Fuel 339 (2023) 127353

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Fuel
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Full Length Article

Effects of non-equilibrium plasma and equilibrium discharge on

low-temperature combustion in lean propane/air mixtures
Yangyang Ban a, Shenghui Zhong a, b, Jiajian Zhu c, Fan Zhang a, *
a
State Key Laboratory of Engines, Tianjin University, Tianjin 300350, China
b
Beihang Hangzhou Innovation Institute Yuhang, Xixi Octagon City, Yuhang District, Hangzhou 310023, China
c
Science and Technology on Scramjet Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Hunan 410073, China

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

Keywords: A zero-dimensional (0D) non-equilibrium plasma assisted ignition/combustion (PAI/PAC) model is established
Non-equilibrium plasma by coupling plasma kinetics and combustion kinetics to investigate the effect of non-equilibrium nanosecond
Low temperature combustion repetitively pulsed discharge (NRPD) plasma and equilibrium discharge on low-temperature combustion (LTC)
Plasma assisted combustion
stage of lean propane/air mixtures. The results show that the NRPD case has the fastest ignition, in comparison to
Propane
equilibrium discharge (ED) with the same discharge energy. With NRPD before LTC, electrons, O(1D), as well as
Plasma/chemical kinetics
O and OH, are formed during discharge, promoting propane consumption dramatically. Electron collision with
propane can promote propyls (NC3H7/IC3H7) and alkenes, but there is a competitive relationship in terms of
discharge energy between them. The formed propyls are mainly consumed to produce propyl peroxyl (NC3H7O2/
IC3H7O2) and accelerate low-temperature product formation, such as ketones and OH. The relaxations of
vibrationally excited states are the dominant pathways of heat release, leading to the continuous temperature
rising after NRPD. Finally, the negative temperature coefficient (NTC) performances under auto-ignition, NRPD,
and ED are investigated. ED only shifts the NTC to the low-temperature zone, while NRPD eliminates the NTC
phenomenon. The provided path fluxes of intermediates show that the promoted NC3H7/IC3H7 and NC3H7O2/
IC3H7O2 induced by NRPD weaken the negative correlation between the oxidation rate of NC3H7/IC3H7 and
temperature. The higher concentrations of NC3H7/IC3H7 and HO2 radicals during discharge can result in an
advanced intermediate/high temperature reaction process.

and spark discharge influence the ignition for a hydrocarbon fuel with a
NTC regime in high pressure is still lacking.
1. Introduction
During non-equilibrium discharge, a large proportion of discharge
energy is used to accelerate electrons leading to higher electron tem­
Low-temperature combustion strategies in ICEs have attracted more
perature instead of converting into heat. There are four major paths of
attention due to low emissions and high thermal efficiencies [1,2].
PAI/PAC summarized in [7] including the thermal effect via electron
However, a lean burn mixture will lead to a longer IDT or even misfire
elastic collision and gas heating, the kinetic effect brought by various
resulting in a limited engine operation range [3]. With a high-energy
excited species and radicals produced during inelastic collisions, the
spark, the ground electrode restrains the high-temperature region and
diffusion transport enhancement by molecular dissociation into frag­
flame kernel size [4]. A significant part of discharge energy is lost by
ments and the convective transport enhancement via ion wind.
heat transfer to the surroundings [5,6], leading to a strict requirement
Numerous researches are devoted to revealing the kinetic effect of non-
for MIE. Non-equilibrium discharge has been used to stabilize or stim­
equilibrium plasma on small hydrogen molecules [8,11–14]. Uddi et al.
ulate ignition in a lean fuel–air mixture [7,8], which suggested the
[12] carried out a 0D simulation of plasma-assisted CH4/air during a
significant advantages compared with a spark in ICEs [9,10]. For
single pulse and found that atomic oxygen is the key species for PAC. Ju
example, with NRPD, IDT was three to four orders of magnitude shorter
et al. [8] confirmed the importance of O(1D) in producing the initial
and approximately 13–17 % narrower in combustion duration than SI
radicals for PAC, while a more important role of O2(a1Δg) than O(1D) in
[9]. Also, the faster flame propagation [10] has been verified during
an NSD-DC hybrid discharge has also been proven [15]. In short, the
NRPD in comparison to SI. However, how do non-equilibrium plasma

* Corresponding author.
E-mail address: [email protected] (F. Zhang).

https://doi.org/10.1016/j.fuel.2022.127353
Received 5 November 2022; Received in revised form 11 December 2022; Accepted 30 December 2022
Available online 7 January 2023
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
Y. Ban et al. Fuel 339 (2023) 127353

region [22] and the disappearance of NTC assisted by non-equilibrium

Nomenclature plasma is also found [7,23]. Filimonova [23] modeled the discharge
impact on multistage ignition of C3H8/air mixture neglecting detailed
0D Zero-dimensional plasma kinetics. The results showed that discharge reduced the induc­
PAI/PAC Plasma assisted ignition/combustion tion period of the LTC stage by one order of magnitude due to the for­
LTC Low-temperature combustion mation of hydroperoxide and O atom promoted by plasma. More
SI Spark ignition recently, Filimonova et al. [24] further investigated the influence of
ED Equilibrium discharge non-equilibrium discharge on the LTC stage in HCCI engines. The results
IDT Ignition delay time suggested that the optimal discharge initiation time is at the beginning
NTC Negative temperature coefficient of the LTHR or ITHR. It is concluded that non-equilibrium discharge can
MIE Minimum ignition energy control the combustion timing and accelerate ignition if the plasma
ICE Internal combustion engine discharge is before LTHR. However, they ignored metastable states and
HCCI Homogeneous charge compression ignition the heat released from relaxation in non-equilibrium plasma, with the
LTHR Low-temperature heat release absence of detailed path fluxes of fuel consumption. In a nutshell, few
ITHR Intermediate-temperature heat release studies have been conducted to investigate low-temperature propane/
HTHR High-temperature heat release air ignition by non-equilibrium plasma with detailed plasma mechanism
EEDF Electron energy distribution function as well as comparison with equilibrium discharge.
NSD Nanosecond discharge In this paper, the discharge and combustion processes are simulated
DC Direct current simultaneously by coupling plasma kinetics solver ZDPlasKin and
HRR Heat release rate combustion solver Chemkin. The non-equilibrium PAI/PAC mechanism
VT Vibrational-relaxation of propane/air is established and validated. With the detailed mecha­
PFA Path flux analysis nism, the effects of non-equilibrium plasma and equilibrium plasma on
LTC of a lean propane/air mixture are investigated when the discharge
timings are before LTC stage. Reaction pathways and heat release rates
of the plasma kinetics and LTC oxidation reactions are carried out to
effect of non-equilibrium plasma on high-temperature ignition of small show the influences of NRPD and ED on NTC.
hydrocarbon fuels has been well-studied.
For LTC assisted by plasma, a few papers have been done recently, 2. Kinetic mechanism and numerical method
focusing on the chemical kinetics of low-temperature pyrolysis and
oxidation of dimethyl ether [16], propane [17,18], and other macro­ 2.1. Kinetic mechanism
molecule hydrocarbon fuels [19–21]. Among these works, it is
concluded that the low-temperature fuel consumption pathways assisted At first, IDTs in the three oxidation mechanisms of C3H8/air are
by non-equilibrium plasma are direct electron impact dissociation, compared with experiments under high pressure and different equiva­
plasma-generated radicals and excited species such as O and O(1D). lence ratios, as shown in Fig. 1. The right-most figure in Fig. 1 is con­
Also, the initiation of H abstraction by plasma can accelerate low- ducted by San Diego mechanism including 58 species and 270 reactions
temperature chain branching reactions and alkyl production. which is highly recommended in [25]. The left-most one is by Petersen
Propane is the smallest alkane fuel with both NTC behavior and LTC mechanism involving 118 species and 663 reactions [26] and the middle
process, and plays a significant role in the understanding of knock and is by Gokulakrishnan mechanism including 966 reactions and 136 spe­
misfire in ICEs [22], providing the best way to investigate the effect of cies [27]. It is found that three mechanisms can predict IDT well at high
non-equilibrium plasma on NTC. Liao et al. found that O3 addition in temperatures and show NTC behavior. While Gokulakrishnan mecha­
propane/air mixture can weaken the slow chemistry of H2O2 in the NTC nism with detailed NOx chemistry at low temperatures provides a rather

Fig. 1. IDT prediction among three mechanisms. Curves are calculations, symbols are experimental data [28].

2
Y. Ban et al. Fuel 339 (2023) 127353

for specie i in reaction j, Rj the reaction rate for reaction j, Ngas the gas
number density, Tgas the gas temperature, γ the specific heat ratio, Pelast
the elastic collision power, [Ne] the electron number density, Qsrc the
source term. δε is the heat release from enthalpy change, which is not
considered in plasma kinetics but in combustion kinetics.
In combustion reaction kinetics, the evolution of mass fractions for
specie k and temperature yields:
dρYk
= Wk ωk + Sρ Yk , k = 1, 2, ⋯, Ns (3)
dt

dρcp Tgas ∑ Ns
+ ρhk ωk = 0 (4)
dt k=1

where Wk, Yk, ωk and hk are the molar mass, mass fraction, chemical
reaction rate and specific enthalpy for specie k. ρ is the mixture density,
and cp is the specific heat at constant pressure. The whole Ns + 1 ordi­
nary differential equations are computed by Chemkin-III [35].
Similar to [13], multiple discharge pulses (100 pulses) are involved,
where both plasma kinetics and combustion kinetics are coupled
Fig. 2. Normalized OH number density during single-pulse nanosecond simultaneously during each pulse duration. Within one time step, the
discharge in C3H8/air plasma. concentrations of various components and temperatures are calculated
by ZDPlasKin [36] and then solved by the constant pressure chemical
good comparison with experimental data and the prediction is better solver Chemkin-III for combustion oxidation. After that, all the species
than the others. Since it has been verified that NOx can enhance com­ and temperatures are returned to the plasma kinetics solver. The inter­
bustion at low temperatures, and reduce IDT [27] and the enhancement action between both solvers repeats until the end of discharge. After a
effect is even greater than that of atomic oxygen production [11]. series of time dependence tests, the time step size of 10-9 s is employed
Then, the mechanism of PAI/PAC C3H8/air is developed based on the for temporal evolution. This model verification can be referred to the
air plasma kinetic mechanism [29], propane/air plasma kinetics [17] previous works [37,38].
and oxidation reactions from Gokulakrishnan [27]. For plasma kinetics, Fig. 2 shows the comparison of OH number density between exper­
there are 1599 reactions involving various processes such as excitation, iment and simulation. The experiment was conducted in C3H8/air
ionization, the relaxation of excited states, and charge exchange re­ mixture during single-pulse nanosecond discharge, where the initial
actions. 187 species are included such as electrons, ions, and vibra­ temperature is 300 K, the pressure of 1 atm, equivalence ratios of 0.1 and
tionally/electronically excited molecules. The collisions between 1.0, discharge duration of 10 ns and a repetition rate of 10 Hz [39].
electrons and intermediate species/products are ignored due to the low During the simulation, the irregular discharge voltage waveform in
concentrations [13]. Rate constants of electron impact reactions experiment is reduced to a square wave. Accordingly, the reduced
depending on EEDF are calculated by two-term approximation Boltz­ electric field is fixed at 120 Td, which is consistent with the breakdown
mann equation using BOLSIG+ [30] based on the corresponding colli­ field in experiment. The initial electron number density is adjusted to
sion cross sections. The collision cross sections of O2 and N2 are taken ensure the same discharge energy as experiments per pulse. Fig. 2 in­
from Phelps [31] and SIGLO [32] databases and the dissociative exci­ dicates a good agreement between simulation and experiment, espe­
tation collision cross sections of propane are computed according to cially the delay time of OH after discharge.
Ref. [33]. It is noteworthy that the dissociation energies of the C–H
bond are larger than that of the C–C bond in propane molecule [34]. 3. Initial condition and computational cases
Thus, the electron collision process can not only produce various radi­
cals such as H atoms and H2 but also smaller hydrocarbon molecules Five cases are carried out to study the effect of ED and NRPD with the
such as C2H4 and CH4. In total, the detailed mechanism consists of 187 same discharge energy on ignition and fuel consumption in Table 1. The
species and 2565 reactions (see Supplementary materials). To the best of discharge time is specified at 0 ms (before LTHR), where the LTHR stage
the authors’ knowledge, experimental data related to non-equilibrium is characterized by the first appearance of the maximum OH [23]. The
PAI/PAC C3H8/air mechanism validation under high pressures is not initial thermo-dynamic conditions for all cases are a pressure of 30 atm
available, however, the air plasma kinetics [29] and propane/air plasma and an equivalence ratio of 0.5. Case 4 and Case 5 are designed to study
kinetics used in this paper are validated in [17]. The full mechanism can the influence of NRPD on NTC. Besides, the repetitive rate of NRPD is 1
be found in the supplementary file. MHz, and the pulse duration is 25 ns [12]. The high discharge frequency
and short pulse duration can avoid the arc transition and ensure a sig­
2.2. Numerical method nificant discharge energy depositing into the formation of excited spe­
cies instead of thermal heating. Within one pulse the reduced electric
For plasma kinetics modeling, the following equations (1)-(2) are field (E/N) is fixed at 100 Td [23,24], while in the pulse interval, no
solved. In energy conservation Eq. (2), the temperature rising caused by energy is inputted (E/N = 0 Td). To keep the same discharge energy at
Joule heating is considered by the penultimate term.
j Table 1
d[Ni ] ∑ max
Initial parameters of simulation cases.
= Qij (t) (1)
dt j=1
Case discharge type discharge time T0 / K φ

j 1 Auto ignition – 700 0.5

Ngas dTgas ∑ max
2 NRPD before LTHR 700 0.5
= ±δε⋅Rj + Pelast ⋅[Ne ] + Qsrc (2)
γ − 1 dt j=1 3 ED before LTHR 700 0.5
4 Auto ignition – 800 0.5
5 NRPD before LTHR 800 0.5
where, [Ni] is the number density for specie i, Qij the rate of production

3
Y. Ban et al. Fuel 339 (2023) 127353

4.2. Comparison between NRPD and ED

It is well recognized that spark discharge, characterized by equilib­

rium plasma, ignites the charge by importing higher temperature,
without chemical selectivity. A comparison of ignition between equi­
librium discharge (ED) and non-equilibrium discharge (NRPD) with the
same discharge power and duration is carried out, as shown in Fig. 4.
The NRPD power is calculated as follows:
p = j × E = ene vdr E (5)

where, j is the discharge current, E the electric field, e the elementary

charge, ne the electron number density and vdr the electron drift velocity,
obtained from BOLSIG+ [30]. According to Eq. (1), the input energy
density by NRPD in Case 2 is 0.715 J⋅cm− 3. The equilibrium discharge is
reduced to an external heat source adding to the energy equation.
In Fig. 4a, it can be found that IDT with ED (Case 3) is shortened by
42 %, while NRPD (Case 2) is 77 % in comparison with autoignition
(Case 1). Under the same input energy, NRPD is more effective than ED
in reducing IDT, which is consistent with the result in Ref. [9]. It is noted
Fig. 3. The distribution of electron energy loss fractions in E/N space. that although using the same input energy, the temperature of Case 3 is
higher than that of Case 2 at 0.1 ms (the end of discharge), indicating
different equivalence ratio cases, the electron density has to be adjusted. that partial energy during NRPD is transferred to the internal energy of
In the current cases, the electron density is specified as 5 × 1011 cm− 3 for molecules. The temperature in Case 3 keeps constant immediately as
φ = 0.5 and kept constant during the simulations. Nevertheless, the
quenching of ions is calculated normally.

4. Results and discussion

4.1. Electron energy loss fraction

The Electron energy loss fraction represents electron energy transfer

direction at a certain E/N, which is conducive to understanding the
discharge energy deposition channels [30]. As shown in Fig. 3, at low E/
N (<30 Td), most of the discharge energy is used to excite vibrational
states of C3H8, O2 and N2. With E/N increasing, electron energy spent in
the dissociation of C3H8, and the excitation of O2 and N2 increases. As E/
N continues to increase, the proportion of electron energy depositing
into the ionization channel boosts and dominates in the discharge. The
gray area represents the current simulation condition where the disso­
ciation of C3H8, vibrationally and electronically excited N2 and O2
should be included. In addition, dissociation and ionization of O2 and N2
are added into the kinetic mechanism, while the C3H8 vibrational states
and C3H+ 8 are not considered for lack of corresponding reactions. Fig. 5. The temporal evolution of mole fractions in terms of key species in Case
2 (solid line) and Case 3 (dotted line).

Fig. 4. Temporal evolution of a) temperature, OH mole fraction, and b) HRR under auto-ignition, ED and NRPD conditions for cases 1–3, respectively.

4
Y. Ban et al. Fuel 339 (2023) 127353

Fig. 7. The temporal evolution of main radical mole fractions at LTC stage and
Fig. 6. The temporal evolution of HRRs of main reactions in Case 2 temperature in Case 2 and Case 1.
after discharge.

soon as the discharge is off. However, after discharge, the temperature in

Case 2 continues to increase and exceeds that of Case 3 at about 0.2 ms.
From Fig. 4b, it can be seen that HRR oscillates with pulsed discharge
and considerable heat has been released during NRPD. While the heat
release during ED can be ignorable. The results also show that for both
discharges, the LTC stage is shortened and then, the ignition event oc­
curs in advance compared with Case 1 without discharge.
The reason for the continuous temperature rising in Case 2 can be
explained in Fig. 5 and Fig. 6. In Fig. 5, the initial repetitive spikes
denote discharge pulses. It is found that there are more excited states
formed during NRPD such as O2(a1Δg), vibrationally excited O2 and N2.
For NRPD in Case 2, alkyls such as IC3H7 and NC3H7 and smaller hy­
drocarbon molecules such as C2H4 are produced in advance compared
with ED in Case 3 due to electron and electronically excited N2 collisions
with propane [17], which will be explained in Fig. 8. Also, an amount of
O, O(1D) and OH are formed during discharge which accelerate propane
oxidation [17,40]. On the contrary, radicals are rarely generated during
ED (before 1 ms).
It is suggested that for propane combustion there are three different
heat release stages, namely, a high-temperature (T > 1200 K), a low-
Fig. 8. PFA of propane integrated into the discharge duration for Case 2.
temperature (T < 900 K), and an intermediate-temperature (T = 1000
Negative values denote specie destruction.
– 1200 K) heat release stage [2,40]. We focus on LTHR stage in cases 2
and 3 where discharge is initiated before LTC stage. Generally, if T is
below LTC region, the ignition of hydrocarbon fuel is initiated by the HRRs of main exothermic reactions after NRPD are plotted in Fig. 6.
abstraction of hydrogen through (I) and (II). Then the formation of It is found that the accumulated alkyls IC3H7 and NC3H7 during
peroxide via (III) and hydroperoxide is followed by hybridization (IV). discharge are oxidized to form propyl peroxy radicals IC3H7O2 and
Subsequently, hydroperoxide combines with O2 to produce O2QOOH NC3H7O2 through R478, R476 and dominate heat release during LTC,
through (V). Finally, hydroxyl radicals and oxygen-containing hydro­ which is illustrated in reactions (I)-(VII). In addition, reactions R2078
carbons are produced via (VI) and (VII). During NTC region, peroxide and R1966 also play a significant role, indicating the importance of
RO2 and hydroperoxide QOOH usually decompose into R, HO2 and electron attachment reaction and O2(vib1) VT process in LTC stage.
alkene via RO2 => R + O2 and QOOH => HO2 + alkene. Thus, the chain Following that, oxidation pathways involving N and H atoms through
branching reactions (VI) and (VII) are replaced and the fuel consump­ reactions R616 and R11 also release a majority of the heat meanwhile.
tion rate is slowed down, leading to the NTC effect. The detailed NTC Fig. 7 shows the key species in terms of OH production at LTC stage
analysis for C3H8/air can be referred to Appendix. during NRPD (Case 2) and auto-ignition (Case 1) processes. Compared to
Case 1, there are much more low-temperature products related to the
RH + O2 = R + HO2 (I) OH low-temperature generation pathway under NRPD, such as NC3H7O2
(RO2), C3H6OOH (QOOH), O2C3H6OOH (O2QOOH) and OC3H5OOH
RH + X = R + XH (X = O, H, OH) (II)
(OQ’OOH) which is known as KETO. Especially during the isomerization
R + O2 = RO2 (III) of O2QOOH and KETO, OH-carriers break down to form OH radicals and
release heat. The more low-temperature products produced during
RO2 = QOOH (IV) NRPD promote OH production and enhance low-temperature reaction
pathways.
QOOH + O2 = O2QOOH (V)
Fig. 8 shows the PFA of propane consumption in Case 2. Here, PFA is
O2QOOH = OQ’OOH + OH (VI) defined as the proportion of the contribution from a certain reaction to
the total production/consumption of one species integrating over the
OQ’OOH = Q’’O + Q’’’O + OH (VII)

5
Y. Ban et al. Fuel 339 (2023) 127353

Fig. 9. PFA of a) O and b) OH before the end of discharge in Case 2.

entire discharge process. Propane dissociation directly from electron reaction i. For electron impact reactions, the sensitivity coefficient is
collision via R2475, R2476 occupies 38.5 % of propane destruction. defined as:
Also, plasma directly generated high energy excited atoms O(1D)
τ(2σi ) − τ(σi )
reacting with fuel (R1000 and R1001) accompanied with the rapid S= (7)
τ(σ i )
generation of IC3H7 and NC3H7 is the second important propane con­
sumption pathway, which can explain the early generation of propyl
where σ i represents the cross sections for reaction i. A negative value
radicals in Fig. 5. Meanwhile, neutral specie OH is still the primary
suggests a positive effect of the corresponding reaction on ignition. A
factor of propane destruction, accounting for 43.7 %. Conversely, H
large absolute value of the sensitivity coefficient implies a great impact.
atoms play a minor role in propane consumption [40], as well as
Fig. 10a shows the sensitivity analysis of IDT for the lean propane/air
N2(A3Σ+ u ) which is not shown for brevity. under NRPD. It can be found that the vibrationally excited states of N2
According to Fig. 8, about 51.4 % of propane is consumed by reacting
and O2 (E + N2 => E + N2(V), E + O2 => E + O2(V)) have positive
with OH and O in total during discharge. Subsequently, Fig. 9 shows the
sensitivity coefficients implying an inhibitive effect on ignition
PFA of (a) O and (b) OH in the whole discharge duration (0.1 ms),
enhancement, consistent with the result in Ref. [41]. When the collision
respectively. Normally, it is difficult to produce an O atom at low tem­
cross sections of N2 and O2 vibrational states are increased according to
peratures since oxygen–oxygen bond energy is relatively high. However,
Eq. (7), more discharge energy is deposited into these channels. Fig. 10a
Fig. 9a shows that almost all O atoms generation is related to plasma
further shows that vibrational states and electronic states have a
reactions which is the kinetic effect of plasma modifying the combustion
competitive relationship [41] leading to less discharge energy deposited
process. N2 electronically excited states and E contribute 23.8 % and 8.3
into electronic states. Similarly, the competition between N2(A3Σ+ u ),
% of O via dissociating O2, respectively. About 37.6 % of O is produced
N2(B3Πg) and N2(C3Πu), N2(a’1Σ-u) in terms of discharge energy and the
due to N oxidation, primarily because of the reaction of N with O2. In
positive effect of O2(a1Δg) and O(1D) on the ignition process can also be
addition, N2 vibrationally excited states via reaction N2(vib1) + O =>
found in the figure and consistent with [7,8,41].
NO + N [11] dominates N production, which is the source of N atom in
Moreover, in Fig. 10a, collision reactions of electron and propane (E
R616 (c.f. Fig. 6). It should be noted that the rate constant for N2(v)
+ C3H8 => E + C3H7 + H) have a positive effect on ignition enhance­
relaxation reactions, i.e., N2(vib1) + O => NO + N is estimated as k =
ment, while reactions producing alkenes (E + C3H8 => E + C3H6 + H2
3.01 × 1013 cm3/(mol⋅s), much larger than that of N2(v) VT relaxation
and E + C3H8 => E + C2H4 + CH4) restrain the ignition. The reason can
with hydrocarbons of 6.02 × 109 cm3/(mol⋅s) in [17]. Besides, elec­
be ascribed that propyls play a more important role in LTC compared
tronically excited molecules of N2 and O2 and O(1D) provide 49.7 % of O
with alkenes.
in total. Electron collision with O2 and N2 can also promote concentra­
Fig. 10b shows the comparison of the sensitivity coefficient for Case
tions of O and N.
1 and Case 2. It can be found that with NRPD (Case 2), the NOx (NO,
In Fig. 9b, the top three pathways of OH at LTC stage are propane
NO2) related reactions R542 and R541 are much more pronounced.
oxidation, O2C3H6OOH isomerization decomposition and HO2 decom­
Similar observations can be found in previous literature [11]. Also, the
position. In detail, 33.4 % of OH is directly formed by the impact of O
typical low-temperature reactions such as R476, R521, R519 and R478
(1D) and O with propane and 28.2 % by the isomerization of
are enhanced by NRPD. In line with Fig. 9, N2(vib1) is beneficial for
O2C3H6OOH. Besides, at low temperature and high pressure, H is usually
reducing ignition delay time by reaction R1149. Other reactions for
consumed to produce HO2 by reaction R11: H + O2(+M) = HO2(+M),
enhancing ignition such as R317, R19, R329, R320 and those inhibiting
which is a chain-termination process [7]. While with the existence of
ignition like R509, R43, R18 can also be found in the sensitivity analysis
NO, a chain branching reaction NO + HO2 = NO2 + OH takes place
from Ref. [42], which are not analyzed for simplicity.
resulting in the HO2 decomposing into OH and benefits the subsequent
combustion [11]. Furthermore, NO2 promotes H atom oxidation to
4.3. NTC under NRPD and ED
produce OH and N2(v) can also promote H by decomposing HO2 as
explained in [14].
At a certain temperature after LTC stage of C3H8/air auto-ignition
Finally, a sensitivity analysis is performed to provide an insight into
process, RO2, QOOH and O2QOOH tend to decompose to produce R,
the effect of NRPD on IDT. The sensitivity coefficient is defined as
alkene and HO2, causing chain termination and lowering the radical
following:
production rate. As a result, the fuel oxidation rate and heat release rate
τ(2ki ) − τ(ki ) slow down, leading to IDT increasing with a temperature rising, which is
S= (6)
τ(ki ) called an NTC effect. The knocking and oscillatory combustion are
closely related to NTC [2]. It has been proven that the non-equilibrium
where τ denotes IDT and ki represents the reaction rate constant for discharge can weaken the NTC effect [7], while detailed physical

6
Y. Ban et al. Fuel 339 (2023) 127353

shortest.
For understanding the NTC disappearance with NRPD, concentra­
tions of key species of low-temperature pathways are compared between
NRPD (Case 5) and auto-ignition (Case 4) for T0 = 800 K in Fig. 12,
where Case 4 is inside of NTC region as shown in Fig. 11. It can be found
that with NRPD, an amount of NC3H7 is formed from the beginning due
to abstraction of H from the fuel oxidation by O, OH and O(1D) as shown
in Fig. 9, and grows dramatically to its peak. Subsequently, NC3H7O2 is
generated from NC3H7 oxygenation via reaction R476 (O2 + NC3H7 =>
NC3H7O2) with a high reaction rate under NRPD in Fig. 12a. While for
the auto-ignition Case 4, due to the relatively low initial temperature,
the reaction rate of R476 is rather low and NC3H7 is hardly to generate
until 0.04 s.
Comparing the major species during the ignition process in Fig. 12b,
a great number of intermediate species C3H6OOH, O2C3H6OOH and
OC3H5OOH have generated during the plasma discharge period and
even two orders of magnitude larger than those of the corresponding
auto-ignition case. It is well recognized that O2C3H6OOH and
OC3H5OOH show a notable impact on LTC [2,40] which results in a
chain branching reaction for OH production. As such, the low-
temperature pathway of OH production is enhanced. An apparent two-
stage ignition and a shorter ignition delay time under NRPD can be
seen even though the initial temperature is inside the NTC region.
The reaction rates of the main reactions for NC3H7 and oxidation
rates of NC3H7/IC3H7 during NRPD in Case 5 are shown in Fig. 13a, b
respectively. New pathways like R1001 and R2483 for NC3H7 produc­
tion are induced by non-equilibrium plasma, besides R317, R318 and
R477. According to Figs. 7 and 8, O produced by excited states and
electrons accelerates the reactions R318 and R327 (C3H8 + O = OH +
NC3H7/IC3H7). Therefore, NC3H7 and IC3H7 concentrations are pro­
moted even in NTC region, which further increases the oxidation reac­
tion rates of NC3H7/IC3H7 in terms of R476 and R478 (O2 + IC3H7 =>
IC3H7O2). However, this cannot be achieved in auto-ignition Case 4
since both the quantities and the reaction rates of R476 and R478 are
low within the NTC region. Finally, the promoted NC3H7O2 and IC3H7O2
concentrations accelerate the production of hydroxy compounds as well
as OH through low-temperature chain branching reactions, leading to a
shorter IDT.
Besides the enhanced low-temperature pathways in Case 5, it is
found another way affecting high-temperature ignition. As expected,
with temperature increasing, the consumption pathway of NC3H7/IC3H7
transfers from oxygen addition to H-abstraction i.e., from R476 and
R478 to R343 and R351 in Fig. 13b. Such that, the low-temperature
pathway weakens while intermediate/high temperature reaction pro­
cesses begin to dominate. Fig. 13b shows an advanced and enhanced H-
abstraction reaction rate from NC3H7/IC3H7. Accordingly, the increased
HO2 radicals contribute to H2O2 and OH formation [2,40]. It is well
Fig. 10. Sensitivity coefficient of IDT for a) electron impact reactions in Case 2
and b) reactions involving neutral species in cases 1–2, where N2(V) and O2(V)
recognized that this process is the major chain-branching reaction
denote the group of N2(vib2-vib8) and O2(vib1-vib4) respectively. pathway at intermediate/high temperature. The detailed pathways are
not shown for brevity. Therefore, the promoted NC3H7/IC3H7 by NRPD
not only increases the production of NC3H7O2/IC3H7O2, but accelerates
understanding is still rare. This section will explore how the NTC during
the production of HO2 and further the intermediate/high temperature
the combustion process of C3H8/air is affected by NRPD.
reaction processes.
From Fig. 11, it can be seen that the NTC region is in the temperature
range of 765–865 K for φ = 1.0 and 772–833 K for φ = 0.5 at the auto-
ignition condition. With the energy of 0.715 J⋅cm− 3 inputted by ED, the 5. Conclusions
NTC region shifts towards the lower temperature range of 733–790 K for
φ = 1.0 and 725–769 K for φ = 0.5, respectively. The reason can be Zero-dimensional plasma kinetics and combustion kinetics are
ascribed to the thermal effect brought by ED. With the enhanced initial coupled to investigate the effect of non-equilibrium plasma and equi­
thermal condition, the NTC phenomenon can be found earlier as the librium discharge on LTC stage and NTC performance of lean propane/
time involves such that the NTC region is “pushed” into a lower tem­ air mixture. The detailed PAI/PAC propane/air mechanism composed of
perature range in Fig. 11a. However, the NTC phenomenon disappears electron collision reactions is established. Results show that NRPD can
in both cases if NRPD is employed in Fig. 11b, where the induction time modify propane consumption pathways and shorten IDT.
decreases monotonically with the growth of the initial temperature For NRPD, electronically excited species such as O(1D), O2(v) and
which is consistent with the results in Ref. [23]. Furthermore, the N2(v) as well as propyl are produced in advance compared to ED. It is
ignition delay time of NRPD mode among the three ignition modes is the found that electrons and O(1D) play a significant role in propane
destruction, and abundant alkyls such as IC3H7 and NC3H7 are formed

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Y. Ban et al. Fuel 339 (2023) 127353

Fig. 11. The evolution of IDT with different initial temperatures for φ = 0.5 and φ = 1.0 under conditions of a) auto ignition and ED, b) auto ignition and NRPD.

Fig. 12. The temporal evolution of a) NC3H7 and R476 reaction rate and b) temperature and key low-temperature species for Case 4 and Case 5.

Fig. 13. A) the primary rop in terms of nc3H7 and b) reaction rate of R343, R351 and mole fraction of HO2 for Case 5.

during the discharge period when the discharge timing is before LTC. O2C3H6OOH and propane oxidation by O(1D) and O contribute to a
Meanwhile N, O(1D) and electronically excited states of N2 and O2 majority of OH which releases heat and shortens LTC stage. The sensi­
produce O atom, accelerating propane oxidation. The decomposition of tivity analysis of IDT indicates that the electron impact reactions of

8
Y. Ban et al. Fuel 339 (2023) 127353

Fig. A2. ROP of NC3H7 under the initial temperature of 905 K for φ = 0.5.
Fig. A1. Reaction rate constants of R343, R351, R476 and R478.
Acknowledgement
producing propyls can promote ignition, while electron impact reactions
producing alkenes have the inhibition effect due to the competitive with We thank Dr. Xingqian Mao for his valuable comments and
the former in discharge energy. proofreading.
Besides, NRPD can eliminate the NTC effect at fuel lean conditions
(φ = 0.5), while ED has a minor effect on the NTC region which shifts the Appendix
NTC region into the lower temperature zone. The negative coefficient
relation between the reaction rate of NC3H7/IC3H7 + O2 => NC3H7O2/ According to Ref. [7,40], with temperature increasing, OH produc­
IC3H7O2 and temperature leads to the NTC phenomenon. With T0 rising, tion and fuel consumption pathways are changed. The appendix ex­
the reaction rate of NC3H7 + O2 => C3H6 + HO2 dominates among plains the reason for the NTC phenomenon and the transition process
NC3H7 consumption pathways and the low-temperature pathways of OH between LTC and intermediate/high temperature stage for C3H8/air in
are replaced. When the T0 is inside the NTC region, plasma-induced detail.
radicals O and O(1D) can promote C3H8 oxidation to produce higher As shown in Fig. A1, the reduction of R476 and R478 reaction rate
concentrations of OH and NC3H7 radicals. The higher NC3H7 concen­ constants with temperature rising will restrain the production of
tration is not only beneficial for NC3H7 oxidation to NC3H7O2 offsetting NC3H7O2/IC3H7O2. Within a wide temperature range, the reaction rates
the low production rate of NC3H7O2 brought by the negative coefficient of R343 and R351 are lower than that of R476 and R478, leading to a
relation between NC3H7 oxygenation reaction and temperature, but also restricted H-abstraction rate at low temperatures. It can be concluded
accelerates the intermediate/high temperature reaction rates to produce that the negative coefficient relation between reaction rate constants of
C3H6 and HO2. As a result, with NRPD the LTC stage in NTC region and R476 and R478 and temperature leads to lower RO2 and OH production
intermediate/high temperature reaction processes are advanced, lead­ rates and finally the NTC phenomenon.
ing to the disappearance of NTC and a shorter ignition induction time. The ROP of NC3H7 for the initial temperature of 905 K is shown in
Funding. Fig. A2 to explain the disappearing NTC phenomenon under the auto-
This work was supported by the National Natural Science Foundation ignition condition. In Fig. A2, the reaction rate of R343 begins to be
of China (Grant No. 51876139) and special funds for the construction of larger than that of R476 at about 0.023 s marked by the dotted line, and
innovative provinces in Hunan (Grant No. 2019RS2028). the consumption path of NC3H7 is changed. Reaction R343 promotes
HO2 production, further accelerating the production of H2O2 respec­
CRediT authorship contribution statement tively by C3H8 + HO2 = H2O2 + C3H7 and 2HO2 = H2O2 + O2. Finally,
OH is promoted by H2O2 decomposition via H2O2(+M) = 2OH(+M), the
Yangyang Ban: Methodology, Software, Validation, Formal anal­ low-temperature generation pathway of which is replaced, and the
ysis, Writing – original draft. Shenghui Zhong: Methodology, Writing – propane consumption is accelerated [7,40].
review & editing, Supervision. Jiajian Zhu: Conceptualization, Funding
acquisition. Fan Zhang: Conceptualization, Methodology, Writing – References
review & editing, Supervision, Funding acquisition.
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