Again, Fig. 10 (b) gives the mole fraction time-histories of the CH3
radical in the IB100, IB50D50, and D100 mixtures. It is found that the
CH3 radicals build up continuously during ignition induction period and
consume rapidly near the ignition, revealing that the CH3 radical is
crucial for the early accumulation of the radical pool. For pure i-butane
oxidation without DME addition, the initiation of radical pool is
administrated by the fuel decomposition reaction IC4H10 (+M) <=>
CH3 + IC3H7 (+M). Besides, IC4H9 <=> C3H6 + CH3 and C3H6 + H <=>
C2H4 + CH3 also make relatively big contributions to the growth of CH3
radials in the early induction time. The reaction CH3 + CH3 (+M) <=>
C2H6 (+M) is the primary channel against the growth of CH3 radical
(Given in the ROP analysis in the Supporting Material). When the CH3
accumulated to sufficient concentrations, the reaction CH3 + O <=>
CH2O + H becomes the governing step of CH3 consumption near the
ignition and lead to the rapid growth of the H radical. DME addition can Fig. 9. Reaction pathway of (a) i-butane and (b) DME for IB100, D100 and
promote the buildup of CH3 radical since the CH3 radical can be readily IB50D50 mixtures at 10 atm, 1300 K,ϕ = 1.0, and 20% fuel consumption
(black: pathway for pure i-butane or pure DME, blue: pathway for binary
generated by DME decomposition and beta - scission of the CH3OCH2
mixture). (For interpretation of the references to colour in this figure legend,
radical. In the meantime, HO2 can be largely produced during DME
the reader is referred to the web version of this article.)
oxidation following the sequence of CH2O → HCO → HO2. This causes
the ignition promoting channel of CH3 + HO2 <=> CH3O + OH
becomes more pronounced after DME addition and enhances ignition. In
addition, the chain-branching channel CH3OCH3 + CH3 <=> CH3OCH2
+ CH4 compete for CH3 and lead to the reduce the chain termination of
CH3 + CH3 (+M) <=> C2H6 (+M) in the early stage.

5. Conclusion

Ignition delay times of DME, i-butane, and their blends were

measured using a shock tube at pressures of 2 and 10 atm, equivalence
ratio of 0.5, 1.0, and 2.0. The experimental data were compared with the
simulations from four representative kinetic models, namely the LLNL
iso-Octane Model, Aramco3.0 Model, Jetsurf2.0 Model, and Reuter
Model. None of the above models can give good predictions on the
ignition delays of both i-butane and DME. Therefore, the LLNL iso-Oc­
tane Model was combined with the DME sub-mechanism from the
Aramco3.0 Model. The assembled LLNL-ARA Model can well capture the
ignition delay times of i-butane, DME, and their binary mixture under
the current conditions.
The reactivity of pure i-butane decreases with increasing equivalence
Fig. 8. Computed fuel consumption profile during ignition the stoichiometric
ratio in this study, indicating that the oxygen concentration has a sig­
DME, i-butane and their mixture at 10 atm, 1300 K using LLNL-ARA Model. (the
nificant effect on the high temperature oxidation reactivity of branched
time was normalized by the ignition delay time of the individual mixture).

8
X. Jiang et al.
Fig. 10. Effect of DME addition on the radical mole fraction at 1300 K, 10 atm, ϕ = 1.0 (a) radical pool mole fraction for H, O, and OH; (b) CH3 radical. (Solid lines:
radical mole fraction, Dash-dot lines: the moment of ignition).
alkane. On the contrary, DME gives the opposite equivalence depen­
dence to i-butane. It is found that the ignition of DME is strongly driven
by the fuel decomposition reaction CH3OCH3 (+M) <=> CH3 + CH3O
(+M) instead of H + O2 <=> H + OH, the CH3 associated kinetic are
important in the high temperature ignition of DME.
Adding DME into i-butane can lead to shorter ignition delay times
under all equivalence ratios. The consumption of i-butane was inhibited
by DME addition, while DME is more rapidly consumed through the high
temperature ignition of the dual mixture. Fuel to fuel interactions be­
tween DME and i-butane were not observed in the current conditions. In
fact, the kinetic coupling effect between the two fuels is mainly reflected
in the following aspects: the high reactivity of DME and its rapid accu­
mulation of the free radicals lead to the promoted ignition delay of i-
butane.
CRediT authorship contribution statement
Xue Jiang: Conceptualization, Methodology, Writing - original
draft, Writing - review & editing, Funding acquisition. Wenlin Huang:
Visualization, Investigation. Hao Zhao: Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This study was supported by the National Natural Science Founda­
tion of China (Grant number: 51876164), China Postdoctoral Science
Foundation Grant (Grant number: 2018 M640987 and 2019 T120907),
State Key Laboratory of Engines, Tianjin University.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2020.119486.
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